ORNL-2548.txt

DISCLAIMER

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Government or any agency thereof.
DISCLAIMER

Portions of this document may be illegible in
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ORNL-2548
Chemistry ~ General
TID-4500 (15th ed.)

Contract No. W-7405-eng-26

REACTOR CHEMISTRY DIVISION

PHASE DIAGRAMS OF NUCLEAR REACTOR MATERIALS

R. E. Thoma, Editor

DATE ISSUED

QOAK RIDGE NATIONAL LABORATORY
Qak Ridge, Tennessee
operated by
UNION CARBIDE CORPORATION
for the
U.S. ATOMIC ENERGY COMMISSION
INTRODUCTION
1.

2. METAL-FUSED-SALT SYSTEMS

3.

.1

LT
1.2.
1.3.
1.4.

2.1
2.2.
2.3.
2.4.
2.5.

FUSED-SALT SYSTEMS

The System LiF~NaF...............
The System LiF-KF.................
The System LiF-RbF...............
The System LiF-CsF...............
The System NaF-KF ...............
The System NaF-RbF .............
The System KF=RbF ...............
The System LiF—-NaF-KF.......
The System LiF-NaF~RbF.....
The System LiF~KF-RbF.......
The System NaF-KF~RbF .....
The System NaBF ,—KBF,.......
The System NaF—FeF, .........
The System NaF-NiF,.............
The System RbF-CaF, ..........
The System LiF~NaF -CaF, ...

3.1
3.2,
3.3.
3.4.
3.5.
3.6.
3.7.
3.8.
3.9

3.10.
3.1
3.12.
3.13.
3.14.
3.15.
3.16.
3.17.
3.18.
3.19.
3.20.
3.2
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 System Silver—Zirconium.

The System Indium=Zirconium

---------------------------------

CONTENTS

..................................................................................................................................

METAL SYSTEMS

.........................................................................................

-----------------------------------------------------------------------------------------

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The System Antimony—ZirCONIUM ..o iieiiirriinecr ittt et et e

The System Lead=Zirconium...

-------

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-----------------------------------------------------------------------------------------

The Sodium Metal~Sodium Halide Systems ...ccoeieviiiiiiceccc e
The Potassium Metal—Potassium Halide Systems ...
The Rubidium Metal-~Rubidium Halide Systems .....ccooveereiiinicieieceec
The Cesium Metal~Cesium Halide Systems .....cocvirociciciiiiciecs e,
The Alkali Metal~Alkali Metal Fluoride Systems ......cccccoovevvieeicei it

The System NaF -MgF,—CaF,

The System NaF-KF-AIF,....
The System LiF~BeF,............
The System NaF-BeF, ..........
The System KF-BeF, ............
The System RbF-BeF, ..........
The System CsF-BeF, ..........
The System LiF-NaF-BeF,...
The System LiF~RbF-BeF,...
The System NaF —KF ~BeF, ...
The System NaF-RbF -BeF , .
The System NaF —-ZnF,, ..........
The System KF~ZnF, ...........
The System RbF—ZnF, ...........
The System LiF~YF ...,
The System LiF~ZrF , ............
The System NaF-ZrF ,.............

.......................

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ves
il
3.34.
3.35.
3.36.
3.37.
3.38.
3.39.
3.40.
3.41.
3.42.
3.43.
3.44.
3.45.
3.46.
3.47.
3.48.
3.49.
3.50.
3.51.
3.52.
3.53.
3.54,
3.55.
3.56.
3.57.
3.58.
3.59.
3.60.

3.61.
3.62.
3.63.
3.64.
3.65.
3.66.
3.67.
3.68.
3.69.
3.70.
3.71.
3.72.
3.73.
3.74.
3.75.
3.76.
3.77.
3.78.
3.79.
3.80.
3.81.
3.82.
3.83.
3.84.

The System KF—-ZrF‘4 ........................................................................................................ 56

The System RBF —ZrF oo, 57
The System CsF—ZrF4 ...................................................................................................... 58
The System LiF---NcF--ZrF:4 ............................................................................................ 60
The System NCJF—KF—ZI'F4 .............................................................................................. 62
The System NaF—RbF—ZrF ..o, 64
The System NaF-CrF,~ZrF ,: The Section NaF.CrF, ~ ZrF , oo, 66
The System NaF—CeF ; —ZrF .o, 67
The System LiF—CeF .t 68
The System NaF —HF .o 70
The System LiF —ThF ;o 72
The System NaF —ThF oot 73
The System KF =ThF , o, 74
The System RBF —ThF ;oo 76
The System BeF ,—ThF , oo 77
The System BeF S UF 4 o 78
The System Mgl:2-Th|:4 .................................................................................................. 79
The System LiF—BeF2--ThF4 .......................................................................................... 80
The System NoF—ZrFA—Th B e e 82
The System LiF-—UF3 ........................................................................................................ 84
The System LiF —UF oo 85
The System NcF-—UF3 ...................................................................................................... 86
The System NaF—UF ; ..o 88
The System KF —UF ;i s 90
The System RBF —UF ;oo s o1
The System CsF—UF ;oo e 92
The System ZrF =UF .ot s 93
The System San-—UF4 ...................................................................................................... 94
The System PbF ,—UF ;oo s 95
The System Th F4—UF4 ...................................................................................................... 96
The System LiF—NaF—UF4 .............................................................................................. 98
The System LiF —KF—UF 4 s 101
The System LiF—RBF—UF , oo s 102
The System NaF —KF —UF .o 103
The System NGF —RbF —UF oo 104
The System LiF~BeF , —UF , o e 108
The System NaF —BeF , —UF ;oo s 110
The System NaF —PbF ,—UF .o e 113
The System KF—PbF ) —UF , ..o 114
The System NaF —ZrF (—UF ;oo e 116
The System LiF—ThF , —UF /(oo 119
The System NaF-ThF,-UF,: The Section 2NaF.ThF ,~2NaF.UF, ...ccccooeccicen. 124
The System LiF—PuF s 125
The System LiCI—FeCl, i, 126
The System KCI=FeCl, ... 127
The System NaCl=ZrCl, .o e 128
The System KCI=ZrCl ..o e 130
The System LiCl-UCH s 131
The System LiCI-UCH oo, 132
The System NaCl-UCH; e, 133
The System NaCl—UCI ;.o e, 134
4.

5.

3.85.
3.86.
3.87.
3.88.

OXIDE AND HYDROXIDE SYSTEMS

4.1.
4.2.
4.3.
4.4,
4.5.
4.6.

AQUEOQUS SYSTEMS

5.1.
5.2.
5.3.
5.4.
5.5.
5.6.
5.7.
5.8.
5.9

5.10.

The System KCI—UCl4 ......................................................................................................
The System RbC|—UC|3 ....................................................................................................
The System CsCl-UCH, .o,
The System KaCrF  =Nag CrF L CrF i,

..........................................................................................

The System SiOz---ThO2 ....................................................................................................
The System LiOH-NGOH ....ooooeeee ettt et ea e enes
The System LiOH—KOH ettt e st e e s sete e e sabsas b e s bs e abteeeensanes
The System NAOH <K OH ...ccocvviiiiiceii ittt sbeeres s e svtesermeesnsssntssaes
The System NAOH<—RDOH .....coooiiiiereeireeereres s e e nv e s eares e sssessae s sresnsssassresneas
The System BCJ(OH)2—-Sr(OH)2 ..........................................................................................

----------------------------------------------------------------------------------------------------------------------

The System U02-P205-—H20, 25°C Isotherm ... vt
The System UO3-H3P04—H20, 25°C 150therm ..coccveiiviieciee e et
The System U(HPO4)2-C1207-—H2O, 25°C Isotherm......ccoiiiriiiiiicec e
The System U0, -Na,0~C0,—H,0, 26°C Isotherm ..ot
Portions of the System ThO,~Na,0-C0,~H,0, 25°C Isotherm.......c.cooerniiniininnnnn.
The System Na,0-CO,-H,0, 25°C Isotherm ...
Solubility of Urany!l Sulfate in Water ..o,

Two-Liquid-Phase Region of UO,S0, in Ordinary and Heavy Water ...

The System UQ3~-SO3 —-H20 ..............................................................................................
Coexistence Curves for Two Liquid Phases in the System

U0,50,,—H,S0, ~H, 0 cvrervrererrsseesmsessssossee s ssssesssssesssssss oo

11. Two-Liquid-lghasde Rezgion of the System U02504—H2504-—H20 ................................

. Two-Liquid-Phase Coexistence Curves for U03—Rich Solutions in

the System UO,-30,~H,0 With and Without HNO ..o

13. Solubility of UO3 in H2504-—H20 MiXEUFES oieii e iieeereccrie s eerereece e erenesentnesatnae sensaaeans
14. Effect of Excess H,SO, on the Phase Equilibria in Very Dilute

i
> o

5.17.
5.18.
5.19.

5.20.

5.21.
5.22.

5.23.
5.24.
5.25.
5.26.
5.27.
5.28.
5.29.
5.30.

UO,50, Solutions ...
Second-Liquid-Phase Temperatures of U02504—Li2504 Solutions .cccocveieeireie.
Second-Liquid-Phase Temperatures for U02504 Solutions Containing

Li2504 or BeSO, i s
Second-Liquid-Phase Temperatures for BeSO4 Solutions Containing UO, v
The Sy stem Ni504-—U02$04~—H20 A 25PC et e et
Phase-Transition Temperatures in Solutions Containing CUSOA,

UO,30,, and HoSO 4o s
The Effect of CuSO, and NiSO, on Phase-Transition Temperatures:

0.04 m UO0,50,; 0.01 m HySO, oot
The System U0, ~Cu0-NiO~50,-D,0 at 300°C; 0.06 m SO; .coovvcvrivrmniiiiciriinnee,
Solubility of Nd,(SO,); in 0.02 m UO,S0, Solution Containing 0.005 m

H,S0, (T80 =300PC) .. eeieeeierreeeeeterereeeeerete et et se st s ere e e e s st bsatsasbasesbes satbesaeeseeensbs e enessaenses
Solubility of Lo2(504)3 in UO,S0, Solutions ...
Solubility of CdSO, in UO,50, Solutions ...,
Solubility of Cs S0, in UO,50, SOlUTIONS it e
Solubility of Y2(2504)3 in UD,S0, Solutions ...
Solubility of A92504 in UO,50, SOlUTIONS i e
Solubility at 250°C of BaSO, in U0,S0,~H,0 Solutions ...
Solubility of H2WO4 in0.126 and 1.26 M U02504 ........................................................
Phase Stability of HWO, in 1.26 M UO,F, o,
Vi

5.31.
5.32.

5.33.
5.34.
5.35.
5.36.
5.37.

5.38.
5.39.
5.40.

5.41.
5.42.

The System UO,(NO,),=H,Oueererieiiiii e
Phase Equilibria of Uéa and HF in Stoichiometric Concentrations

(AQUEOUS SYSTOM) .. ittt ettt e et rere b er e e erssrasesecbenssnessrnsbeessnessanenn
Solubility of Uranium Trioxide in Orthophosphoric Acid Solutions ....coccvveevvinccnnnnnn.
Solubility of Uranium Trioxide in Phosphoric Acid at 250°C ........cccoviveevvieniienrens
Solubility of UQ, in H3PO, Solution ..
The System UO,CrO, —H,0 .o
Variation of Li,CO, Solubility with UO,CO, Concentration at Constant

CO, Pressure (250°C) oottt ittt sttt e e e e es s
The &ystem Li,0-UO, ~CO,—H,0 at 250°C and 1500 pi.....vrerrerermerocrine
The System ThINO, )y ZH 0 oo
Hydrolytic Stability of Thorium Nitrate—Nitric Acid and Uranyl

NItrate SOlUTIONS ¢ e e sbs e b e s ses e b e banenenens
The System ThO,~CrO;—H, 0 at 25°C ..o,
Phase Stability of ThO,-H,P0,-H,0 Solutions at High Concentrations

OF ThO ettt st et e e bbb s
PHASE DIAGRAMS OF NUCLEAR REACTOR MATERIALS

INTRODUCTION

This compilation presents the phase diagrams for possible materials for nuclear reactors
developed at the Oak Ridge National Laboratory over the period 1950-59. 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

1

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

2=6

referred to other recently published compilations of phase diagrams and to the several new

works dealing specifically with nuclear reactor materials.” =7

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. A
brief description of the status of the work is presented in each case; in o 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 Systems, ORNL-2396 (Nov. 19, 1958),

2). F. Hogerton and R. C. Grass (eds.), The Reactor Handbook, vol 2, AECD-3646 (May 1955).

371, Lyman (ed.), Metals Handbook, American Society for Metals, Cleveland, Ohio, 1948.

4F, A. Rough and A, A, Bauer (eds.), Constitution of Urantum and Thorium Alloys, BMI-1300 (June 2,
1958).

SE. M. Levin, H. F. McMurdie, and F, P. Hall, Phase Diagrams for Ceramists, The American Ceramic
Society, Columbus, Ohio, 1956.

6E. M. Levin, H. F. McMurdte, and F. P, Hall, Supplement to Phase Diagrams for Ceramists, The
American Ceramic Society, Columbus, Ohio, 1959,

’B. Yates, Materials for Use in Nuclear Reactors, Information Bibliography, IGRL-1B/R-15 (2nd ed.),
1958,

8H. H. Hausner and S. B. Roboff, Materials for Nuclear Power Reactors, Reinhold Publishing Corp.,
New York, 1955,

9B. Kopelman (ed.), Materials for Nuclear Reactors, McGraw-Hill Book Co., New York, 1959.
1. METAL SYSTEMS
1.1. The System Silver=Zirconium

J. O. Betterton, Jr., and D. S. Easton, ‘“‘The Silver—Zirconium System,'’ Trans. Met. Soc.
AIME 212, 47075 (1958).

A detailed investigation was made of the phase diagram of silver—zirconium, particularly in
the region 0 to 36 at. % Ag. The system was found to be characterized by two intermediate
phases, Zr,Ag and ZrAg, and a eutectoid reaction in which the B-zirconium solid solution de-
composes into a-zirconium and Zr,Ag. 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.
TEMPERATURE (°C)

UNCLASSIFIED
ORNL-LR-DWG 18989

T
860 /
850 —
B+y |
S 840 |
o
Ll
@ 830
)
g . l A
Al
@ 820 4
% O at+B+y
w810 7 I 7
v 5 NulE PHASE
800 T S NGLE PHASE WITH A TRACE OF SECOND PHASE n
OAV TWO PHASE
790 { THREE PHASE _
FILLED SYMBOLS NDICATE METALLOGRAPHIC SAMPLES
280 WHICH WERE CHEMICALLY ANALYZED FOR SILVER CONTENT |
3 4 5 6
SILVER (at %)
Fig. 1.1a. The System Silver=Zirconium in the Eutectoid Region (0-6
at. % Ag)-
UNCLASSIFIED
ORNL-LR-DWG 189884
1400 {
AN
\ LIQ |
1300 | N\
N
N
| AN
y +L1Q j
1200 \‘_,_
'Y w
[ | [ | A*
d A
1100 —
y+8
1000 i i
A A
800 r T r
SN
800 f— T — — — — -
a A A
/ O SINGLE PHASE
a+y
’ ] DAV TWO PHASE
700 I, FILLED SYMBCLS INDICATE METALLOGRAPHIC SAMPLES
L WHICH WERE CHEMICALLY ANALYZED FOR SILVER CONTENT
0 5 10 15 20 25 30 35

SILVER {at %)

Fig. 1.15. The System Silver~Zirconium in the Region 0-36 at. % Ag.
1.2. The System Indium-Zirconium

J. O, Betterton, Jr., and W. K. Noyce, “‘The Equilibrium Diagram of Indium=Zirconium in the
Region 0-26 at. pct In,"”’ Trans, Met, Soc. AIME 212, 340-42 (1958),

The zirconium-rich portion of the indium—zirconium phase diagram was determined as a
study of the effect of alloying a trivalent B-subgroup element, indium, with zirconium in group
IVA, The temperature of the allotropic transition was found to rise with indium, terminating in a
peritectoid reaction, (5(9.3% In) + ¥(22.4% In) == a(10.1% In) at 1003°C. In this respect the

effect of indium is analogous to that of aluminum in zirconium and titanium alloys.

UNCLASSIFIED
ORNL-LR—DWG 18987
1300 :
|
1200 o/
100 o
Bty
1000
o Bty
w
o
P
E 900
o
Lt
0o
=
Ll
Z |
800 | -
700 B i I
/ |
600 —+ - l — —_—
¥ @
500
0 2 4 6 8 10 12 14
INDIUM (at %)

Fig. 1.2a, The System Indium—Zirconium in the Peritectoid Region {(0-13
of. % ln).
BLANK
BLANK
UNCLASSIFIED
ORNL-LR-DWG 18983

1400
1300 74
B
0 0
1200 roooO 5 O 0
B+Zr,Sb
;GHOO OOOrI’DG 0 &,
L
a
P
<
< 1000 /
o
l_
KT
900 8,
A ]
|
800 s
a+Zr25b
700

O 1 2 3 4 5 6 I 8 9
ANTIMONY {(at. %)

Fig. 1.3b, The System Antimony~Zirconium in the Peritectoid Region (0—6 at. % Sb).
1.4. The System Lead=Zirconium

G. D. Kneip, Jr., and J. O. Betterton, Jr., cited by E. T. Hayes and W. L. O'Brien,
““Zirconium Equilibrium Diagrams,”’ p 443-83 in The Metallurgy of Zirconium, ed. by B, Lustman
and F. Kerze, Jr., McGraw-Hill Book Co., New York, 1955,

UNCLASSIFIED
ORNL—LR—DWG 1375

1200
1100 o —0 0—o0 oo}
B

1000 .
o . | Bty
m
xr -
>
£ 900
@
L
a
=
L
l_

800 -

700 // o SINGLE PHASE

/ » TWO PHASE
4 THREE PHASE
&00
0 2 4 6 8 10 12
LEAD (at. %)

Fig. 1.4 The System Lead-Zirconium in the Peritectoid Region (0-12

at. % Pb)l
2, METAL-~-FUSED.SALT SYSTEMS

2.1. The Sodium Metal=Sodium Halide Systems
M. A. Bredig and J. E. Sutherland, ‘“High-Temperature Region of the Sodium~Sodium Halide

Systems,'’ Chem. Ann. Prog. Rep. June 20, 1957, ORNL-2386, p 119. Subsequent report on these
systems to be published.

UNCLASSIFIED
ORNL-LR-DWG. 21894 A

X <— MOLE FRACTION MX
98 765 4.3.2 4 9
1T 1 [

876 .54 .3.2 4
4200 HSOO‘I ‘ ‘8 T T T T T T T 4200
o COOLING CURVES, THIS WORK
. X EQUILIBRATION, MAB,JWJ WTS
‘:, A EQUILIBRATION, HRB, MB
1100 1080° — 1400
1000 — 4
: TWO LIQUIDS 000
o0 X °G
005° NaGl - Na A
900 X {900
2 X
800|— \fi%_o_c 795 800
SOLID SALT + LIQUID METAL
700 700
CsF-Cs
600 600
1100+ ONE LIQUID ONE LIQUID 144100
1026° 1033°
1000 |- ¢ —1000
°C x % X X oC
TWO LIQUIDS \ / Two LiouiDs \
900 - £ \ \- 900
% NaBr - Na . \ { \
x -
800 \ e Nal Na 800
) 740° x| [ \
[ss2] & ‘x
?00——80 caLT . \ T?OO
+ o
LID SALT + LIQUID METAL { ¢ e
I O I I | S?U[f SALT T HIAPIB MERAL ,
6
O3 456780 12 3456789 o
MOLE FRAGTION OF METAL—> MOLE FRACTION OF METAL —>

Fig. 2.1, The Sodium Metal-Sodium Halide Systems.
2,2, The Potassium Metal =Potassium Halide Systems

J. W. Johnson and M. A, Bredig, ‘‘Miscibility of Metals with Salts in the Molten State. Ill. The
Potassium—Potassium Halide Systems,’’ ]. Phys. Chem. 62, 604 (1958),

Complete miscibility of metal and salt exists in the KX=K systems, X = F, Cl, Br, and I, at
and above 904, 790, 727, and 717°C, 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.

SIFIED
R-DWG 21481B

I I I I I I I I

g04° 0,56,® COOLING CURVES
x EQUILIBRATION AND SAMPLING __

900

850

800 —

©
| | | I | I | I | \

10 20 30 40 50 60 70 80 90
mole % K

Fig. 2.2. The Potassium Metol —Potassium Halide Systems,

10
2.3. The Rubidium Metal=Rubidium Halide Systems

M. A, Bredig and J. W. Johnson, ‘‘Rubidium~Rubidium 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° l l —
\ /,—-—X-—-..x\
N, /RbF-Rb
SV . N
773° ~
~
750 — —
1 706°
700 =X WRBGI=Rb ~*~ —
OC X 696 ° X )
RbBr—-Rb \x
—_
650 y— T _
\\x 6349 . \\\\\\
Ko Y T — X
AN " RbI-Rb N\
o X
- .9 X X X X X
X 615°
600 | — \x '\ |
\
550 | |

25 50 75
MOLE % Rb METAL

Fig. 23. The Rubidium Metai—=Rubidium Halide Systems.

11
2.4, The Cesium Metal=Cesium Halide Systems

M. A, Bredig, H. R. Bronstein, and W. T. Smith, Jr., ‘‘Miscibility of Liquid Metals with
Salts. 1l. The Potassium—Potassium Fluoride and Cesium—Cesium Halide Systems,' J. Am.
Chem. Soc. 77, 1454 (1955),

Miscibility in all proportions of cesium metal with cesium halides at and above the melting
points of the pure salts, and of potassium metal with potassium fluoride 50° above the melting
point of the salt, occurs. The temperature-concentration range of coexistence of two liquid
phases decreases in going from sodium to potassium systems and disappears altogether for the
cesium systems, The solubility of the solid halides in the corresponding liquid alkali metals,

at a given temperature, increases greatly with increase of atomic number of the metal.

UNCLASSIFIED
ORNL-LR-DWG. 37011

| [ T
700 B
CsF-Cs
650 - —
CsCl-Cs
600 —
°C
CsI-Cs
550 —
500 - 1
CESIUM METAL-HALIDE SYSTEMS
450 ' ' |
0 25 50 75 100

MOLE % METAL

Fig. 2.4. The Cesium Metal -Cesium Halide Systems,

12
2.5. The Alkali Metal=Alkali Metal Flyoride Systems
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.

UNCLASSIFIED
ORNL-LR-DWG. 31067A

1300

1200

1100

1000 4 —
°C
900 T
\
|
800 4
700 ]
CsF - Cs
| | |
60Oo 25 50 75 100

MOLE % METAL

Fig. 25. The Alkali Metal-Alkali Metal Fluoride Systems,

13
3. FUSED-SALT SYSTEMS

3.1. The System LiF-NaF

A. G. Bergman and E. P. Dergunov, ‘‘Fusion Diagram of LiF-KF-NaF,"”’ Compt. rend. acad.
sci. U.R.S.S. 31, 753-54 (1941).

The system LiF-NaF contains a single eutectic at 60 LiF~40 NaF (mole %), m.p. 652°C.

UNCLASSIFIED
ORNL-LR-DWG 20457

i /"

/

1000

200 /

800

700

TEMPERATURE (°C)

652°C

600

500
LiF 10 20 30 40 5C 60 70 80 90 NaF

NaF {(mole %)

Fig. 3.1. The System LiF-NaF.

14
3.2. The System LiF=KF
A. G. Bergman and E. P. Dergunov, ““Fusion Diagram of LiF~-KF-NaF,"’ Compt. rend. acad.

sci.

U.R.S.S. 31, 753~54 (1941).

The system LiF~KF contains a single eutectic at 50 LiF=50 KF (mole %), m.p. 492°C.

1000

TEMPERATURE (°C)

300

700

600

500

400

UNCLASSIFIED
ORNL—-LR—DWG 35483

LiF

10 20 30 40 50 60 70 80 30 KF
KF {moie %)

Fig. 3.2. The System LiF—KF.

15
3.3. The System LiF-RbF
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

Invariant .
Mole % LiF Temperature Type of Equilibrium Phase Reaction
in Liquid ©C) at Invariant Temperature
44 470 Eutectic L ——RbF + LiF:RbF
47 475 Peritectic L +LiF ==LiF:RbF

General characteristics of the system have been reported by E. P. Dergunov, ‘‘Fusion Dia-

grams of the Ternary Systems of the Fluorides of Lithium, Sodium, Potassium, and Rubidium,”’
Doklady Akad. Nauk S.5.S.R. 58, 1369-72 (1947).

16

TEMPERATURE (°C)

900

700

600

500

400

300

UNCLASSIFIED
ORNL-LR-DWG {6145

— T T

— —— — —

e — ——

LIF RbF

10 20

30

40

50

LiF {mole %)

60

Fig. 3.3. The System LiF-RbF,

80

90

LiF
TEMPERATURE (°G)

3.4. The System LiF-CsF
C. J. Barton, L. M. Bratcher, T. N. McVay, and W. R. Grimes, unpublished work performed
at the Oak Ridge National Laboratory, 1952-54,

Preliminary diagram.

Invariant Equilibria

Invariant
Mele % CsF Temperature Type of Equilibrium Phase Reaction
in Liquid (°C) at Invariont Temperature
55 495+ 5 Peritectic LiF + L =— LiF.CsF
63 475 £ 5 Eutectic L =—LiF:CsF + CsF

900

UNCLASSIFIED
ORNL- LR-DWG 14632

800

700

600

500

400

300

LiF GCsF

20

30

40

50
CsF (mole %}

60

Fig. 3.4 The System LiF-CsF.

70 80 90 CsF

17
3.5. The System NaF-KF

A. G. Bergman and E. P. Dergunov, ““Fusion Diagram of LiF-KF~NaF,'” Compt. rend. acad.

sci. U.R.5.S. 31, 75354 (1941).

. 900 \

TEMPERATURE (°C)

18

The system NaF-KF contains a single eutectic at 40 NaF-60 KF (mole %), m.p. 710°C,

UNCLASSIFIED
ORNL-LR--DWG 35484

1000 g 1

T~

800 \ /

700

600

500

400
NaF 10 20 30 40 50 60 70 80 a0 KF
KF {(mole %)

Fig. 3.5. The System NaF-KF,
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.

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

General characteristics of the system have been reported by E. P. Dergunov, ‘‘Fusion Dia-

grams of the Ternary Systems of the Fluorides of Lithium, Sodium, Potassium, and Rubidium,’
Doklady Akad. Nauk S.5.S.R. 58, 1369~72 (1947).

UNCLASSIFIED
ORNL-LR-DWG 3571

900 \
J\

850

800 \

TEMPERATURE (°C)

700 AN i bd

- ) . ¢ o of °
o f P’ < .
650
NaF 10 20 30 40 50 60 70 80 a0 RbF
RbF {mole To)

Fig. 3.6, The System NaF-RbF,

19
3.7. The System KF-RbF
C. J. Barton, J. P. Blakely, L. M. Bratcher, and W. R. Grimes, unpublished work performed
at the Oak Ridge National Laboratory, 1951.

Preliminary diagram. The system KF-RbF contains a solid solution minimum at 28 KF-
72 RbF (mole %), m.p. 770 + 10°C.

UNCLASSIFIED
ORNL—LR—DWG 35486
t000

900

700

TEMPERATURE (°C}

600

500 m——

400

KF 10 20 30 40 50 60 70 80 20 RbF
RbF (mole %)

Fig. 3.7. The System KF—-RbF.

20
3.8. The System LiF=NaF=KF

A. G. Bergman and E. P. Dergunov, ‘“Fusion Diagram of LiF~KF~NaF," Compt. rend. acad.
sci. U.R.S.5. 31, 753-54 (1941).

The system LiF-NaF-KF contains a single eutectic at 46.5 LiF-11.5 NaF-42.0 KF
(mole %), m.p. 454°C.

UNCLASSIFIED
ORNL- LR-DWG 11394

NaF
930

TEMPERATURE IN °C
COMPOSITION IN mole %

950

900

850

800

750

710 652
R 700 /

650 A

600

550 o
— /
3 2
v o
A2 A
& Q o
. 22) & \Z e 7/
/ / \ N/
/ \\ Ay
KF \ \/ A / / \U LiF
856 454 492 845

2]
3.9. The System LiF=NaF=RbF
C. J. Barton, L. M. Bratcher, J. P. Blakely, and W. R. Grimes, unpublished work performed

at the Oak Ridge National Laboratory, 1951.
Preliminary diagram. The system LiF-NaF-RbF contains a single eutectic at 42 LiF-6

NaF-52 RbF (mole %), m.p. 430 £ 10°C. 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 Dia-
grams of the Ternary systems of the Fluorides of Lithium, Sodium, Potassium, and Rubidium,"’
Doklady Akad. Nauk S.5.S.R. 58, 1369~72 (1947). Dergunov lists the composition and tempera-
ture of the ternary eutectic as 46.5 LiF-6.5 NaF-47 RbF (mole %), m.p. 426°C.

UNCLASSIFIED
ORNL-LR-DWG 1200A

TEMPERATURE IN °C
COMPOSITION IN mole %

435

/

LiF-RbF
/
/
O

Q
Qg) e
& S A\
,\0
O

AD o

\ &
NaF LiF
990 650 845

Fig. 3.9. The System LiF-NaF-RbF,

22
3.10. The System LiF=KF~RbF

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

Preliminary diagram. The system LiF-KF~RbF contains a single eutectic at 40 LiF=32.5
KF-27.5 RbF {mole %), m.p. 440 £ 10°C.

General characteristics of the system have been reported by E. P. Dergunov, ‘‘Fusion Dia-

grams of the Ternary Systems of the Fluorides of Lithium, Sodium, Potassium, and Rubidium,"
Doklady Akad. Nauk S.S.S.R. 58, 1369-72 (1947).

RbF

795 UNCLASSIFIED
ORNL-LR-DWG 35479

TEMPERATURE (°C}
COMPQSITION (mole %)

S /

A
ss MINIMUM 770 ' P
/\
0
&

850

KF
856

LiF
845

Fig, 3.10. The System LiF~-KF—RbF,

23
3.11. The System NaF-KF-RbF

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

Preliminary diagram. The system NaF-KF-RbF contains a single eutectic at 21 NaF-5
KF~74 RbF (mole %), m.p. 621 1 10°C.

RbF
795 UNCLASSIFIED
ORNL-LR-DWG 35482
TEMPERATURE (°C)
COMPOSITION {mole %) N
>
o
70
e,
£ 675 £ 770
~1£ 621
o
S\ O
Q
| \
(@]
(@]
- ~
2 3
)
[@)]
2]
%
o 3
dc‘) o
\9 .
% \
9
(o)
O \ C&
(@]
VARV, NERVA VL VA WV \/ v BN L
990 £ 740 856

Fig. 3.11. The System NaF-KF-RbF.

24
3.12. The System NaBF ,-KBF,
R. E. Moore, J. G. Surak, and W. R. Grimes, unpublished work performed at the Oak Ridge

National Laboratory, 1957.

Preliminary diagram. The system NaBF ,-KBF, contains a single eutectic ot 88 NaBF ,-

12 KBF , (mole %), m.p. 355°C. The dotted line was obtained from thermal effects representing

incompletely understood solid-phase transformations of KBF , and NaBF ,.

700

500

400

TEMPERATURE {°C)

300

200

UNCLASSIFIED
ORNL-LR-DWG 35487

! !

D-..,__. ‘./.

P
—
—

[ Pl s

— —

Py Nl

20

30 40

50
NaBF, (mole %)

&0 70 80 S0 NoBF,

Fig. 312 The System NoBF4—KBF4.

25
3.13. The System NaF-FeF,
R. E. Thoma, H. A. Friedman, B. S. Landau, and W. R. Grimes, unpublished work performed
at the Oak Ridge National Laboratory, 1957.

Preliminary diagram.

Invariant Equilibria

~

26

Fig. 313 The System NaF—FeFZ.

FeF, (mole %)

{nvariant
Mole % FeF2 Temperature Type of Equilibrium Phase Reaction
in Liquid (°C) at Invariant Temperature
30 680 Eutectic L ¥ NaF + NaF-FeF,
50 783 Congruent melting point L= NoF-FeF2
63 745 Eutectic L = NaF:FeF, + FeF,
UNCLASSIFIED
ORNL-LR-DWG 22345
1200 T ‘
1100 | I p
l | | ‘
] L
1000 + ! W
| | |
| |
S | L | | | | |
< 900 { | | | { |
U]
: ] | |
- |
x
w 800 ; ' / :
>
700 E l?
‘ I i ‘ |
o !
600 i . i !
| Ly |
=z
\
500 ‘ J
NaF 10 20 30 40 50 60 70 80 90 FeFo
3.14. The System NoF-NiF,
R. E. Thoma, H. A. Friedman, B. S. Landau, and W. R. Grimes, unpublished work performed

at the Oak Ridge National Laboratory, 1957.

Preliminary diagram.

Invariant Equilibria

Invariant
Mole % N'F2 Temperature Type of Equilibrium Phase Reaction
in Liquid (°C) at Invariant Temperature
23 795 Eutectic L == NaF + NaF:NiF,
50 1045 Congruent melting point L ‘_—_..3 NaF-NiF2
57 1040 Eutectic L &= NaFNiF, + NiF,
UNCLASSIFIED
ORNL-LR-DWG 22344
1300 L~
1200 //
1100 //
3 /
2 1000 yd
[IT]
ax
: \
= \
1
w
S <00
wt
e \
800 \/
700 —
=
w
o
2
600
NoF tO 20 30 40 50 60 70 80 90 NiF,
NiFy (mole %)

Fig. 3.14. The System NaF~NiF ..

27

3.15. The System RbF-CaF,
C. J. Barton, L. M. Bratcher, R. J. Sheil, and W. R. Grimes, unpublished work performed at
the Oak Ridge National Laboratory, 1956.

Preliminary diagram.

Invariant Equilibria

Invariant
Mole % CaF, Temperature Type of Equilibrium Phase Reaction
in Liquid °C) at Invariant Temperature
9 760 Eutectic —— RbF + RbF-CaF2
50 1110 Congruent melting point L= RbF-CaF2
57 1090 Eutectic L == RbF.CqF2 + CQFZ
UNCLASSIFIED
ORNL—LR —DW3 17668R
1500
1400 | + +— - F— - A
-
-
O THERMAL ANALYSIS DATA //
® VISUAL OBSERVATION DATA P
\ rd
1300 — — — — — = - —///— -
rd
rd
”~
7~
e
Ve
200 - — —_— — = - — —
s
— | /
o s ‘
s | | \ |/ |
W .
CD: 1100 /f_!'Xé - . - . _ -
2 e e ]
« ( |
b [
a
=3
ul
‘_
1000 — — T o=
u l
S | | |
900 —o — = —_ — — = -
al
o
| ! |
800 — — — - -
|
_a ‘ |
700 L J | |
RbF 50 60 e 80 90 CCJ#':2

Caf, (mole To)

Fig. 3.15. The System RbF-CaF,,

28
3.16. The System LiF-NaF-CaF,
C. J. Barton, L. M. Bratcher, and W. R. Grimes, unpublished work performed at the Oak
Ridge National Laboratory, 1955-56.

Preliminary diagram. The system LiF-NaF~CaF, contains a single eutectic ot 53 LiF-
36 NaF~11 CaF, (mole %), m.p. 616°C.

UNCLASSIFIED
ORNL —~LR—DWG 12779R

TEMPERATURES ARE IN °C
COMPQOSITION IN mole Ta

660
6154 663,620

X 5o /.
715 / 660,615 ais
, ¢ 950
/ NaF
845 Y G- 990

LIF

Fig. 3.16. The System LiF—NoF—Cqu.

29
3.17. The System NaF -MgF,-CaF,

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

at the Oak Ridge National Laboratory, 1955-56.

Preliminary diagram.

Invariant Equilibria

Composition of Liquid

{(mole %) Temp:rqfure Type of Solids Present
Q) Equilibrium at Invariant Temperature
NaF CmF2 MgF2
65 23 12 745 Eutectic NaF, NoF-Mng, and C0F2
35 28 37 905 Eutectic Can, Mng' and NaF-MgF2
UNCL ASSIFIED
ORNL-LR-DWG 47575R
Cafy
1418
fjso
’
2% COMPOSITION IN mole %
TEMPERATURE IN °C
4250
210
N 200
i
205 1150
10
%0 985
7N
950
90
813 0
850
905
©
940 * o
745 Js
S
. /o /\
S
3 = S
@ o Ny
S & 9
% B\
[ (4] Q
) &)
9, & &
O
\ VAN A/
NgF 830 NaF MgF, 990 MgF,
290 1030 1270

Fig. 3.17a. The System NoF -MgF ,—CaF ..

30
The minimum temperature along the quasi-binary section NaF.MgF,-CaF, occurs at the
composition 36 NaF-36 MgF ,-28 CaF, (mole %), at 910°C.

The existence of the compound NaF-MgF, was previously reported by A. G. Bergman and
E. P. Dergunov, Compt. rend. acad. sci. U.R.S.S. 31, 755 (1941).

Ternary systems of alkali fluorides with MgF, have been reported by Bergman et al. as
follows: the system LiF-NaF-MgF, by A. G. Bergman and E. P. Dergunov, Compt. rend. acad.
sci. U.R.S.S. 31, 755 (1941); the system LiF-KF-MgF, by A. G. Bergman and S. P. Parlenko,
Compt. rend. acad. sci. U.R.S.S. 31, 818-19 (1941); the system NaF~KF-MgF, by A. G. Bergman
and E. P. Dergunov, Compt. rend. acad. sci. U.R.5.5. 48, 330 (1945).

UNCLASSIFIED
ORNL—LR—DWG 12780

1500 ‘ |

1400 , s

ol
o
Q
N
\

TEMPERATURE {°C)

NaMgF; 10 20 30 40 50 60 70 80 90 CdF,
CaF, (mole %)

Fig. 3.176. The Subsystem NaF+«MgF ,~CaF ,

31
3.18. The System NaF-KF-AIF,

C. J. Barton, L. M. Bratcher, and W. R. Grimes, unpublished work performed at the QOak
Ridge National Laboratory, 1951-52.

Preliminary diagram. No study has been made at the Oak Ridge National Laboratory of the
phase relationships occurring within the system NaF-KF-AIF,. Phase diagrams have been
reported for the AIF, binary systems, NaF-AIF; [P. P. Fediotieff and W. P. lljinsky, Z. anorg.
Chem. 80, 121 (1913); also N. A. Pushin and A. V. Baskow, 5:d. 81, 350 (1913)] and KF-AIF,
[P. P. Fediotieff and K. Timofeef, Z. anorg. u. aligem. Chem. 206, 265 (1932)].

UNCLASSIFIED
DWG 17406

%

/

oG
600 685°C
570°

Fig. 3.18, The System NaF-KF-Al F,.

32
3.19. The System LiF-BeF,

This phase diagram is a composite from several published sources!~

3 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 Laberatory (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 Equilibria

Invariant
Mole % BeF2 Temperature Type of Equilibrium Phase Reaction
in Liquid (°C) at Invariant Temperature
33.5* 454 Peritectic L+LiIF== 2LiF-B¢eF2
52 355 Eutectic L ¥ 2LiF+BeF, + BeF,
- 280 Upper temperature of 2LiF-BeF2 + BeF2 — LiF-B-;-.F2
stability for LiF-BeF,
*Ref 3.

Roy, Roy, and Osborn have reported the presence of the compound LiF.2BeF, in the system
LiF-BeF, although neither the Mound Laboratery nor the ORNL data have indicated the exist-

ence of this compound.

]D. M. Roy, R. Roy, and E. F, Osborn, J. Am. Ceram. Soc. 37, 300 (1954).

2A. V. Novoselova, Yu. P. Simanov, and E. |. Yarembash, J. Pbys. Chem. (U.S.5.R.) 26, 1244 (1952).

3 John L. Speirs, The Binary and Ternary Systems Formed by Calcium Fluoride, Lithium Fluoride, and
Beryllium Fluoride: Phase Diagrams and Electrolytic Studies, Ph.D. thesis, University of Michigan, May
29, 1952.

UNCLASSIFIED
ORNL—LR—DWG 164 26R

200

800 \ —

700 \
I
3
2 800 —— Lif + LIQUID \

[

w \

14

2

=

& \ L ——
a

= 500 \

[

! / BeFp + LIQUID
400 2LIF- EA A

LIF + 2LIF- BeFy

2LIF-BeFp + Befy (HIGH QUARTZ TYPE)

[ [ !

I |

LiF - BeFp + BeFp (HIGH QUARTZ TYPE)

J | L

LiF - BeFo+ BeFp (LOW QUARTZ TYPE;
LIF 10 20 30 40 50 60 70 80 80 BeFy

BeF, (male %)

300

2LIF - BeFy

2LIF- BeFg
+
LiF+ BeFy

LiF - BeFp

200

Fig. 3.19. The System LiF-BeF.,.

33
3.20. The System NaF ~BeF,
D. M. Roy, R. Roy, and E. F. Osborn, ‘““Flucride Model Systems: |[l}. The System NaF-
BeF, and the Polymorphism of Na,BeF, and BeF,,” J. Am. Ceram. Soc. 36, 185 (1953).

Invariant Equilibria*

Invariant
Mole % BeF'2 Temperature Type of Equilibrium Phase Reaction
in Liquid ©C) at Invariant Temperature

31 570 Eutectic [ 7= NaF + a-2NaF-BeF,
33.3 600 Congruent melting point L = a-2NaF-BeF,

- 320 Inversion a-2NaF«BeF, —= a"2NaF:.BeF,

- 225 inversion a-2NaF-BeF, = -2NaF:BeF,
43 340 Eutectic L = a-2NaF:BeF, + [-NaF:BeF,
50 376 £ 5 Congruent melting point L == B"NaF-BeF,
55 365 Eutectic L— ,B’-NOF-Ber + Bel:'2

*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
TEMPERATURE (°C)

UNCLASSIFIED
ORNL-LR-DWG 16425R

900

800 \

\
NoF + LIQUID
oe = ORNL DATA
700 HQ = HIGH QUARTZ
LQ = LOW QUARTZ
fi a~2NaF BeF,+ LIQUID
600 p *
L J - Lf b d
/"'—_—0

500 \ // .

a- 2NaF BeF,+NaF '~ NaF BeF, BeF,(HQ} + LIQUID

+ LIQUID ‘
400 N - BeRHO) 4 BNoF BeR |
/,—-<7“ 4
-2NaF BeF,+/3 -NaF BeF, \

]a aF Be % {3 -NaF BeF, L \ |

1 | B-NaF Bef,-+1IQUID
300 —————— 4/-2NoF BeF. +NaF B - NaF Bef, I |

@ -enak Berpria + BeF,(HQ) + B-NaF BeF,

E | a’-2NaF BeF,

B ~NaF BeF,+y -2NaF Bef, BeF,(LQ) + 8- NaF BeF,

y-2NaF BeF2+NcF g | !
200 .

NafF 10 20 30 40 50 60 70 80 30 Bef,

BeF, (mole %)

Fig, 3.20. The System NaF-BeF ..

35
3.21. The System KF-BeF,

R. 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.

Preliminary diagram.

Invariant Equilibria

Invariant
Mole % BeF2 Temperature Type of Equilibrium Phase Reaction
In Liquid °C) at Invariant Temperature
19 720 Eutectic L &= KF + 3KF:BeF,
25 740 Congruent melting point L == 3KF:BeF,
27 730 Eutectic L T 3KF:BeF, + a-2KF:BeF,
33.3 787 Congruent melting point L &= a-2KF-BeF,
- 685 Inversion a-2KF-BeF, = [-2KF-BeF,
52 390 Peritectic B-2KF-BeF, + L 7= KF:BeF,
59 330 Eutectic L & KF:BeF, + 5-KF*2BeF,
66.7 358 Congruent melting point L &= a-KF:2BeF,
- 334 Inversion a-KF-2BeF, = B-K F-2BeF,
72.5 323 Eutectic L T (-KF-2BeF, + BeF,

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 KF-BeF, System,”
Zbur. Neorg. Khim. 1, 2071-82 (1956).
UNCLASSIFIED

ORNL-LR-DWG {7574R

200
800 \\ /'
a-2KF Bef,
]
700
S
600
wl
o
o
=
<{
[0 g
Ifil:l /
= 500 & 7
[§4] %)
i E; . \
v ‘G
s @ \
W /
X
400 L \
@, a- KF - 2BeF,
P\
o
300 o i
L m
& o
L T
< i
@
200
KF 10 20 30 40 50 60 T0 80 Q0

BeF, (mole %)

Fig. 321, The System KF-BeF..

BeF,

37
3.22, The System RbF-BeF,

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 petformed at the Oak Ridge National Laboratory,
1955-56.

Preliminary diagram.

Invariant Equilibria

Invariant
Mole % BeF2 Temperature Type of Equilibrium Phase Reaction
in Liquid (°C) at Invariant Temperature
16 675 Eutectic L T RbF + 3RbF:BeF,
25 725 Congruent melting point L= 3RbF-BeF2
27 720 Eutectic L= 3RbF:BeF, + 2RbF-BeF,
33.3 800 Congruent melting point L # 2RbF-BeF2
50.5 442 Peritectic L + 2RbF:BeF, = RbF-.BeF,
61 383 Eutectic L = RbF:BeF, + RbF-2BeF,
66.7 464 Congruent melting point L ;—'\ RbF-?Ber
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-BeF, System and of Its Relationship to the BaO-Si0, System,’’ Doklady
Akad. Nauk §.5.5.R. 114, 316 (1957).

38
900
\ZRbF Bef, +LIQUID
800
3ALF Bef,
+LiQUID
o
700 [+LIQUID \\// N
3 3RbF BeF,
& +
IE:J 600 2RbF Bef,
>
| 2RbF Bef,
& +L1QUID /
o
& s00 RbF 2BeF, +LIQUID — ]
o \ RbF BeF,
3RLF BeF, \ | TLQuid
+ RbF BEF2 + LIQUID
400 -
e
© 2RbF BeF
%5 u e
w
€ & TDF Befo | o o
300 U £ &
i o
z w o ROF Bef "
€ rof 28eF, |& RbF 2BeF,+ BeF,
200
RbF 10 20 30 40 50 60 70 80 90
Ber(mole To)

UNCLASSIFIED
CRNL —LR-DWG 16955

Fig. 3.22 The System RbF-BeF .,

BeF;

39
3.23. The System CsF-BeF2

0. N. Breusov, A. V. Noveselova, and Yu. P. Simanov, ‘‘Thermal and X-Ray Phase Analysis

of the System CsF-BeF, and Its Interrelationships with MeF and BeF, Systems,’’ Doklady

Akad. Nauk S.5.5.R. 118, 935-37 (1958).

Invariant Equilibria

Invariant
Mole % BeF2 Temperature Type of Equilibrium Phase Reaction
in Liquid (°C) at Invariant Temperature

14 598 Eutectic L == CsF + [3-3CsF-BeF,
23.5 659 Peritectic a-2CsF-BeF, + L =— a-3CsF-BeF,

- 617 Inversion a-3CsF.BeF, == [-3CsF:BeF,
33.3 793 Congruent melting point L — (1.-2CsF-BeF2

- 404 Inversion a-2CsF-BeF, & [3-2CsF-BeF,
48 449 Eutectic L == CL—2CsF-BeF2 + OL-CsF-BeF2
50 475 Congruent melting point L & a-CsF-BeF,

- 360 Inversion a-CsF.BeF, = [-CsF:BeF,

- 140 Inversion B-csF-BeF2 = ¥-CsF:BeF,
58.4 393 Eutectic L & a-CsF-BeF, + [5-CsF-2BeF,
66.7 480 Congruent melting point L — a-CsF.2BeF,

- 450 Inversion a-CsF:2BeF, == [-CsF-2BeF,
77.5 367 Eutectic L 7= f3-CsF-2BeF, + BeF,

40
TEMPERATURE (°C)

UNCLASSIFIED

ORNL-LR-DWG 354814

900

800

700

600

500

400

300

200

3CsF-BeF2

ZCSF‘E!(-'.*F2

CsF-BeF2

CsF-ZBeF2

100

CsF

10

20

30

40

50
BeF, {mole %)

60

Fig. 3.23. The System CsF—Ber.

70

80

90

E

41
3.24. The System LiF-NaF-BeF,

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.

Preliminary diagram.

Invariant Equilibria*

Composition of Liguid

Invariant Solids P A
(mole %) o olids Presen
Temperature Type of Equilibrium at |nvariant Point
LiF NaF BeF, °C)
15 58 27 480 Eutectic NaF, LiF, and 2NuF-BeF2
23 41 36 328 Eutectic LiF, 2NaF°BeF2, and
2Nc:|:-LiF-ZBeF2
20 40 40 355 Congruent melting point 2NOF'LiF'2BeF2
5 53 42 318 Eutectic NaF'Ber, 2NoF-BeF2,
and 2N<:1f"'-LiF-2BeF2
31.5 31 37.5 315 Eutectic 2LiF-BeF2, LiF, and

2NoF-LiF-2BeF2

*Invariant equilibria shown in the phase diagram by the intersections of dotted-line boundary curves
have not been determined with sufficient precision to be listed in the table.

Minimum Temperature on Alkemade Lines

Compeosition of Liquid {(mole %)

Temperature Alkemade Line
LiF NaF BeF, (°C)
16 56 28 485 2NaF-BeF ,-LiF
26 37 37 340 2NaF-LiF-2BeF ,—LiF
1 44 45 332 NaF+BeF ,—2NaF-LiF+2BeF,
16 45 39 343 2NaF:BeF ,=2NaF:LiF+2BeF,
30.5 31 38.5 316 2LiF+BeF ,~2NaF LiF+2BeF,

Phase relationships of two of the ternary compounds in this system have been reported by
W. Jahn [**Silicate Models. V. Nali(BeF,), a Model Substance for Monticellite, CaMg(SiO,);"’
Z. anorg. w. allgem. Chem. 276, 113-27 (1954); ‘‘Silicate Models. VI. Na,Li(BeF,),, a New
Compound in the Ternary System NaF-LiF~BeF,, and lts Relation to Merwinite, Ca,Mg(Si0 ),,"’
Z. anorg. u. allgem. Chem. 277, 274-86 (1954)).

42
UNCLASSIFIED
ORNL-LR-DWG 16424R

DOTTED LINES REPRESENT
INCOMPLETELY DEFINED
PHASE BOUNDARIES AND
ALKEMADE LINES TEMPERATURE (°C)

- COMPOSITION (moie Y)

356 e

290
(LIF -BeF,) e 275‘)\ NaF - BeF,
274 72 NoF - LIF -2 BeF, p, -« 380
400 - 355\ 350

45 e

550 (5 NaF-LIF-3 BeF,)

2 L|F-6%eF;2 (NOF'LIIF-BGF ) 2 Ngg-sBer

500 v 240 2 - — 570
550 ' o - 650
600 700
650 750
800
2\ 850

900

LF 800 750 700 649 700 750 800 850 900 950 NaF
844 980

Fig. 324 The System LiF-NaF-BeF ..

43
3.25. The System LiF—RbF-BeF,
T. B. Rhinehammer, D. E. Etter, C. R. Hudgens, N. E. Rogers, and P. A. Tucker, unpublished
work performed at the Mound Laboratory.

Preliminary diagram.

Invariant Equilibria and Singular Points

Composition of

Temperature Type of
Liquid {mole %) P yp
©c) Equilibrium Solid Phases Present

LiF RbF BeF2
40.0 20.0 40,0 485+ 5 Congruent 2LF+<RbF.2Be F2

melting pont
33.3 33.3 33.3 544 + 5 Incongruent

melting point of

LIF-RbF-BeF2
33.0 8.0 59.0 295t 5 Eutectic 2L|FoBeF2, 2L|F-RbF-ZBeF2, and BeF2
26,0 12.0 62.0 305-320 Peritectic 2L|F-RbF‘2BeF2, RbF-2BeF2, and BeF2
12.0 29.0 59.0 334 £ 5 Quasi-binary 2L|F-Rb|:-2BeF2 and RbF-ZBeF2

eutectic
11.0 34.0 55.0 3005 Eutectic 2L|F-RbF-2BeF2, RbF-Ber, and RbF.2Bef 2
1.5 35.5 53.0 3355 Peritectic 2L|F-RbF-2BeF2, LlF-RbF-Ber, and RbF-BeF2

9.0 40.0 51.0 380t 5 Peritectic LIF‘RbFOBer, 2RbF-BeF2, and RbF-BeF2

50.0 8.0 42,0 426 t 5 Peritectic L.F, 2L|F‘RbF-2BeF2, and 2L|F-BeF2
41,5 19.5 39.0 473 5 Quasi-binary LiF and 2LrF-RbF-2BeF2

eutectic
35.0 25,5 39.5 470 £ 5 Peritectic L.F, 2L1F-RbF-2BeF2, and LaF-RbF-BeF2
23.0 40.0 37.0 530t 5 Peritectic L:F, 2RbF-BeF2, and LIF-RbF-BeF2
30.0 35.0 35.0 544 + 5 Maximum on the LiF and LIF«RbF:«Be F2

boundary
41.0 39.5 19.5 640 £ 5 Quasi-bmnary LiF and 2RbF-BeF2

eutectic
43.0 50.0 7.0 527 t 5 Peritectic iF, 3RbF-BeF2, and 2RbF-BeF2
43,0 54.0 3.0 470 £ 5 Peritectic L)F, L1F.-RbF, and 3RbF-BeF2
43.0 55.0 2.0 462 t 5 Eutectic

LiF-RbF, RbF, and 3RbF-BeF,

44
LiF <«

Be FE

TEMPERATURE °C
COMPOSITION mole %%

UNCLASSIFIED
ORNL-LR—-DWG 38143

Fig. 3.25. The System LiF-RbF-BeF,.

RbF

45
3.26. The System NaF-KF-BeF,

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.

Preliminary diagram. Phase relationships within the system NoF-KF-BeF, have not yet
become so well defined at the Oak Ridge National Laboratory that the compositions and tem-

peratures of the invariant points may be listed.

UNCLASSIFIED
ORN_L— LR—DWG 38114

TEMPERATURE IN °C

I COMPOSITION IN mole %
A

KF 2 BeF,

£-370

£-365

P- 390
NaF BeF, KF 2 BeF,
340 /
4 550 —— 0o,
/ INGF KF 2 BeF, b =
2NaF Bef, O o coene Z 700 2KF BeF,
£-570 —— 500 650

.
— £B833 E;jf BeF
== \ -

£-710 856

Fig. 3.26. The System NuF—KF—Ber.
3.27. The System NaF=RbF=BeF,
R. E. Moore, C. J. Barton, L. M. Bratcher, and W. R. Grimes, unpublished work performed
at the Oak Ridge National Laboratory, 1954-57.

Preliminary diagram.

Invarlant Equilibria and Singular Points

Composition of

. Temperature
Liguid (mole %) ©c) Type of Equilibrium Solids Present at Invariant Temperature
NaF  RbF BeF2
20.5 68.5 11.0 610 Eutectic RbF, NaF, and 3RbF-BeF2
50 37.5 12.5 640 Quasi-binary eutectic 3RbF-BeF2 and NaF
46 38 16 635 Eutectic 3RbF-BeF2, 2RbF-BeF2, and NaF
45 37 18 650 Quasi-binary eutectic 2RbF-BeF2 and NaF
37 33 30 570 Peritectic 2RbF-BeF2, NaF, and 2NaF-4RbF-3BeF2
52 15 33 477 Eutectic 2NaF-4RbF-3BeF2, NaF, and 2Nc:F-Be|'-'2
33 33.7 33.3 580 Peritectic 2RbF-BeF2 and 2NeF-4RbF-3BeF,
51.7 15 33.3 480 Quasi-binary eutectic 2Nc1F-4RbF-3BeF2 end 2N<:FoBeF2
UNCLASSIFIED
ORNL~-LR-DWG 22343R2

BE BINARY EUTECTIC

BP BINARY PERITECTIC

CM CONGRUENT MELTING POINT

IM  INCONGRUENT MELTING PCINT

TE TERNARY EUTECTIC

TP TERNARY PERITECTIC

TEMPERATURES Bef>
ARE IN °C CM 543

2RbF Bef,
CM 800

COMPOSITION IN mole Y

Fig. 3.27. The System NaF-RbF-BeF ..

47
3.28. The System NoF-ZnF,

C. J. Barton, L. M. Bratcher, and W. R. Grimes, unpublished
Ridge National Laboratory, 1952.

Preliminary diagram.

Invariant Equilibria

work performed at the Oak

Invariant
Mole % ZnF2 Temperature Type of Equilibrium Phase Reaction
in Liquid ©C) at Invariant Temperature
33 635 Eutectic L == NaF + NuF-ZnF2
50 748 £ 10 Congruent melting point L — NaF-ZnF2
69 685 Eutectic L — NaF-ZnF2 + ZnF2
UNCLASSIFIED
DWG 14627 R
1000 I l r I | |
900 —
;G 800 —
N
s
=
'_
<
0.
u 700—
a
=
Ll
—
6 00— —
LLN
~
500|— a —
=]
=
| l | | | J i
4OONOF 10 20 30 40 50 60 70 80 90 Znf,

ZnF, (mole %)

Fig. 3.28. The System NaF-ZnF,,

48
. 3.29. The System KF-ZnF,

C. J. Barton, L. M. Bratcher, and W. R. Grimes, unpublished work performed at the QOak
Ridge National Laboratory, 1952.

li’relimincry diagram.

Invariant Equilibria

TEMPERATURE (°C}

fnvariant
Mole % ZnF2 Temperature Type of Equilibrium Phase Reaction
in Liquid (OC) at Invariant Temperature
21 670 Eutectic L ¥—=KF + 2KF:ZnF,
30 720 Peritectic L +XK F'°Zn|=2 :AZKF‘Zan
50 850 Congruent melting point L t-___\KF-ZnF2
80 740 Eutectic L &—=KF-ZnF, + ZnF,
UNCLASSIFIED
DWG 14626 R
1000
T
300

800

700

600

500

400

300

u™ %?
- L S _

N ('

L b

¥

[aN]

| I I | l | | |
KF 10 20 30 40 50 60 70 80 90
ZnF, {mole %)

Fig. 3.29. The System KF-ZnF.,.

ZnF,

49
3.30. The System RbF-ZnF,
C. J. Barton, L. M. Bratcher, and W. R. Grimes, unpublished work performed at the Oak
Ridge National Laboratery, 1952.

Preliminary diagram.

Invariant Equilibria

Invariant
Mole % ZnF2 Temperature Type of Equilibrium Phase Reaction
in Liquid (°C) at Invariant Temperature
21 595 £ 10 Eutectic L —— RbF + 2RbF-ZnF2
32 620 + 10 Peritectic L + RbF-ZnF, — 2RbF-ZnF,
50 730 + 10 Congruent melting point L= RbF-ZnF2
70 650 Eutectic L= RbF-ZnF2 + ZnF2
UNCLASSIFIED
DWG 15349 R
1000
300

TEMPERATURE (°C)

T00

600
e L
N ™~

500 I— . . o
b 5
e [Vl
oJ

400 1

RbF 10 20 30 40 50 60 70 80 90 ZnF2
ZnF, {mole %)

Fig. 3.30. The System RbF-ZnF »
3.31. The System LiF-YF,

R. E. Thoma, C. F. Weaver, and H. A. Friedman, unpublished work performed at the Qak

Ridge National Laboratory, 1958-59.

Preliminary diagram.

Invariant Equilibria

Invariant
Mole % YF3 Temperature Type of Equilibrium Phase Reaction
in Liquid C) at Invariant Temperature
19 695 Eutectic I_.:L|F+L|F-YF:3
49 815 Peritectic L+ YF,=—LiF.YF,
UNCLASSIFIED
ORNL LR-DWG 384416

| |

1400 } } I / !
S | o ! _ J

1300
© RESULTS FROM THERMAL GRADIENT QUENCHING EXPERIMENTS
® RESULTS FROM THERMAL-ANALYSIS EXPER MENTS |
| I
1200 —_ — — —
| |
Mmoo —  ——+ [ — Jfi

1000

9C0

TEMPERATURE {°C)

1T

BREWER 1387°

800

700

600

500

YF5 (mole 7o)

Fig. 3.31. The System LiF-YF ..

20 YF.

51
3.32. The System LiF-ZrF,

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.
Preliminary diagram.

Invariant Equilibria

Invariant
Mole % ZrF , Temperature Type of Equilibrium Phase Reaction
in Liquid Q) at Invariant Temperature
21 598 Eutectic L —3LiF +a-3LiF-ZrF,
25 662 Congruent melting point L= a-3LiF-ZrF ,
- 475 Inversion a-3LiF-ZrF , &= [-3LiF-ZrF,
- 470 Decomposition /5-3|_s|=-zri=4 = LiF + 2LiF-ZrF,
29.5 570 Eutectic L == a-3LiF.ZrF , + 2LiF-ZrF,
33.3 596 Congruent melting point L— 2LiF-ZrF4
49 507 Eutectic L &= 2LiF-ZrF , + 3LiF-4ZrF ,
51.5 520 Peritectic L + ZeF , = SLiF-4ZrF,
- 466 Decomposition 3LiF-4ZrF, = 2LiFZrF  + ZrF

52
{000

900

800

TEMPERATURE (°C)
~
Q
<

o2}
o
(@]

500

400

300

UNCLASSIFIED
ORNL—LR-DWG 46951

T
| | | | ' |
| | |
i
. o
l | , : i ]
l T t - *T o /
|
| \ | ! !
\ | ! \ ‘ ! \ i J
|
| \ | ‘ |
Kcz—3L|F ZrF, +LIQuID ! i |
LIF+ LIQUID [ : ‘
| Qu : ZrF+ LIQUID
2LIF ZrF4+L_IOUID |
|
a- 3L ZrF4+2L|F ZrF4 ‘ ‘ | | ‘ '
™~ 2LIF ZrF, 3LIF 4ZrF+LIQUID [
LIF+a-3LF Irfy, +LIOUID
i : 7 2LIF ZeF, + 3LsF 4ZrF, \L SLiIF 4ZrFy+ Zrky
| |
LLli-'+[3’—3L|F ZrF4 T
3LIF 47ZrF,
2L1F ZrF4+,G’—3L|F ZFF4 e t —_— = ———— = — 1 - i—
N | ! |
LIF+ 2LIF ZrF4 w 2 LIF ZFF4+ZFF4 |
pu|
~N
. | | . . !
LIF [1e} 20 30 40 50 60 70 80 90

Zrf, (mole %}

Fig. 3.32, The System LiF-ZrF ,

53
3.33. The System NaF-ZrF
C. J. Barton, W. R. Grimes, H. Insley, R. E. Moore, and R. E. Thoma, ‘‘Phase Equilibria
in the Systems NaF-ZrF ,, UF ,~ZrF ,, and NaF-ZrF ,~UF ,,'" J. Pbys. Chem. 62, 665-76 (1958).

Invariant Equilibria

Invariant
Mole % ZrF4 Temperature Type of Equilibrium Phase Reaction
in Liquid ) at Invariant Temperature
20 747 Eutectic L == NaF + 3NoF-ZrF4
25 850 Congruent melting point L # 3NaF-ZrF4*
- 523 Inversion a-5NaF.2ZrF, == [3-5NaF.2ZrF
30.5 500 Eutectoid a-5NaF-2ZrF ss — [5-5NaF.2ZrF +
+ Ye2NaF*Zr Fq
34 640 Peritectic L + 3NaF:Zr F4(ss, ca. 27.5 mole %
ZrF4) = a-5Na F-2ZrF4
39.5 544 Peritectic L+ a-SNaF-ZZrF4(ss, 30 mole %
ZrFA) — a-2NaF-ZrF4
- 533 Inversion a-2NaF-ZrF :.:‘B-ch.F.sz4
-~ 505 Inversion [3-2NaF+ZrF , == y-2NaF-ZrF
40.5 500 Eutectic L #’)/-2N0F-er:4 + 7NaF-6ZrF4ss
46.2 525 Congruent melting point L= 7N<:F"'6Zr|'_‘4
49.5 512 Eutectic L= 7Nc:|:°6ZrF4 + 3N‘:1F-AZ|'F4
56.5 537 Peritectic

L+ ZrF4 —;___—3 3Nc:|=-42rF4

*A determination of the crystal structure of 3NaF-ZrF4 has been reported by L. A. Harris, **The Crystal

Structures of Nq3ZrF7 and Na3HfF7," Acta Cryst. 12, 172 (1959).

54
UNCLASSIFIED
ORNL -LR-DWG-22405

Y3174 4ONE

Piizg 4ONL

—

7 %7z Jong

|

1000

r\.\l..\ 741z _doNg
1
o Y1172 4ONG ——
—————d 1
I S N
/ Y1z 4ong
/
o] o o j&] o [
o O O Q O (@)
o [eu] - {e] I's] <

(Do) 3HNLYYIJNGL

300

10 20 30 40 50 60 70 80 g0
ZcF, imale %o}

NaF

Fiz 3.33. The System NaF-ZrF ..

55
3.34. The System KF-ZrF ,
C. J. Barton, H. Insley, R. P. Metcalf, R. E. Thoma, and W. R. Grimes, unpublished work

petformed at the Oak Ridge National Laboratory, 1951-55.

Preliminary diagram.

Invariant Equilibria

Invariant
Mole % ZrFy Temperature Type of Equilibrium Phase Reaction
in Liquid ©c) at Invariont Temperature
14 765 Eutectic L Z—KF + 3KF°ZrF4
25 910 Congruent melting point L — 3K F-ZrF,
36 590 Peritectic 3KF-ZeF  + L ;”‘2!(F-Zrlz4
40.5 412 Peritectic 2KF+ZrF, + L :3KF°2ZrF4
42 390 Eutectic L — 3K F-2ZrF , + KF-ZrF
50 475 Congruent melting point L= KF-ZrF,
55 440 Eutectic L == KF-ZrF4 + ZrF4
UNCLASSIFIED
ORNL-LR-DWG 18965
{1000 '
!
|
200 /t \ ; - //
800 \\// \ //
¢
; /
w 700 - —
& /
>
=
<
o
W
¥ /
5 600 \
-
E
500 \//
u W \
400 A A <1\ —
s X [
fYs) o N us
o [a
. N
w .
X 0.
~y p's
300
KF 10 20 30 40 50 60 70 80 a0 ZrF,
ZrF, (mole %)

56

Fig. 3.34 The System KF-ZrF ..
3.35. The System RbF=ZrF,
R. E. Moore, R. E. Thoma, C. J. Barton, W. R. Grimes, H. Insley, B. S. Landau, and H. A,
Friedman, unpublished work performed at the Oak Ridge National Laboratory, 1955-56.

Preliminary diagram.

Invariant Equilibria

Invariant
Mole % ZrF4 Temperature Type of Equilibrium Phase Reaction
in Liquid ©C) at Invariant Temperature
10 710 Eutectic L :—‘RbF+3RbF"-ZrF4
25 897 Congruent melting point L &— 3RbF-ZrF4
34 620 Peritectic L 4+ 3RbF+Zr F4ss = a.-ZRbF-ZrF4
- 460 Inversion a-2RbF.ZrF, :__—‘B-szF-sz4
- 370 Lowered inversion CL-QRbF-ZrF4ss . fi-2RbF-ZrF4ss
and decomposition
42 410 Eutectic L =— a-2Rb F:ZrF ss + 5RbF-4ZrF ,
44.4 445 Congruent melting point L == 5RbF-4ZrF,
48 390 Eutectic L = 5Rb F-4ZrF4 + [5-Rb F-ZrF4
50 423 Congruent melting point L — a.-RbF-ZrF4
- 3N Inversion a-RbF.ZrF, == [S-RbF.ZrF
54 400 Eutectic L — a-RbF-ZrF4 + RbF-2ZrF4
57 447 Peritectic L+ ZrF4 =5 RbF-2ZrF4
UNCLASSIFIED
ORNL-LR—-DWG 14029R
1000 1 ~ ‘ T \
200 ‘ } |
/\\
\
1
|
\
800 ] —
oy
- ]
[&] |
< ' /
& 700
& /
2 600 b— A ]
!
| \
| \
: \ |
5 - - - —
00 ; ‘ll \ l} |
)
«| | ot
e =
400 [———— = — :T’L ——;}‘T\‘ = —\/ 7 T
R it B N [ |
I \ 5 N w
'} | [ L x
300 1 1 L v} & |
RbF 10 20 30 40 50 60 70 80 20 zrF,

ZrF, {mole%)

Fig. 335. The System RbF—ZrF .
3.36. The System CsF-ZrF,

C. J. Barton, L. M. Bratcher, and W. R. Grimes, unpublished work performed at the Oak

Ridge National Laboratory, 1952-53.

Preliminary diagram.

Invariant Equilibria

Invariant
Mole % ZrFy Temperature Type of Equilibrium Phase Reaction
in Liquid °C) at Invariant Temperature

9 640 Eutectic L &= CsF + 3CsF-ZrF,
25 775 Congruent melting point L == 3CsF-ZrF4
35 520 Peritectic L +3Cs FoZrF4 — 2CsF.Zr F4
40 420 Eutectic L= 2CsF-ZrF4 +a-Cs F-Zer
50 515 Congruent melting point L — a-CsF-ZrF,
- 320 Inversion a-Cs F~ZrF4 = ,B-Cs F-ZrF4
59 470 Eutectic

L= OL-CsF-ZrF4 + ZrF4

58
TEMPERATURE (°C}

UNCLASSIFIED
ORNL—LR—DWG 18963

1000 )
| i
900 — o | prd
|
800 - - o / -
|
. / / \ N | )
600 — / e
500 R TN / !
F \/: J
LLw
"\‘.-‘ u
N .
400 & ™ 1 n
I :'u; ™~
« %
(@)
300
CsF 10 20 30 40 50 60 70 80 30 zZrF,

ZrF4(mole To}

Fig. 336. The System CsF-ZrF .

59
3.37. The System LiF-NaF-ZrF

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.

Preliminary diagram,

Invariant Equilibria

Composition of Liquid

(mole %) Temperature Type of Solids Present
(°C) Invariant at Invariant Temperature

LiF  NaF  ZrF,
37 52 n 604 Eutectic NaF, LiF, and 3NaF.ZrF,
55 22 23 590 Eutectic a-3LiF-ZrF ,, 3NaF-ZrF ss, and LiF
32 36 32 450 Peritectic ~ [-3LiF.ZrF,, 3NaF-ZrF ,ss, and 2LiF.ZrF,
31 35 34 448 Peritectic ~ 3NaF.ZrF,, a-5NaF.2ZrF ;ss, and 2LiF.ZrF
31 34.5 34.5 445 Peritectic ~ 2NaF-ZrF,, @-5NaF-2Z¢F ss, and 2LiF.ZrF,
26 37 37 425 Eutectic 2NaF-ZrF,, TNaF-6ZrF ,, and 2LiF-ZrF
29 25.5 45.5 449 Eutectic 7NoF-6ZrF ,, 3NaF-4ZrF ss, and 2LiF.ZrF,
29 24.5 46.5 453 Peritectic ~ 3NaF.4ZrF  ss, 3LiF:4ZrF ;ss, and 2LiF-ZrF,
28 24 48 475 Peritectic

3NuF-4ZrF4ss, 3LiF-4ZrF4ss, and ZrF4

60

NaF
990

P-537"7
F-512._,
7 NaF + 6 Zrfg -

UNCLASSIFIED
ORNL-LR-DWG 38145

ZrF, 912

TEMPERATURE IN °C
COMPOSITION IN mole %

== INDICATES SOLID SOLUTION

2LIF - ZrFy

R —
2 NaF - ZrF, —f~—— % BE——
) m’ —————— s - fi£-570

5NoF 2ZrFy~- A\-w R 4807 e

]
e

N 5 O
3INaF « ZrF,— a_#—.-nfll 'm-_ 990 6 “SLiF - Zrfy
a” FREEEET T

E-747-4

—£-605

£-6562

Fig. 3.37. The System LiF—NaF-Z«F

LiF
845

61
3.38. The System NaF-KF-ZrF,
R. E. Thoma, C. J. Barton, H. Insley, H. A. Friedman, and W. R. Grimes, unpublished work
performed at the Oak Ridge National Laboratory, 1951-35.

Preliminary diagram.

Invariant Equilibria*

Composition of

. Inveriant

P *

Liquid (mole %) Temperature Type of Equilibrium Solids Present at Invariant Point

NaF  KF  ZrF, ©C)

34 58 8 695 E utectic NaoF, KF, and 3KF-Z:‘F‘4

45 38 17 720 Eutectic NaF, 3KF-ZrF4, and 3Nt:F-3KF"-2ZrF4

61 19 20 710 Eutectic NaF, 3NuF-ZrF4, and 3NaF-3KF°22rF4

52 17 31 Peritectic 3NuF-ZrF4, 3NaF-3KF-2ZrF,, and
NaF-KF-ZrF4

48 18 34 Peritectic 3NaF:ZtF ,, NaF*KF*ZrF ,, and
5NaF-2ZrF4

33 32 35 Peritectic 3N0F-3KF'ZZrF4, 3KF-ZrF ,, and
NCIF-KF-ZrF4

12 51 37 Peritectic 3KF-ZrF ;, 2KF+ZrF ,, and
NaF-KI":-ZrF4

40 21 39 Peritectic 5Na F-?ZrF4, 2NaF.ZrF ,, and
NaFoKF-ZrF4

39 21 40 Peritectic 2Na F-ZrFA, 7NaF.6ZtF ,, and
NaF.KF-ZrF ,

11 49 40 Peritectic 2KF-ZrF4, 3KF-22rF4, and
NaF-KF-ZrF4

10 48 42 385 Eutectic 3KF-2ZrF4, KF-ZrFA, and
NuF-KF-ZrF4

15 40 45 Eutectic KF-ZI'F4, NaF-KF-ZrF4, and
ZNGF-3KF'521‘F4

22 33 45 Peritectic NuFoKFoZrF4, 7NoF-6ZrF4, and
2N0F-3KF°521'F4

25 25 50 Eutectic 7NaF+6ZtF ,, 3NaF-4ZrF ,, and
2NaF-3KF-52rF4

21 29 51 Eutectic 3NaF-4ZrF4, ZrF4, and
2Nc:|:-3|(f=-52rF4

20 30 50 432 Congruent melting point 2N0F-3KF-SZrF4

*Three solid phases have been observed routinely in the composition region 30~50 mole % ZrF4 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-DWG 35480
ZrF, 912
g0o0
TEMPERATURE IN °C
COMPOSITION IN mote 7o A 2NaF 3KF 5ZrF,
850

B NoF KF ZrF,
C 3NaF 3KF 27rF,

800
750
700
890
600
550
3NaF 4ZrF,
P 537 500 450 £440
250
£ 542 > N KF ZrF,
7NaF 6ZrF o \
£ 500 ° - e - £ 390
VA syt 450 - P 412
550 - IKF 2ZrF,
- P 530
P 640 __.._..._/ = 550
2NaF Zri, 750 - 2KF ZrF,

a\
790 0
SNoF 2Z¢F, 200 / / " 80 850’\#;
3NaF ZrF, %// /C — e 2,
£ 747 ,_,K; 4 4A

£ 765
&8
- 900 S0

T N Y\ Y VRN,

KF
£ 710 856

Fig. 3.38. The System NoF—KF—ZrF4. The isotherms for the temperatures 600, 650, and 700°C

between the 30 and 40 mole % ZrF, compositions have been omitted in order not to obscure the phase
relationships in this polythermal projection.

63
3.39. The System NaF-—RbF—ZrF4 .
R. E. Thoma, H. Insley, H. A. Friedman, and W. R. Grimes, unpublished work performed at
the Oak Ridge National Laboratory, 1951-56.

Preliminary diagram.

Invarlant Equilibria

Composition of

Invariant
Liquid (mole %) Temperature Type of Equilibrium Solids Present at Invariant Point
NeF  RbF  ZrF, c)
23 72 5 643 Eutectic NaF, RbF, and 3RbF-Z|’F4
50 27 23 720 Eutectic NaF, 3RbF-ZrF4, and 3N<:|F-ZrF4
37 32 31 605 Eutectic 3NaF-ZrF4, 3RbF-ZrF4, and
NaF-RbF-ZrF4
39 26 35 545 Peritectic 3Na F-ZrF4, SNGF-ZZrF4, and
NOF-RbF-ZrF4
36.3 24,2 39.5 427 Peritectic 5N0F-ZZrF4, 2NaF-ZrF ,, and
NcF‘RbF-ZrF“
345 24 41.5 424 Peritectic 2NaF-ZrF , NaF:RbF:ZrF,, and
3NaF.3RLF-4ZrF
34 23.5 42,5 422 Peritectic 2NaF-ZrF4, 7NuFo6ZrF4, and
3chF-3|'\’|:>F-AZrF4
33 23.5 43.5 420 Eutectic 7Na F«6ZrF,, 3NaF-3RbF-4ZrF ,, and
NoF-RbF-ZZrF4
28.5 21.5 50 443 Eutectic 3NoF-4ZrF4, 7NaF-62rF4, and
NaF-RbF.2ZrF ,
28 21.5 50.5 446 Peritectic 3Na F-AZrF4, ZrF4, and
NaF-RbF-2ZrF4
23.5 39.5 37 470 Peritectic NaF.Rb F-ZrF4, 2RbF-ZrF4, and
3RbF«ZrF
4
21 40 39 438 Peritectic NoF-RbF-Zer, 2RbF-ZrF 4, and
3NaF:3RbF-4ZsF
8 50 42 400 Eutectic 3NaF-3RbF-42rF4, ZRBF-ZrFA, and
SRbF-tinF4
8.5 47 44.5 395 Eutectic 3NaF-3RbF-42rF4, 5RbF-ZrF4, and
NuF-RbF-2ZrF4
6.2 45.8 48 380 Eutectic NaF-RbF~22rF4, 5RbF-4ZrF4, and
RbF-ZrF4
5 42 53 398 Eutectic NaFoRbF-ZZrF4, RbF+ZrF ,, and
RbF-2ZrF
6.5 39 54.5 423 Peritectic ZrF4, NaF-RbF-QZrF4, and
RbF«2ZrF
4
33.3 33.3 33.3 642 Congruent melting point Na F-RbF-ZrF4
25 25 50 462 Congruent melting point ~ NaF:RbF.2ZrF .

64
Minimum Temperatures on Alkemade Lines

Composition of Liquid (mole %)

Temperature Alkemade Line
NaF RbF ZeF, (°c
24.75 24,75 51.5 455 NaF:RbF.2Zr F4—-Zr F4
6 44 50 402 thF-RbF-2ZrF4—RbF-ZrF4
7.5 46.5 46 405 NaF-RbF-2ZrF4—5Rb F-4ZrF4
8.5 48.5 43 405 3NaF-RbF-4ZrF4—5RbF-4Zr F4
28 28 44 435 3N<:|F-RbF-AZrF4—NaF-RbF-2ZrF4
22 40 38 442 3N<:|F-3RbF-4Zr|=4--2F2bF-ZrF‘1
29 41.5 49.5 450 NaF«Rb F-2ZrF4-7Na F-6ZrF’4
37 24.5 38.5 610 NuF-RbF-ZrF4~3NaF-ZrF4
47 28 25 732 3Na:1I"'-ZrF:“—-SRl:.vl"'-ZrF4
36 48 16 777 NaF-3RbF.Zr F4
30 36.7 33.3 598 NaF-RbF-ZrF4-3RbF-ZrF4
UNCLASSIFIED
QORNL-LR-DWG 46960A
ZrF, 910
300
COMPOSITION N mole 7 g NoF RbF 2ZrF,
TEMPERATURE N °C b 3NaF 3RbF 4;,;:4
850 ¢ NaF RbF 2rF,
800
~e— 00— "\ RbF 22rE,
3INaF 4ZrF, - - ]
I N
——— £ ~ RbF-Z1F, 423
S £ 390
TNoF 8Zrk, T SRbF 4ZrF, 445
£ 500 8 -~ £440
P 544 500
550
£ 640 Soeggo ¢ 60C P E20
2NaF ZrF, = 650 500 2Hor ZrF,
SNOF 2ZrF, 700 %0 150790 @/
3NaF Z¢F, 3RbF ZrF, 897
£ 747
£ 710
NaF RbF
980 £675 790

Fig. 3.39. The System NaF-RbF-Z¢F ..

65
3.40. The System NaF-CtF,—ZrF,: The Section NaF.CrF, — ZrF,

at the Oak Ridge National Laboratory, 1956-57.

Preliminary diagram.

R. E. Thoma, H. A. Friedman, B. S. Landau, and W. R. Grimes, unpublished work performed

No invariant equilibria occur for compositions lying on the section

NaF.CrF =ZrF .
2 4
UNCLASSIFIED
ORNL-LR-DWG 19367R
1000
900 ~ T Zrfy +LIQUID
800 N /
s \ Crfy+ Zrf, + LIQUID
t
W \\ |
2 |
£ 700 ! —
< /
& <
s NaF - CrFp + LIQUID W |
w a-NoF - CrF,-2ZrF, ~N |
= + LIQUID O |
600 . & ! —
© a—NaF CrFyp 2ZrFy + ZrFy
NaF - CrF, + a-NaF : CrF,- 2 ZrF, s
=z
500
NoF:Crfp + B-NaF - Crfp- 22rF, B—NaF-CrFp: 2ZrF4 + ZrFy
400 } l
NaF - CrFp 10 20 30 40 50 60 70 80 90 ZrF,

66

Fig. 3.40. The Section NaF:CrF ,~ZrF

ZrF, {mole %)
3.41. The System NaF -CeF,-Z/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 NaF-ZrF, and NaF-ZrF ,-UF
Solvents,”” J. Chem. Eng. Data (in press).

UNCLASSIFIED
ORNL-LR-DWG 29164R

CeF3 (1387°C)

———————

NaF 800°C 50 %o ZrF, (918°C)

Fig. 3.41a, The System NaF-CeF ,-Z¢F .

UNCILLASSIFIED
ORNL-LR~-DWG 29165R

PROBABLE NaF-ZrF, PRIMARY PHASE FIELDS

A Zrl:4 D 2NaF- ZrF4
B 3NoF-4ZrF4, E 5NaF - ZZrF4
C ?NcF-GZrF4 F 3NaF- ZrF4

30%2rF,  “E o 50% 70% ZrF,

Fig. 3415, The System NaF —~CeF ;~Z¢F ; in the Region 30-70 Mole % NaF,
0-20 Mole % CeF 3¢ 30--70 Mole % ZrF4.

67
3.42. The System LiF-CeF,

C. J. Barton, L. M. Bratcher, R. J. Sheil, and W. R. Grimes, unpublished work performed at
the Oak Ridge National Laboratory, 1956-57.

Preliminary diagram. The system LiF-CeF, contains a single eutectic at 81 LiF=19 CeF,
(mole %), m.p. 755 £ 5°C.

68
TEMPERATURE (°C)

1300

1200

1100

000

S00

700

600

UNCLASSIFIED

ORNL-LR-DWG 19365

LIF

Cefy (mole %)

Fig. 3.42. The System LiF-CeF .

7
oG
4
/\
L
/ ’
p.
e
/
/
b—O0—0—O0——0— 0 0 O 4 L o e e ]
10 20 30 40 50 60 70 80 90

CeF,

69
3.43. The System NaF -HfF
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, 1956-~58.

Preliminary diagram.

Invariant Equilibria

Invariant
Mole % HfF4 Temperature Type of Equilibrium Phase Reaction
in Liquid ) at Invariant Temperature
18.5 695 Eutectic L == NaF + 3NaF.HfF,
25 863 Congruent melting point L T 3NaF-HfF *
34 606 Peritectic L + 3NaF-HfF , == a-5NaF.2HfF
- 535 Inversion a-5NaF2HfF , = [3-5NaF-2HfF
35 586 Peritectic L + a-5NaF-2HfF = [3-2NaF-HfF
- Below 350 Inversion [3-2NaFHfF , = y-2NaF-HfF
- Below 350 Inversion ¥-2NaF HfF , = 8-2NaF-HfF ,
43 510 Eutectic L 7 [3-2NaFHfF , + 7NaF.6HfF
45 531 Peritectic L + NaF+HfF , == 7NaF.6HfF
50 557 Congruent melting point L & NaF-.HfF,
53 535 Eutectic L = NaF-HfF , + HIF,

*A determination of the crystal structure of 3NaF-HfF4 has been reported by L. A, Harris, **The Crystal
Structures of ch3ZrF7 and NaaHfFr" Acta Cryst. 12, 172 (1959).

70
TEMPERATURE (°C)

UNCLASSIFIED

ORNL-LR-DWG 35488

1050
950 \
850 A Va \
750 VI \
650
550 i
\//
us e
uTl = uY “~—
as0 SHEe Pt
w | U W T
j=) (=] [=] [=] u
z|=z Z 2| o
o o -
350
NaF 10 20 30 40 50 S0 Hffi;
HfF, (mole 7o}

Fig. 3.43. The System NaF —HfF ,.

71
3.44. The System LiF-ThF,
R. E. Thoma, H. Insley, B. S. Landau, H. A. Friedman, and W. R. Grimes, ‘‘Phase Equilibria
in the Fused Salt Systems LiF~ThF, and NaF-ThF ,,"" J. Phys. Chem. 63, 1266-74 (1959).

Invariant Equilibria

Invariant
Mole % ThF4 Temperature Type of Equilibrium Phase Reaction
in Liquid °C) at Invariant Temperature
23 568 Eutectic L = LiF + 3LiF-ThF4
25 573 Congruent melting point L= 3LiF-ThF4
29 565 Eutectic L = 3Lif‘7-ThF4 + 7LiF-6ThF4
30.5 597 Peritectic LiF-2ThF4 +L = 7LiF-6ThF4
42 762 Peritectic LiF-4ThF, + L & LiF.2ThF,
62 897 Peritectic ThF, + L — LiF+4ThF,
UNCLASSIFIED
GRNL-LR-DWG 26535A
150 T i i :

1050 S AN U S N N e gt
Y

S 950 u / U
" | A |
5 850 I S S 0 R I
= ] \/ |
i L | | | |
a 0 — — S . — -
> | | ‘ | |
|
“eso; N - A1 el
N L
l l H |
550 = | ] s
3LIF- hF4*-—7L!|F-6ThF4-- L_||F ThE, - l
] | | |

450

LIF 10 20 30 40 50 60

-~
O
09]
@)
Q0
o
—
-y

~n

Fig. 3.44. The System LiF-ThF ,

72
3.45. The System NaF-ThF,

R. E. Thoma, H. Insley, B. S. Landau, H. A. Friedman, and W. R. Grimes, ‘'Phase Equilibria
in the Fused Salt Systems LiF—ThF4 and NoF-—ThF4," J. Phbys. Chem. 63, 1266-74 (1959).

Invariant Equilibria

Invariant
Mole % ThF4 Temperature Type of Equilibrium Phase Reaction
in Liquid C) at Invariant Temperature
21.5 645 Peritectic NoF + L =—— a-4NoF-ThF4
22.5 618 Eutectic L = a-4Na F-ThF4 + 2NaF+Th Fq
- 604 Inversion -4Na F-ThF4 pr— fi-4NaF-ThF4
- 558 Decomposition ,B-4NaFoThF4 ¥ NaF + 2NaF.ThF,
33.3 705 Congruent melting point L —— 2NaF-ThF4
37 690 Eutectic L = 2Na F-Th!:4 + 3!‘«1<:|F-2ThF4
40 712 Congruent melting point L — 3NaF-2ThF4
41 705 Eutectic L— 3NcF-2ThF4 + a-NaF-ThF4
- 683 Decomposition 3NaF:2ThF , == 2NaF:ThF, + a-NaF-ThF,
- 45.5 730 Peritectic NaFs2ThF, + L‘—:‘-a-NaF-ThF4
58 831 Peritectic ThF4 + L/ NaF-ZThF4
UNCLASSIFIED
ORNL-LR-DWG 28528AR
1150
1050 L~
950 [\ //
G AN /
: \ /
& 850 /
o \
g \ y \
750 ' A —
g \ z \
E 1 i
= 650 \ / « L~ e
\Val = LS =
E et oJ
|_. .
550 L 's
4NaF-ThF, R 2
| 2Naf Tf, " J
450 !
NaoF 10 20 30 40 50 60 70 80 90 Thh,

ThF, (mole %)

Fig, 3.45. The System NaF -ThF ..

73
3.46. The System KF-ThF

W. J. Asker, E. R. Segnit, and A. W. Wylie, *‘The Potassium Thorium Fluorides,”’ J. Chem.

Soc. 1952, 4470-79.

This system has also been reported by A. G. Bergman and E. P. Dergunov, Doklady Akad.
Nauk §.5.5.R. 53, 753 (1941) and by V. S. Emelyanov and A. J. Evstyukhin, ‘*An Investigation
of Fused-Salt Systems Based on Thorium Fluoride — [I. NaF-KF-ThF ,, NaF-ThF ,, and KF-
ThF,,”" J. Nuclear Energy 5, 108-14 (1957).

Invariont Equilibria

Invariant
Mole % ThF4 Temperature Type of Equilibrium Phase Reaction
in Liquid ©c) at lnvariant Temperature
14 694 Eutectic L &= KF + 8-5KF-ThF,
- 635 Inversion (.L—f)KF-ThF4 — 3-5K F-ThF4
- 712 Peritectic L +3KF-ThF, = a-5KF.ThF,
25 865 Congruent melting point L rT\‘_— 3KF-ThF4
- 570 Decompos ition 3KF.ThF, — [B-5KF-ThF, + 3-2KF-ThF
31 691 Eutectic L —=3KF.ThF, + a-2KF.ThF,
- 747 Peritectic L + KF-ThF, —= a-2KF-ThF,
- 645 Inversion a-2KF-ThF, == [3-2KF-ThF,
50* 905 Congruent melting point L— I(F-ThF"'4
—_

56 875 Eutectic L KF-ThF4 + KF-ZTH:'4
66 930 Peritectic L+ KF-3T|1F4 — KF-2ThF4
75 990 Congruent melting pawint L— KF-3T|'\F4
78 980 Eutectic

L= |(i"‘-3ThI"'4 + ThF4ss

*|t has been shown that the compound labeled by Asker et al. has the actual formula 7K F-6ThF4, cf. R.

E. Thoma, Crystal Structures of Some Compounds of UF4 and ThF

40 (December 11, 1958).

74

4 with Alkal: Fluorides, ORNL CF-58-12-
TEMPERATURE (°C)

1200

{100

1000

900

800

T00

600

500

UNCLASSIFIED

ORNL—LR—DWG 18966

3KF-ThE, \

u_v
&
J hy mn
Y ) = .
[ e
od X
w
X
uy ue u
£ 2 £
o .
% v =
KF 10 20 30 40 50 60 70 80 a0
ThF, (mole %)

Fig. 3.46, The System KF--ThF4.

ThF,

75
3.47. The System RbF—ThF4
E. P. Dergunov and A. G. Bergman, “Complex Formation Between Alkali Metal Fluorides
and Fluorides of Metals of the Fourth Group,”’ Doklady Akad. Nauk S.5.5.R. 60, 391-94 (1948).

Invariant Equilibria

76

ThF, (mole %)

Invariant
Mole 7% ThFd Temperature Type of Equilibrium Phase Reaction
in Liquid ©C) at Invariant Temperature
15 664 Eutectic L = RbF + 3RbF-ThF4
25 974 Congruent melting point L = 3RbF-ThF4
37 762 Eutectic L &= 3RbF-ThF, + RbF.ThF,
50 852 Congruent melting point L= RbF-ThF4
54 848 Eutectic L= Rl:oF-ThF4 + F&‘bF-3ThF"4
75 1004 Congruent melting point L= RbF-3ThF4
80 1000 Eutectic L= RbF-3ThF4 + ThF4
UNCLASSIFIED
ORNL~LR—DWG 20464
1200 ] ‘ ‘
l i i !
l ! | l ! 1114°
1100 ! ' - | 1
J 1
1004° o
1000 "~ 1000
97& ~
£ 900 / \
5 / 852° 848°
2
<
& / /
a 800 _ -
S i
5 780 \ \/ 762°
™ —
700 -
664° \I |
|
£ u fg !
600 " - = o f——
¢ | s 5
" { a 14
|
500 ‘
RbF 10 20 30 40 50 60 70 80 90 ThE,

Fig. 3.47. The System RbF-ThF ,
3.48. The System BeF,~ThF,

R. E. Thoma, H. Insley, H. A. Friedman, and C. F. Weaver, *‘Phase Equilibria in the Sys-
tems BeF,-ThF, and LiF-BeF,~ThF,,” paper to be presented at the 136th National Meeting
of the American Chemical Society, Atlantic City, N. J., Sept. 13-18, 1959.

The system BeF,—ThF, contains a single eutectic at 98.5 BeF,-1.5 ThF, (mole %), m.p.
526 + 3°C.

UNCLASSIFIED
ORNL-LR-DWG 24551
1200
1100 ="
/
/
1000

900 p
/
800 /

700 /
600 \/

500
BeF, 10 20 30 40 50 60 70 80 90 Thf,

ThF, (mole %)

TEMPERATURE (°C)

Fig. 3.48. The System Ber—ThF4.

77
3.49. The System BeF,.UF,

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

Preliminary diagram. The system BeF,-UF, contains a single eutectic at 99.5 BeF2—0.5
UF, (mole %), m.p. 535 £2°C,

UNCLASSIFIED
ORNL LR DWG 28598
I

[[le]0] T T T T | T T T T T [ T

1000

LIQUID

900+

et

00f-
UFg4 +LIQUID

TEMPERATURE

©-0-00—0-0—0-0-0- 000 =0=0—0 00— 0—O—§——Tr - o —-— - o o - o o ———
QHIGHBeF2 +UF,
400 i l ! | L 1 1 ! ! | L | ! l | I | )
0 10 20 30 40 50 60 70 80 90 100
BeFo MOLE PERCENT UF4 UFy

Fig. 3.49. The System Ber—UFd.

78
3.50. The System MgF ,~ThF,
J. O. Blomeke, An Investigation of the ThF ;~Fused Salt Solutions for Homogeneous Re-
actors, ORNL-1030 (June 19, 1951) (declassified with deletions).

Invariant Equilibria

Invariant
Mole % ThFA Temperature Type of Equilibrium Phase Reaction
in Liqutd (°C) at Invariant Temperature
25 915 Eutectic L — ThF4+MgF2-2ThF4
33.3 937 Congruent melting point L= Mng-ZThF4
40 925 Eutectic L — MgF2-2ThF4 + MgF:Z
UNCLASSIFIED
ORNL-LR-DWG 20465
12C0 |
|
1100 - |
| /V
1000 s
. é/
£ g — Qo &
2 900 —— ]
x
W
a
= C
= %
800 £
o
b=
700
600
ThF, 10 2C 30 40 50 60 70 80 90 MgF2

MgF, (mole %)

Fig. 3.50. The System MngnThF4.

79
3.51. The System LiF-BeF,-ThF,

R. E. Thoma, H. Insley, H. A. Friedman, and C. F. Weaver, ‘‘Phase Equilibria in the Sys-
tems BeF,~ThF, and LiF-BeF,~ThF,,”” paper to be presented at the 136th National Meeting
of the American Chemical Society, Atlantic City, N. J., Sept. 13—-18, 1959.

Invariant Equilibria

Composition of Liquid Invariant

Type of Solids Present
{mole %) T R
emperature Invariant at Invariant Point
LiF BeF, ThF, (°C)
15 83 2 497 t 4 Peritectic ThF4, LiF-AThF4, and BeF2
33.5 64 2.5 455 t 4 Peritectic LiF-4ThF4, LiF-2ThF4, and BeF2
47 51.5 1.5 356 £ 6 Eutectic 2LiF-BeF2, LiF-2ThF4, and BeF,
60.5 36.5 3 433 5 Peritectic LiF-2ThF4, 3LiF-ThF4ss, and
2LiF-BeF
2
65.5 30.5 4 444 T 4 Peritectic LiF, 2LiF<BeF,, and
3LiF-ThF4ss
63 30.5 6.5 448 £ 5 Peritectic 3LiF-ThF4ss, 7LiF-6ThF4, ond
LiF-2ThF
4
UNCLASSIFIED
ORNL-LR-DWG 374204
Th, 4141
TEMPERATURE IN °C
COMPOSITION IN mole To
LIF 4ThE,
7LIF 6ThE——ag , A
3LIF ThF4 sie‘.i 348 LFZThEJ'
433]  LF2ThE
2LF Bt-:F2
LF 6ThE,
P 762
P 597
£ 565
LFThE ¥ X
£ 568
) Ny
%, P % Q
S, O &o X\ £ 526
uF O\/\Q\ N YA =, BeF,
845 2LIF BeF; 5001450 400 400 450 500 548

£ 465 £ 370

Fig. 3.51a, The System LiF-BeF ,—ThF ..

80
Limits of Single-Phase 3LIF-ThF, Solid Solution

Composition (mole %)

LiF BeF, ThF,
75 0 25
58 16 26
59 20 2]

A three-dimensional model of the system LiF-BeF ,~ThF , is shown in Fig. 3.515.

LUNCLASSIFIED

PHOTO 3253]

Fig. 3515. Model of the System LiF—Ber—ThF4.
3.52. The System NaF-ZrF -ThF,

R. E. Thoma, H. Insley, B. S. Landau, H. A. Friedman, and W. R. Grimes, unpublished work
performed at the Oak Ridge National Laboratory, 1956-57.

Preliminary diagram.

Invariant Equilibria

Composition of Liquid

Invariant )
(mole %) Temperature Type of Equilibrium SOI'ds_Presenf
NaF ZrF4 ThE °C) at Invariant Point
77 3 20 645 Peritectic NaF, CL-4N0F-T|1F4, and 3NaF-ZrF4
75.5 2.5 22 618 Eutectic a-4NaF-ThF4, 2NaF-ThF4, and
3NaF-ZrF
4
63 6 31* 683 Decomposition point 3NaF-2ThF4, 2NaF-ThF4, and
of 3NaF-2ThF4 in Na F-ThF‘1
ternary system
65.5 21.5 13 622 Peritectic 2NGF'ThF4, 3NaF-ZrF4, and
NuF-ThF4
65.5 24.5 10 615 Peritectic 3NaF-ZrF4, NaFoThF4, and
CI.-SNc:F-2Zr|:4
64.5 25.5 10 593 Peritectic a-SNuF-2ZrF4, NoF-ThF4, and
NaFozThF4
58 38 4 538 Peritectic a-SNqF-ZZrFA, a-ZNcF-ZrF4, and
thF-2TI'|F4
58 40 2 495 Eutectic /8-2NaF-ZrF4, NaF+2ThF ,, and
7NaF«6Zr F4—3N0F-2ZrF4ss
53 42 4 510 Peritectic NaF-2ThF4, Th(Zr)F4ss , and
INaF.6Zr F4—3N0F-2Th F4ss
49.5 48 2.5 505 Eutectic

7NaF.67Zr F4, 3NcF-4ZrF4, and
Zr(Th) F4 sS

*Approximate composition.

Note: The boundary curve maximum on the Alkemade line 7NaF.6ZrF ,~ThF , is unlikely to

fall exactly on this line, because pure ThF, does not occur along this line. Since ThF, forms

solid solutions with both ZrF, and NaF.2ThF ,, it is not readily determined on which side of

the Alkemade line this maximum occurs.

82
UNCLASSIFIED
ORNL—LR- DWG 20466A

l |
\ TEMPERATURES ARE IN °C
COMPOSITION IN mole Y%

NaF-2ThFs

MINIMUM 870
4NaF - ThFg
- 900
NaF ~ Lt T SO <+ 0o N iy ZrFy
990 S S N8 N a8 5§ b B 5 912
| AN - Pt w | R
7] w . L o o w B ul a .,
[=] L. e . [T
= =] Z [=] =}
"n = o = =
uw) ™~ m

Fig. 3.52, The System NaF—-ZrF ,—ThF ..

83
3.53. The System LiF-UF,

C. J. Barton, V. S. Coleman, L. M. Bratcher, and W. R. Grimes, unpublished work performed
at the Oak Ridge National Laboratory, 1953-54.

Preliminary diagram. The system LiF=UF, contains a single eutectic at 73 LiF-27 UF,
(mole %), m.p. 770°C,

UNCLASSIFIED
ORNL-LR—OWG 2923

1000

950 S

900 ’

800 \Q\ o

750 —0 1

TEMPERATURE (°C)
o
C
—C
o
o}

700

650

600

550

0 10 20 30 40 50 60 70
UF3 (mole %)

Fig. 3.53. The System LiF—UF3.

84
3.54. The System LiF-UF,

C. J. Barton, H. A. Friedman, W. R. Grimes, H. Insley, R. E. Moore, and R. E. Thomaq, ‘‘Phase
Equilibria in the Alkali Fluoride~Uranium Tetrafluoride Fused Salt Systems: 1. The Systems
LiF-UF, and NaF-UF,,”" J. Am. Ceram. Soc. 41, 63-69 (1958).

Invariant Equilibria

Invariant .
Mole % UF4 Temperature Type of Equilibrium Phase Reaction
in Liquid €C) at Invariant Temperature
- 470 Decomposition t‘lLiF-UF4 — LiF + 7LiF-6UF4
26 500 Peritectic LiF+L — 4LiF.UF,
27 490 Eutectic L & 4LiF-UF, + 7LiF-6UF
40 610 Peritectic L+ LiF-4UF4 = 7LiF-6UF4
57 775 Peritectic L + UF, &= LiF.4UF,
UNGLASSIFIED
ORNL —LR-DWG 17457
1100

| |

1000 , /

i
900 : /

800 |—— | —r i /

f
I i

700 : /!
i

N
N

TEMPERATURE (°C)

/ e

500 \/ W v
pd © < |

I
4LIF UF, 3 =
| j ]

400
(s {0 20 30 40 50 60 70 80 Q0 UF,
UF, {mole %)
. Fig. 3.54. The System LiF-UF

85
3.55. The System Naf -UF,

C. J. Barton, V. S. Coleman, T. N. McVay, and W. R, Grimes, unpublished work performed
at the Oak Ridge National Laboratory, 1953-54.

Preliminary diagram.

Invariant Equilibria

Mole % UF,
in Liquid

Invariant

Temperature

(°C)

Type of Equilibrium

Phase Reaction

at Invariant Temperature

27

35

715

775

595

Eutectic

Peritectic

Inversion

L == NoF + a-NaF-UF,
L+ UF3\=‘ a-NaF-UF,

a-NaF-UF, = -NaF-UF,

86
TEMPERATURE (°C)

UNCLASSIFIED
ORNL-LR-DWG 2224R

1100 | | { \ l T
o MIXTURES PREPARED IN SEALED CAPSULES
e MIXTURES PREPARED IN OPEN CRUCBLES | -~
1000 ‘
IN A HELIUM ATMOSPHERE e
\L\ 4 MIXTURES PREPARED IN OPEN /
500 | STIRRER - EQUIPPED CRUCIBLES — 4
" VL
o . c Q
¢ @ i
700 C-STTTrTTTTo AT —a—0—@ S Bt intalintet |
o] [ ] L]
S
0 a p
600 s ; T 8 o] o - o= O o
U_m
-
500 5
400
0 0O 15 20 25 30 35 40 45 50
NaF UFz (mole %)

Fig. 3.55. The System NaF—UF3.

87
3.56. The System NaF-UF

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: |. The Systems
LiF-UF, and NaF-UF ,,”" |. Am. Ceram. Soc. 41, 63-69 (1958).

Invariant Equilibria

Invariant
Mole % UF,  Tqrmoerature Type of Equilibrium Phase Reaction
in Liquid ©c) at Invariant Temperature

21.5 618 Eutectic L Y_T-‘OL-SNaF-UF4 + NaF
25 629 Congruent melting point L & a-3NaF-UF,

- 528 Inversion a-3NaF:UF, == [-3NaF.UF

- 497 Decomposition S-3NaF-UF, == NaF + 2NaF.UF,
28 623 Eutectic L &= a-3NaF-UF, + 2NaF.UF,
32.5 648 Peritectic L + 5NaF-3UF, — 2NaF.UF,
37 673 Peritectic L + 7NaF+6UF , == 5NaF.3UF,

- 630 Decomposition 5NaF:3UF , == 2NaF.UF, + 7NaF:6UF
46.2 718 Congruent melting point L — 7NaF-6UF,
56 680 Eutectic L = 7NaF-6UF, + UF,

- 660 Upper stability limit 7NaF:6UF , + UF , = NaF-2UF,

of NaF-2UF4

88
C)

TEMPERATURE (°

UNCLASSIFIED
ORNL-LR-DWG 19364

1100
1000 f/
900 N /
800 /
700
~7
e
\/
600 - S
5 5| 9] & o
s s 7 @ =
= =z L w Sy
18] o 2 g Llc-)
Te}
=
500 ™
400
NaF 10 20 30 40 50 60 70 80 90 UF,
UFR, {mole %)

Fig. 3.56. The System NaF-UF ,.

89
3.57. The System KF-UF
R. E. Thoma, H. Insley, B. S. Landau, H. A. Friedman, and W. R. Grimes, ‘“Phase Equilibria
in the Alkali Fluoride—Uranium Tetrafluoride Fused Salt Systems: |1l. The Systems KF-UF,
and RbF—UF4," ]. Am. Ceram. Soc. 41, 538-44 (1958).

Invariant Equilibria

90

lnveriant
Mole % UF4 Temperature Type of Equilibrium Phase Reaction
in Liquid °C) at Invariant Temperature
15 735 Eutectic L & KF + 3KF.UF,
25 957 Congruent melting point L= 3K F-UF4
- 608 Decomposition 2KF-UF, == 3KF.UF, + 7KF+6UF,
35 755 Peritectic 3KF.UF, + L. = 2KF-UF,
38.5 740 E utectic L=—2K F-UF, + 7KF-6UF
46.2 789 Congruent melting point L—7K F‘6UF4
54.5 735 Eutectic L & 7KF-6UF, + KF.2UF,
65 765 Peritectic UF, + L &= KF.2UF,
UNCLASSIFIED
ORNL—LR—DWG 28526
1100 [ { { i | r
|
\
|
1000 | L | //
|
_ 7 TN | |
C 900 f ) ; s
Q I |
& / \ % |
= 800 :
~ [/ |
l<_[ T \// \/ \
i e |
a (00 = i}
= ‘ L \
L { '
- | ol
c00 : : L | ]
usr <+ o ‘
D L o |
LL - 1 \
500 f o - < X | ]
| " ¥
N L -
400 | 1
KF 10 20 30 40 20 60 70 80 290 UR,

UF4 {mole %)

Fig. 3.57. The System KF-UF .,
3.58. The System RbF-UF,

R. E. Thoma, H. Insley, B. S. Landay, H. A. Friedman, and W. R. Grimes, ‘‘Phase Equi-

libria in the Alkali Fluoride~Uranium Tetrafluoride Fused Salt Systems:

UF, and RbF-UF,,"" J. Am. Ceram. Soc. 41, 538-44 (1958).

Invariant Equilibria

{l. The Systems KF-

Invariant
Mole % UF4 Temperature Type of Equilibrium Phase Reaction at
in Liquid °C) Invariant Temperature
10 710 Eutectic L —=RbF +3RbF-UF4
25 995 Congruent melting point L— 3RI)F-UF4
38 818 Peritectic L +3Rl:oF~UF4 = 2RbF-UF4
43.5 675 Eutectic L &= 2RbF.UF, + 7RbF-6UF
44 693 Peritectic RbF.UF, + L == 7RbF-6UF ,
50 735 Congruent melting point L ;"\‘RbF-UF4
55 714 Eutectic L ‘-fil-'\’bF-UF“+2RbF-3UF4
56.5 722 Peritectic Rl:F-3UF4+L:ZRbFJUF4
57 730 Peritectic RbF-6UF4+ L= RbF-3UF4
70.5 832 Peritectic UF4 + L —= RbF-6UF4
UNCLASSIFIED
ORNL-LR-DWG 28525
$100 W
1000
— 900 / \ /
O / \
Ll
o 800 A
s ‘ 4
< ~
i 700 A
=
L u™ Yy
~ 600 T I ) > - ny
o - W0 L o >
L W L 2w r ©
21 2 Tl o # W W
500 r+—o r+—5-x ol e
A9)] oJ ™~ o o [0 ot
400 \
RbF 10 20 30 40 50 60 70 80 90 UF4

UFs (mole %)

Fig. 3.58, The System RbF-UF .

91
3.59. The System CsF-UF,

C. J. Barton, L. M. Bratcher, J. P. Blakely, G. J. Nessle, and W. R. Grimes, unpublished

work performed at the Oak Ridge National Laboratory, 1951-53.

Preliminary diagram.

Invariant Equilibria

Invariant
Mole % UF4 Temperature Type of Equilibrium Phase Reaction
in Ligquid ©C) at Invariant Temperature
7.5 650 Eutectic L. —=CsF + 3Cs F-UF4
25 970 Congruent melting point L ——= 3Cs F-UF4
34 800 Peritectic L+ 3(.:s.F"-UF4 —— 2Cs F.-UF,
41 695 Eutectic L \——2C5;F-UF4 +cl-CsF-UF4
50 735 Congruent melting point L— Cl,-CsF-UF4
- 550 Inversion a-CsF-UF, &= [(-CsF-UF,
53 725 Eutectic L #Q-CsF-UF“ + UF,
UNCLASSIFIED
1100 ORNL-LR-DWG. 18915
! } ] ! | ! ] 1 '
1000 |— —
900 — -
e
w 800 — —
g
.—
L9
x
o
2700 ]
.—
600 — -
- u¥
500 [— 5 > —]
5|4 :
voo | ! ! | | | | |
CsF 10 20 30 40 50 60 70 80 90 UF,

uf, (mole %)

Fig. 359. The System CsF—UF4.

92
3.60. The System ZrF ,.UF,
C. J. Barton, W. R. Grimes, H. Insley, R. E. Moore, and R. E. Thoma, ‘‘Phase Equilibria
in the Systems NaF-ZrF ,, UF ,~ZrF ,, and NaF-ZrF,~UF ' J. Phys. Chem. 62, 665-76 (1958).
The system ZrF ,~UF , forms a continuous series of solid solutions having a minimum melting

temperature of 765°C at 77 ZrF ,-23 UF, (mole %).

TEMPERATURE (°C)

1050

1000

950

300

850

800

750

700

UNCLASSIFIED
ORNL—LR—DWG 19887

A LIQUIDUS POINTS FROM THERMAL GRADIENT QUENCHING EXPERIMENTS
\ @® SOLIDUS POINTS FROM THERMAL GRADIENT QUENCHING EXPERIMENTS
\ \\ ‘I/
® -
& \ \ A
'y
\' \
\ ™.
\ ‘
[ ] \t\ y
r"'"—.J
UF4 1Q 20 30 40 50 60 70 80 90 ZrF,

Zr&_(mde%fl

Fig. 3.60. The System ZrF 4—UF4.

93
3.61.

(July 1959).

The System SnF,-UF,
B. J. Thamer and G. E. Meadows,

Invariant Equilibria

The Systems UF4—SnF2 and PuF ;—-SnF ),

LA-2286

Invariant
Mole % UF4 Temperature Type of Equilibrium Phase Reaction
in Liquid ©c) at Invariant Temperature
0.5 212 Eutectic L= .."ml:2 + 2SnF2-UF4
4.5 340 Peritectic L+ San-UF4 p—— 2SnF2'UF4
7.8 371 Peritectic L + UF, = SnF,UF,
UNCLASSIFIED
ORNL—LR— DWG 36864
1400
1000 - /
900 //
800 //
/ 450 l ‘
400 -~ ]
700 Ve LL /
(3 — a7 A
-~ [®) Pl
— P 350 —A
[0 ul AT
2 600 E 300 PR A SOLUBILITIES BY FILTRATION ]
= / & v A LiQUIDUS POINTS FROM DTA
& i / HEATING CURVES
z 2 250 b ¥ LIQUIDUS POINTS FROM DTA
== - L /‘ COOLING CURVES
A
500 200 [ - N
150
/ 0 " 2 3 a4 5 6 7 8 9 10
400 UR, (mole %) ]
| | |
300 /
200
u us
o )
L;_N o
[ =
oy
o
100
SnF2 10 20 30 40 50 60 70 80 90 UE‘
UF4 (mole 079)

94

Fig. 361. The System SnF ,—-UF .
. 3.62. The System PbF,..UF,

C. J. Barton, L. M. Bratcher, J. P. Blakely, G. J. Nessle, and W. R. Grimes, unpublished
work performed at the Qak Ridge National Laboratory, 1950-~51.

Preliminary diagram,

Invariant Equilibria

Invariant _
Mole % UF4 Temperature Type of Equilibrium Phase Reaction
in Liquid €c) at invariant Temperature
14.3 920 Congruent melting point L 6PbF2-UF-'4
35 835 Eutectic L :_6|:’13F2‘UF4+3F’|:>F2-2U|':4
40 840 Congruent melting point L = 3PbF,-2UF,
62 762 £ 10 Eutectic L \-fi3PbF2'2UF4+ Ul‘:4

The eutectic at quite high PbF, concentrations is not shown on this diagram. The authors

examined thermal data but found no evidence of a eutectic thermal effect.

TEMPERATURE (°C)

1050

UNCLASSIFIED
DWG14633R

1000 [—

950 —

9200 —

850 [—

800 —

750 —

700

6 PbF, - UF,

f f

3PbF,- 2UF,

30

40 50

UF, (mole %)

60 70 80 90 UR,

95
3.63. The System ThF4—UF4

C. F. Weaver, R. E. Thoma, H. A, Friedman, and H. Insley, ‘‘Phase Equilibria in the Systems
UF ,~ThF, and LiF-ThF ,~UF ,,”" paper presented at the 61st National Meeting of the American
Ceramic Society, Chicago, Ill., May 17=21, 1959,

The system ThF ,~UF, forms a continuous series of solid solutions without a minimum.

96
TEMPERATURE (°C)

1200

LUNCLASSIFIED
ORNL-LR-DWG 27913

1100 P

1000

‘—YL:::: _____ —m==t==== + ===

IQUID + Th¥F, -UF, SOLID SOLUTION

\

300

800

Th,—UF, SOLID SOLUTION

]

20 30 40 50 60 70 80 Q20 UF,
UF, {mole %)

Fig. 363. The System ThF ,-UF

97
3.64. The System LiF-NaF-UF,

R. E. Thoma, H. Insley, B. S. Laondau, H. A. Friedman, and W. R. Grimes, ‘‘Phase Equilibria
in the Alkali Fluoride=Uranium Tetrafluoride Fused Salt Systems: Ill. The System NaF-LiF-~
UF,,'" J. Am. Ceram. Soc. 42, 21-26 (1959).

Invariant Equilibria

Composition of Liquid

invariant

(mole %) Temperature - T)tpl ?f Solid IPhas'es P:s.ent

NoF L UF4 c) quilibrium at Invariant Point

60 21 19 480 Eutectic 2NaF-UF4, NaF, and LiF

65 13 22 497 Peritectic 5-3N0F~UF4, 2NaF-UF4, and NaoF

7 65.5 27.5 470 Peritectic 7LiF-6UF4ss,* 4LiF.UF,, and LiF
35 37 28 480 Eutectic 2NaF-UF4, 7NaF-6UF4ss, and LiF

57 13 30 630 Peritectic 2NaF-UF ,, 5NaF-3UF4, and 7NaF-6UF4ss
24.3 43.5 32.2 445 Eutectic 7NaF-6UF4ss, LiF, and 7LiF-6UF4ss
24,5 29 46.5 602 Eutectic NaF-2UF4, 7LiF-6UF4ss, and 7NaF-6UF4ss
24.3 28.7 47 605 Peritectic NaF-2UF4, LiF-4UF4, and 7LiF-6UF455
23.5 28 48.5 640 Peritectic UF4, NaF-2UF4, and LiF.-4UF,

37.5 10.5 52 660 Peritectic

UF4, NaF-QUF4, and 7N0F-6UF4ss

*The compounds 7LiF-6UF4 and 7Nc:F-6UF4 as they occur in the ternary system are members of the solid
solution 7LiF-6UF4—-7NuF-6UF4.

98
UNCLASSIFIED
ORNL—LR—DWG 28244R

COMPOSITION IN mole %
TEMPERATURE IN °C

TNaf - 6UF,

P&73
. 2NaF - UF, —

PEAS /e,

£623 ‘\
) 3NGEF6.4:F4‘ \

850
950 900
VAN
NaF
990

Fig. 3.64a, The System LiF-NaF-UF .

99
TEMPERATURE (°C)

100

UNCLASSIFIED

255 ORNL-LR—DWG 2979
\
\
700
\
|
\ LIQUID
675 \\
\ o
650 \ =
\ \ S
\ +
: LiF+ 4UF
\ 7NGF+6UF, ss L + LIouiD
625 ! + LIQUID L f’o
\ w
\ —
™~
a l ———
T e
600 — 3 1 \
K , l LiF+4UF, +
Zo ' l 7L|F-6UF4 SS
~ , | + LIQUID
7 NoF'GUF4 5S
] ; l.
913 | 7LiF- 6UF, ss |
' 4 l ?L:F-GUQ ss
| |
|
550 l |
7NaF «6UF, 10 20 30 40

LiF {mole %)

Fig. 3.645. The Join 7NaF.6U F4—7LiF-6UF4.

50 7L||'-'-6UF4
3.65. The System LiF-KF-UF,

C. J. Barton, J. P. Blakely, L. M. Bratcher, and W. R. Grimes, unpublished work performed
at the Oak Ridge National Laboratory, 1950~51.

Preliminary diagram. The system LiF~KF-UF, 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.

UNCLASSIFIED

ORNL—LR~DWG 28633R

UF, 1035
1000

TEMPERATURE (°C) 950 —LiF 4UFf,

COMPOSITION (mole %)

900
KF 2UFf,— 850
P 765 800

A 750 A

-P 775
70
E735- © ot
650 Al =
7KF GUFq— —-7TLIF GUF4 'A
600
—P 810
E740- 199 550 S
700 ~ ‘
P 7674 -
2KF UF, N a5, ™ 650 P .
600 Q0=

LiF 845

Fig. 365, The System LiF—KF--UF4.

101
3.66. The System LiF-RbF-UF,

C. J. Barton, J. P. Blakely, L. M. Bratcher, and W. R. Grimes, unpublished work performed
at the Oak Ridge National Laboratory, 1950-51.

Preliminary diagram. Phase relationships within the system LiF-RbF-UF, have not yet

become so well defined at the Oak Ridge National Laboratory that the compositions and tem-
peratures of the invariant points may be listed.

UNCLASSIFIED
ORNL-LR~0OWG 28634R

UF, 1035
S 10002
RbF SUF, _
TEMPERATURE IN °C
COMPOSITION IN mole 7o 950 \- LIF 4UF,
900
P-832
850
2RbF 3UF, _ BOO
7
P-730 _ -
p-722 750 P77s
E-714 700 &
RbF UF, -

Q
7RbF 6UF, - - TLF GUF,
P-693 A& 600 R
E-6757%
A \- P 610
P-818-
550
A N
2RbF UF, - 550 500 N

600
58 Q_£490
3RbF UF, - 700 650

- P500
750 L
950 lele) y - 4LIF UF,
300 850 700
‘ 750 =
E-710 -
r 800
750 _ £-450
RbF N AV, RV AN RV LLIFEJ
790 E-470 8

Fig. 366, The System LiF-RLF-UF .

102
3.67. The System NaF-KF-UF
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 NaF-KF-UF, have not yet
become so well defined at the Oak Ridge National Laboratory that the compositions and tem-

peratures of the invariant points may be listed.

UNCLASSIFIED
ORNL—LR-DWG 38112

UF, 1035
THIS DIAGRAM HAS BEEN DERIVED ENTIRELY
FROM TA DATA

COMPOSITION IN mole %
TEMPERATURE IN °C
* NoF KF UF,

‘A, 4 2 F
2NGF UF, T L , -
Peag A - /550 ‘\\ P /@Q © 4

£623 /X &\ G of o0 4
3NaF Ufy ™/ 3KF Uy
£ 648 = 0

faum = 700 900—2

£ 710 856

Fig. 3.67. The System NaF-KF-UF .

103
3.68. The System NoF -RbF-UF,

R. E. Thoma, H. Insley, H. A. Friedman, and W. R, Grimes, unpublished work performed at
the Oak Ridge National Laboratory, 1955=56.

Preliminary diagram.

Invariont Equilibria

Composition of Liquid

Invariant

(mole %) Temporature ETYTTZ crf Solidl Pha?es F';re.sem

oF e oF, C) quilibrium at Invariant Point

18 73 9 670 Eutectic RbF, NaF, and 3RbF-Ul’-‘4

46 33 21 470 Eutectic NaF, NaF-RbF-UFd, and BI%F-UF4

44 33 23 500 Peritectic NqF-RbF-UFd, 2RbF-UF4, and .'SRbF-UF4
45 30 25 485 Peritectic NaF, 2NaF-UF4, and Nc:F-RbF-UF4

52 23 25 500 Decomposition 3NaF-UF4, NaF, and 2NaF-UF4

41 26 33 555 Peritectic 2RbF.UF4, 2NaF-UF4, and N.,F.RbF.UF4
57 8 35 630 Decomposition 2NaF-UF4, 5NaF-3UF4, and 7NuF-6UF4
33 30 37 535 Eutectic 2RbF-UF4, 2NaF-UF4, and ‘/'RbF-éUF4
32 29 39 340 Peritectic 7RbF-6UF4, 2NoF-UF4, and 7N<:F-¢5UF4
26 27 47 620 Eutectic 7RbF-6UF4, 7NqF-6UF4, and RbF-UF4
25 25 50 630 Eutectic 7NcF-6UF4, RbF-UF4, and 2RbF-3UF4
27 22 51 633 Peritectic 7NaF-6UF4, 2RbF-3UF4, and RI:F-BUF4
33 14 53 655 Peritectic 7NaF~6UF4, RbF-3UF4, and RbF-6UF4
42 3 55 678 Peritectic

7NqF-6UF4, RbF-éUFA, and UF,

104
{000

900

800

TEMPERATURE (°C)
-~
@]
(@]

600

500

400

TEMPERATURES ARE
IN DEGREES CENTIGRADE

COMPOSITIONS
IN MOLE PERCENT

7NF BUF,

SNaF_3UF,
673

UNCLASS FIED

ORNL LR DWG 1674(AR

RGF BUF,

.

NoF 2UF, b 800

RGF UF,
_‘« TROF GUFq

——
= e\ 93

2

To

Fig. 3.68a, The System NaF-RbF-UF ,.

RbF
a0

UNCLASSIFIED
ORNL~-LR—DWG {7665R

3RbF - UF, + LIQUID

5NaF-3UF, + LIQUID
"-./ 4

— 2 NeF - UF, m}~\/

/

2RbF -UF, + LIQUID

Fig. 3.68b. The Section 2NaF-UF4—2RbF-UF4.

2NoF - UF, + 2RbF - UF,
& +
uY W %
E 2NoF UF +Naf RbF Uf, 5 Naf - RbF - UF, + 2RbF - UF,
L e 4 %
2 5 X
o z ‘ o
0 10 20 30 40 50 60 667
RbF {moie %)

105
106

TEMPERATURE {C)

UNCLASSIFIED

ORNL LR DWG 417666

650

600

/
550 /
2NaF  UF,
2RbF UF4 + LIQUID + 2RbF  UF,
/ + L QUID
N
NoF + LiQUID G L@
ast
500 \ / wof |
- 2NaF UF4 + NaF RbF UF,; + LIQUID
NaF + 2NoF  UF, oNaF UFat LIQUID 4 4
+ LIQUID
Iy
2
NaF + NoF RbF UF, E
w
2
450
55 50 45 40 35

NaF (mole %)

Fig. 3.68c. The Section NaF-NaF«RbF:UF ,,

30
TEMPERATURE {°C)

UNCLASSIFIED

ORNL-LR-DWG 17667R

1000 N
//———'—
SO0 / [
/ 3RbF - UF, + LIQUID
800 7 N

700 //x
A

600

Z2RbF UF, + LIQUID

uE

/2RbF UF; + 2NoF UF; + LIQUID

~

l
500 NaF _RDF UFs * 2RbF UFs + LIQUID
uwr NaF ROF UF, + 3RbF UFy + LIQUID .
! 3 '
- ’ B
Es]
e u.
" NoF RbF UF, + 3RbF UF, 8
2 l | -
400
333 35 40 45 50 55 60 65 70 75
RoF {male % )

Fig. 3.684. The Section 3RbF-UF4—NuF0RbF-UF4.

107

3.69. The System LiF—BeF,-UF,

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 LiF-BeF ,—UF  Ternary Fused Salt
System, MLM-1080 (Aug. 24, 1959).

UNCLASSIFIED
MOUND LAB NO
1035 56-41-29 (REV)

UFy

ALL TEMPERATURES ARE IN °C

£ = EUTECTIC
F = PERITECTIC LIF‘4UF4
UF,| = PRIMARY PHASE FIELD
£
P
4LIF-UF, '\

Fig. 3.69a. The System LiF-BeF ,—UF ..

108

Preliminary diagram.

Invariant E quilibria

Composition of Liquid

Temperature Solid Phases Present
(mole %) (°C) Type of Equilibrium

at Invariant Temperature

LiF BeF2 UF4

72 6 22 480 Peritectic (decomposition 4L'|F-UF4, LiF, and 7LiF-6UF4
of 4LiF-UF4 in the

ternary system)

69 23 8 426 Eutectic LiF, 2LiF-BeF2, and 7LiF-6UF4

48 51.5 0.5 350 Eutectic 7LiF-6UF4, 2LiF-BeF2, and BeF2
45.5 54 0.5 381 Peritectic LiF-4UF4, 7LiF-6UF4, and BeF2

29.5 70 0.5 483 Peritectic UF4, I_iF-4UF4, and Be F2

The minimum temperature in the quasi-binary system 2Lil'-'»E'>eF2—7LiF-6UF4 occurs at 65
LiF-29 BeF -6 UF, (mole %) at 438°C.

A three-dimensional model of the system LiF-BeF ,-UF, is shown in Fig. 3.695.

UNCLASSIFIED
PHOTO 24247

Fig. 3.695. Model of the System LiF—BeF o—UF 4

109
3.70. The System NaF=BeF,=UF,
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, 1956~57.

Preliminary diagram.

invariant Equilibria

Composition of

. Temperature Solid Phases Present at
Liquid (mole %) ey
ec) Type of Equilibrium Invariant Temperature
NaF BeF2 UF4
74 12 14 500 Peritectic (decomposition of 3NaF-UF4, NaF, and ZNOF-UF4
3Nc|F-UF4 in ternary sys-
tem)
72.5 17 19.5 486 Eutectic NaF, 2NaF-UF4, and 2N&:|F-Be|:2
64.5 9 26.5 630 Peritectic (decomposition of 5N0F-3UF4, 2NuF-UF4, and 7NaF-6UF4
5Nc:F-3UF4 in the ternary
system)
57 42 1 378 Peritectic 2NaF-BeF2, 2N0F-UF4, and 7NaF-6UF4
56 43.5 0.5 339 Eutectic 2NaF-BeF2, NuF-BeF2, and 'I'Nc:F-6UF4
43.5 55.5 1 357 Eutectic 7NaF-6UF4, BeF,, and NaF-BeF,
41 58 1 375 Peritectic 7NaF-6UF4, NaF-ZUF4, and BeF2
26 63 1 409 Peritectic NuF-2UF4, NuF-4UF4, and BeF,
44 18 38 665 Peritectic 7NaF-6UF ,, UF,, and NaF.2UF,
40 47 13 548 Peritectic UF4, NuF-2UF4, and NaF-4UF
27 72 1 498 Peritectic UF4, BeF,, and NaF-4UF4

The minimum temperature in the quasi-binary system 2NaF.BeF,—~2NaF.UF, occurs at 66.7
LiF-25 BeF,-8.3 UF, (mole %) at 528°C. The minimum temperature in the quasi-binary system
NaF.BeF ,~7NaF.6UF, occurs at 50.5 NaF-48.5 BeF,~1.0 UF, (mole %) at 367°C.

A three-dimensional model of the system NaF-BeF,-UF, has been constructed by the
authors and is shown in Fig. 3.705.

110
UNCLASSIFIED
MOUND LAB NO

56—11-30 (REV}

UF,

ALL TEMPERATURES ARE IN °C

m
i

= EUTECTIC
P = PERITECTIC
= PRIMARY PHASE FIELD

7 NaF 6UF, ‘

5NaF 3UF,
5NaF 3UF, P
2 NaF UF4/"'I‘
/
P

3NaF UF,

3NaF UF, [~ 2L
N

7 NoF su

- N
TS Y RN
V. = NN W

b~ | A4 Av4
/ £ \ £ BeF,
2 NaF BeF, NaF BeF,

Fig. 3.70a. The System NuF—Ber—UF4.

1M1
oy
W
TP
%4
<2
Ho
Or
Za
)

~BeF

Model of the System NaF

& 706.

g

F

112
3.71. The System NaF -PbF ,—UF,

C. J. Barton, J. P. Blakely, G. J. Nessle, L. M. Bratcher, and W. R. Grimes, unpublished
work performed at the Oak Ridge National Laboratory, 1950-51.

Preliminary diagram. No study has been made at the Oak Ridge National Laboratory of the
phase relationships within the system NaF-PbF ,~UF .

UNCLASSIFIED
ORNL—LR~DWG 20455R

1035

TEMPERATURE IN °C
COMPOSITION IN mole T

NoF-2UF,

7NaF - 8UF,

5NaF- 3UF,
2NaF-UF, 650 /

3NaF-UF, 4 / /

£ L, i \
AN /] 2N .
NaF / Wd‘%\ \ \\ Gé‘o S0p.\ 550 ‘

kY, ~ Y *%0

290 815

Fig. 3.71. The System NaF-PbF,-UF

113
3.72. The system KF~PbF_-UF,

C. J. Barton, J. P, Blakely, G. J. Nessle, L.. M. Bratcher, and W. R. Grimes, unpublished
work performed at the Oak Ridge National Laboratory, 1950-51.

Preliminary diagram. No study has been made at the Oak Ridge National Laboratory of the
phase relationships within the system KF—PbF ,-UF ,.

114
UNCLASSIFIED

OWG 115144
UF,
1035
TEMPERATURE IN °C
COMPOSITION IN mole % 800
~Q
850
L 800 A
KF 2UF, ¢
&
7
2 %0 h
7KF BUF, ¢ !
X 3PbF, 2UF,
A 840
2KF UF, g
AN
3KF UF4 g \
X 6PbF, UF,

210

Fig. 372. The System KF-PbF,-UF ..

115
3.73. The System NaF-ZrF4-—-UF4
C. J. Barten, W. R. Grimes, H. Insley, R. E. Moore, and R. E. Thoma, “Phase Equilibria

in the Systems NaF—ZrF4, UF4-ZrF4, and NaF-ZrF4-UF4,” J. Pbys. Chem. 62, 665~-76 (1958).

UNCLASSIFIED
ORNL—LR—DWG 19886R

ALL TEMPERATURES ARE IN °C

TAN
A /\
NcF-2UF—'4
A
{\ )Y
A
7NaF-6UF, ‘Q

5NaF-3UF,
A
2NaF-UF, 800
/\ ‘ 750
3NoF-UF, ll
/V 765
750 \? \
800 A
850 AU\ 675 50
900 Al 3 600 700 BOO VA
950 \ W 650 850
\ ‘ \m . 900
NoF : VA MW AL, U\ Irfy
990 3NaF-Zrf, fl 3NaF-2Zrf, 3NaF-4Zrf, 942
5NaF.2 ZrF

4 PNaF-ZrF

a 7NaF-6Zrfy

NaF+ZrF,

Fig. 3.73a. The System NoF -ZrF ,~UF .,

116
Invariant Equilibria and Singular Points

Composition of Liquid

(mole %) Temperature T ¢ Ecuilibei Solids Present
(°C) ype of Lquilibrium at Invariant Point
NaF ZrF4 UF4
69.5 4.0 26.5 646 Maximum temperature 3Nc1F-(U,Zr)F4 and 2Na I:-UF4
of boundary curve
68.5 5.5 26.0 640 Peritectic 3NaF-(U,Zr)F4, 2NaF-UF4,
and 5NoF-3UF4ss
65.5 12.0 22.5 613 Peritectic or SNGF-(U,Zr)FA, 5NoF-3UF4ss,
decomposition and 7NuF-6(U,Zr)F4
64.0 27.0 2.0 592 Peritectic 3Na F-(U,Zr)F4, SNaF:2Zr F4ss,
and 7Nc1F-6(U,Zr)F4
61.5 34.5 4.0 540 Peritectic 5NaF-2ZrF4ss, ZNGF-ZrFA,
and 7NaF-6(U,Zr)F4
50.5 47 2.5 513 Peritectic 7Na F-6(U,Zr)F4, (U, Zr)F4,
and 3N¢:|F-¢IZrF4
UNGLASSIFIED
850 ORNL—LR—DWG 19888
.
800 /t//
750 - //
= A
£ 700 /
‘E'c-’ /
]
q
: P e
i 650 < e -
E ‘ . A .El I
600 A LIQUIDUS POINTS FROM THERMAL GRADIENT QUENCHING EXPERIMENTS -——
® SOLIDUS POINTS FROM THERMAL GRADIENT QUENCHING EXPERIMENTS
B LIQUIDUS POINTS FROM THERMAL ANALYSIS
A INITIAL COMPOSITION OF FILTRATION MIXTURES
O FILTRATION RESIDUE COMPOSITIONS
550 © FILTRATE COMPOSITIONS -
500
3NaF+UF, 5 10 15 20 3NaFZrF,

Zrf, (mole %)

Fig, 3735, The Subsystem 3NaF'UF4—3NuF-ZrF4.

117
UNCLASSIFIED
ORNL -LR-OWG 176694

800

750

"
650 ,/ / /
_—]

TEMPERATURE (°C)

co0 = /

550 ///// )

500

TNoF- 62rF, 10 20 30 40 50 60 70 80 90  7Naf-6UF,

7NoF - 6UF, (mole %)

Fig. 3.73¢c. The Subsystem 7NaF6ZrF ;~7NaF+6UF .

118
3.74. The System LiF—ThF4-UF4
C. F. Weaver, R. E. Thoma, H. Insley, and H. A. Friedman, *‘Phase Equilibria in the Systems

UF ,~ThF, and LiF-ThF ,~UF,,”” paper presented at the 61st National Meeting of the American
Ceramic Society, Chicago, ill., May 17-21, 1959.

Invariant Equilibria

Composition of Liquid Invariant

(mole %) Temperature  1YPe ©f Solids Present at Invariant Point
LiF ThF4 UFA (°c) Equilibrium
72.5 7.0 20.5 500 Peritectic  LiF, 3LiF+(Th,U)F ,, and 7LiF-6(U, Th)F
72.0 1.5 265 488 Evtectic  LiF, 4LiF-UF,, and 7LiF-6(U, Th)F,
53 18 19 609 Peritectic  7LiF-6(U, Th)F ,, LiF-2(Th,U)F ,, and LiF-4(U, Th)F,

A three-dimensional model of the system LiF-ThF ,~UF , is shown in Fig. 3.74e.

ThF,
MM UNCLASSIFIED
ORNL-IL.R-DWG 28215AR2
PRIMARY-PHASE AREAS
TEMPERATURE IN °C
{a) UF,~ThE, (ss)
COMPOSITION IN mole o
¢ (b) LiF- 4UF LIF 4ThE, (ss)
(c) LiF 2Th UIF, (ss)
LIE 4ThE (d) 7LIF BUF,~7LIF 6ThF, (ss)
4 (€) 3LIF Th{UIF, (ss)
(f) LF
LiF 2ThE,
P 897 AN
A
(@)
A B
7,
7TLIF 6ThE, OOO
P 762 S,
A % \
K}
®
o (a) \
P 597 & % '
£ 565
3LIF ThE,
£ 568
A PGO
’c‘a
o % Q
Alf) ‘%5 AN\
3 B /3500
2 \\
LIF (\) W \ \ i\ \61-488 by \/ UF4
845 auF uFy” P500" £430 P 610 \ P 775 LIF 4UF, 1035
TLIF BUF,

Fig. 3.74a, The System LiF-ThF ,~UF .

119
120

TEMPERATURE (°C)

575

550

525

500

475

450

UNCLASSIFIED
ORNL-LR-DWG 35503R

LIQUID + 3LiF - ThF, ss

LiF + LIQUID

LiF+ 3LiF« ThF, ss + LIQUID

LiIF+7LiF -6ThF, —7LIF-6UF, ss + LIQUID
4LiF-UR + LIQUID + LIF

4LiF-UR + LIQUID

4LiF-UR +7LiF-6ThE —7LIF-6UFR ss + LIQUID
3LiF - ThF, ss

3LIF - ThF, ss + 7LiF - 6Thk, = 7LIF - 6 UFy ss + LiF
LiF + 7LiF - 6 ThF,— 7LiF - 6 UF4 ss

LiF + 4LiF -UF, + 7LIF -6 ThF, —7LIF - 6 UF,; ss

4 LIF «UF, + 7LiF - 6 ThF, ~ TLiF - 6 UF, 55

—
A THERMAL DATA
® QUENCH DATA
O TIE LINE DATA

(@)

LIQUID

10 15 20 25
UF, (mole %)

Fig. 3.74b, The System LiF-ThF ,—UF ,;: The Section at 75 Mole % LiF.
TEMPERATURE {°C)

850

800

750

700

650

600

550

UNCLASSIFIED
ORNL-LR-DWG 27917

UF, (mole %)

] ! ‘
| I
LIQUID
\‘\\‘ ‘
AN »
Q‘\ 2
NN
NN LIQUID + LiF - 4ThF,— LIF 4UF,
N SOLID SOLUTION — ™
~
LIQUID +LiF-2ThF, |\ \\ ‘ \[q
SOLID SOLUTION N r
NN |
O N\t LQUID + LIF- TR, - LF - 4UF, SOLID SOLUTION +
K )( LiF - 2ThF, SOLID SOLUTION
N S N S SR N
P’— __\_______ —_— T _____L———T———'
LIQUID + LiF - 2ThF, SOLID SOLUTION + (uomo + LiF - 4ThF, — LiF - 4UF, SOLID SOLUTION
7LIF 6ThF, — 7LiF - 6UF, SOLID SOLUTION + 7LIF - 6ThF, — 7LiF - 6UF, SOLID SOLUTION
7LIF-6ThF, — 7LIF - 6UF, SOLID SOLUTION
0 5 10 5 20 25 30 35 40 a5

Fig. 3.74c. The System LiF-ThF ;~UF ;: The Section at 53.8 Mole % LiF,

121
UNCLASSIFIED
ORNL-LR-DWG 35506R

(@) UFa—ThF, ss + LIQUID

() LIF-4UF,— LIF: 4ThF+ LIQUID

(¢) UF,—ThF, ss + LIQUID + LiF - 4UF, —LiF - 4ThF, ss

(d) LIF-2ThF, ss + LIQUID + LIF- 4UF, — LIF - 4ThF, ss

() LiIF- 4UF, ~LiF- 4ThF, ss + LIQUID + 7LIF- 6 UF, — 7LIF - 6ThF, ss

(F) LIF-2ThF,ss

(g) LIF- 4UFy~LIF- 4ThFs ss + 7LIF-6UF4—7LiF -6ThFass

(#) LiF- 4UF, —LIF-4ThF, ss + 7LIF-6UF, —7LiF - 6 ThF, ss +LIF - 2ThF, ss

1100 ‘
A THERMAL BREAKS
® QUENCH RESULTS
O TJIE LINE INTERSECTION
1000
(@ 7 T~ (&)
LIQUID (6) ‘

900
E)
o
wl
o
D
5 800 |
Vel
&
= 2
—
700 l
800 4 ]
_\(8) |
(g}
500
30 40 50 60 66 2/3

UF, {(mole %)

Fig. 3.74d. The System LiF-ThF ,~UF ;: The Section at 33.3 Mole % LiF,

122

r-

UNCLASSIFIED
_PHOTO 34246

H
+
£
¥
3
)
LIF-
=
7
5
£
&

Fig. 3.74¢c. Model of the System LiF-—ThF4—UF4.

123

v

3.75. The System NaF~ThF,~UF : The Section 2NaF-ThF ;=2NaF.UF
R. E. Thoma, H. Insley, H. A. Friedman, and C. F. Weaver, unpublished work performed at
the Oak Ridge National Laboratory, 1958-59.

Preliminary diagram.

UNCLASSIFIED
ORNL-LR-DWG 34986

725 !

/BZ—- 2NaF - Thi, + LIQUID

700 P~ - 5-2NaF UThF,
f M SOLUTION AND LIQUID
|
— SNaF - 3UF,
675 \‘\, —~ AW LIQUID\
650 \\\ =
625 \

T

I
5NaF - 3UF,
+8 -2NaF - U(ThiF
\ AND LIQUID
B, 2NaF - Th(U)F, \ \
600 (— +8-2NaF -U(ThF, /\'

TEMPERATURE (°C)

SOLID SOLUTIONS

575 \\
550
SOLID SOLUTION

SOLID SOLUTION

\\ 5 - 2NaF - U{ThiF,

525 ‘
500
2NaF - ThF, 5 10 15 20 25 30 2NaF-UF,

UF4 {rmole %}

Fig. 3.75. The Section ZNoFOThF4—2NqF°UF4.

124
3.76. The System LiF-PuF,

C. J. Barton and R. A. Strehlow, ‘‘Phase Relationships in the System Lithium Fluoride—
Plutonium Fluoride,’’ paper presented at the 135th National Meeting of the American Chemical
Society, Boston, Mass., Apr. 5-10, 1959.

The system LiF-PuF, contains a single eutectic at 80.5 LiF~19.5 PuF; (mole %), m.p.
743°C.

UNCLASSIFIED
ORNL-LR—DWG 34847

|
1425°C
1400 >~

”
”

TEMPERATURE (°C)
S
@)
N
\

PuF3 (mole %)

Fig., 3.76. The System LiF-PuF .,

125
3.77. The System LiCl=FeCl,
C. Beusman, Activities in the KCI-FeCl, and LiCl-FeCl, Systems, ORNL-2323 (May 15,
1957).

The system LiCl-FeCl, forms a continuous series of solid solutions with a minimum at 60

LiCl—-40 FeCl, (mole %), m.p. 540°C.

UNCLASSIFIED

ORNL-LR-DWG. 20942
700

T | |

08 600
wh
@
>
.—
z
w500 — —
a
=
1Y)
-

400 |- —

300 i | | | ] ] | | |

o] {e] 20 30 40 50 60 70 80 30 100

MOLE % FeCl,

Fig. 3.77. The System LiCl-FeCl,,

126
3.78. The System KCI-FeCl,

C. Beusman, Activities in the KCl-—FeC12 and LiCl-FeCl, Systems, ORNL-2323 (May 15,
1957). Anearly 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,’” J. Am. Chem. Soc.

79, 6149-50 (1957).

Invariant E quilibria

Invariant _
Mole % FeC|2 Temperature Type of Equilibrium Phase Reaction
in Liquid C) at Invariant Temperature
35 385 Peritectic L+KCl—= a-2KCl-FeCl,
- 255 Inversion a-2KCl-FeCl, :fiQKCI-FeCIz
39 355 Eutectic L ‘:\a-2KC!-FeC|2+a-KC|-FeC|2
50 400 Congruent melting point L= C(.-KCI-FeCl2
- 300 Inversion a-KCl+FeCl, == 3-KCI-FeCl,
53 390 Eutectic L \-T\-«-—G.-KChFeCiz + FeCl2
UNCLASSIFIED
ORNL-LR-DWG. 20940R
800

700

600
e)
Qe
w
g
2500
<
o
i
a
=
Lot
’-—.

400

e A
® [ ] hd v 3850 390° L ] L J
Y
L K ]
356  ® e Kol-FeCl,
2KCI- FeCl,—=—
300 PO ) hd ?eo - —
. - L] '] S _lo *—eo-
0O IO 20 30 40 50 60 70 80 a0 100

MOLE % FeCl,

Fig. 3.78. The System KCl-—FeCIz.

127
3.79. The System NaCl~Z(Cl,
C. J. Barton, R. J. Sheil, and W. R. Grimes, unpublished work performed at the Oak Ridge

National Laboratory, 1956.

Preliminary diagram,

Invariant Equilibria

Invariant
Mole % ZrCl4
in Liquid Temperature Type of Equilibrium Phase Reaction at Invariant Temperature
(°C)
28.0 535 %5 Peritectic L + NaClI F‘:'_."“ 3Na Cl'ZrCl4
- 44515 De composition 3INa Cl'ZrCI4 = NaCl + C\’.-2Na(.':l'Zr('_:|4
28.5 525t5 Eutectic I..='13N4::CI°ZrC|4 + a-2NaC|'ZrC|4
33.3 626 + 5 Congruent melting point L &= a-2NaCl*ZrCl,
~ 370 5 Inversion @-2NaCl+ZrCl ;==/5-2NaCI+ZCl ,
58 3525 Peritectic L + B-2NaCl+ZrCl , &= a.-3NaCl4ZrCl ,
- 31215 Inversion a-3NaCl+4ZrCl , T===/3-3NaCl*4Z:Cl
63 3125 Eutectic L .\:"“-,8-3N0CI°4ZrCI4 + ZeCl,

Previous reports on the system Nc:CI-ZrCI4 have been made by N. A. Berlozerskts and O. A.
Kucherenko, Zhur. Priklad., Kbhim. 13, 1552 (1940), |. S. Morozov and B. G. Korshunov, Zhur.
Neorg. Kbhim. 1, 145(1956), and H. H. Kellogg, L. J. Howell, and R. C. Sommer, Physical Chem-
ical Properties of the Systems NaCl-ZrCl,, KCI-Z:Cl , and NaCI-KCl-ZrCl,, Summary Report,
NYO-3108 (April 7, 1955).

128
TEMPERATURE (°C)

UNCLASSIFIED
ORNL—LR~-DWG 17671

900 -
800 l
700 N l
| 3NaCl ZrCl, +a2NaCl ZrCl,
NaCl + LIQUID
/~a2NOCI ZrCly + LIQUID
|
600 — -~ | /N —- i
3NaCl ZrCl, + LIQUID
o)
~ (@]
500 NaCI+ 3NaCl ZrC, aZNO‘CI ZrCl, + LIQUID —T ]
400 | NaCl+a2NacCl ZI’C|4 o -0 | | ‘ ™
—B2NaCl ZrCl, +LIQUID
—-o-Bo—o | ZrCl,+ LIQUID
HFOO—O—O——
‘ @) a3NaCl 4ZrCl,+32NaCl ZrCl, Z:\;"‘:
d_ O ¥ (@)
300 ——— 00— O == P — — == =
| a3NaCl 4ZrCl, + LIQUID
NaCl + B2NaCl ZrCl,
[ B2NaCl ZrCl,+B3NaCl 4ZrCl, B3NaCl 4ZrCl,+ZrCl,
NaCl 10 20 30 40 50 60 70 80 90 zrci,

ZrCl, (mole %)

Fig. 3.79. The System NaCl-Z(Ci .

129
3.80. The System KCI-Z(Cl,
C. J. Barton, R. J. Sheil, and W. R, Grimes, unpublished work performed at the Oak Ridge
National Laboratory, 1955.

Preliminary diagram.

Invariant Equilibria

Mole % ZrCl4 Invariant Phase Reaction at
] L. Temperature Type of Equilibrium )
in Liquid o Invariant Temperature
(-C)
23 600+ 5 Eutectic L ¥==KC! + 2KCI*ZrCl,
33.3 7905 Congruent melting point L :— 2KC|°ZrC|4
48 565 £ 5 Peritectic L+ .'ZKCI'ZrCl“'-‘fia.JKCPéZrCI4
i . — - .
- 222t 4 Inversion a-7KClI 6ZrCl4T——- 7KClI 6ZrC|4
65 225 + 4 Eutectic L T==0a-7KCI*6Z¢Cl, + ZrCl,

Some phase work on this system has been reported by H. H. Kellogg, L. J. Howell, and R. C.

Sommer, Pbhysical Chemical Properties of the Systems NaCl-ZrCl,, KCI-ZrCl,, and NaCl-
KCl-ZyCl,, Summary Report, NYO-3108 (April 7, 1955).

UNCLASSIFIED
ORNL—-LR-DWG 16152

800
'\ fl
o \\ / |
_ - L)
600 el ® ] —
— — ¢
S g \
o 5
500 2
w Z |
S i
}_
é g — o
& = \ e
£ 400 § —
z . g |
Q o
N S L
300 ) N
g : v
od _
(&)
¢ |
M~
—— ) g ] U= = W e e e e e —— T —— v
|
KCI 10 20 30 40 50 60 70 80 90 ZeGl,

130

ZrGl, (mole %)

Fig. 3.80. The System KCI-ZrCl .
3.81.

Ridge National Laboratory, 1953,

TEMPERATURE (°C)

The System LiClI-UCI,

C. J. Barton, A. B. Wilkerson, and W. R. Grimes, unpublished work performed at the QOak

Preliminary diagram. The system LiCl-UCI, contains a single eutectic at 75 LiCI-25 UCI,
(mole %), m.p. 495 + 5°C.

UNCLASSIFIED

DWG 22252
900
/C)
800 //
700 r.\t‘-(fi
L~
]
c/
. pd
N‘. /
L\ /
500 . S —————— N
® ® 104 L4 ® ORI Ts é)
400
300
LiCl 10 20 30 40 50 &0 70 80 90 UCIS
UCI5 (mole %)

Fig. 3.81. The System LiCl-UCI,

131
3.82. The System LiCl=UCI,

C. J. Barton, R. J. Sheil, and W. R. Grimes, unpublished work performed at the Oak Ridge
National Laboratory, 1953.

Preliminary diagram.

Invariant Equilibria

Mole % UCI Invariant Ph R i
ole % ULl Temperature Type of Equilibrium ase Reaction at
in Liquid ©c) Invariant Temperature
29 415 Eutectic L &= 2LiCl-UCI, + LiCl
33.3 430 T 10 Congruent melting point L =2Liclucl,
48 405 Eutectic

L= 2LiCZ|'UC|4 + UCI4

TEMPERATURE (°C)

132

Some data on this system were 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).

700

UNCLASSIFIED
DWG 19904R

600

500

400

300

200

100

LiClI

UCl, (mole %)

Fig. 3.82. The System LiCI—UCI4.

80 90 ucl,
3.83. The System NaCI-UCI,

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 NaCl-UCl, contains a single eutectic at 67 NaCl-33 UCI; (mole %), m.p. 525°C.

UNCLASSIFIED
ORNL-LR-DWG 20464

900 [

) /
.
L)
o
2 600 /
& \\/,/
x .
=
1l A Y A ¢
- L) V' ¥4 &,

500 o—

400

300

NacCl 10 20 30 40 50 60 70 80 90 UCly
UCIS {mole %)

Fig, 3.83. The System NoCI—UCI3.

133
3.84. The System NaCl=UCI,
C. J. Barton, R. J. Sheil, A. B, Wilkerson, and W. R. Grimes, unpublished work performed at
the Oak Ridge National Laboratory, 1953.

Preliminary diagram.

Invariant Equilibria

Invariant
Mecle % UC]
in Liquid 4 Temperature Type of Equilibrium Phase Reaction at Invariant Temperature
in Liqui
) (°C)
30 430 =5 Eutectic L &==NaCl + 2NaCl*UCI,
33.3 440 t 5 Congruent melting point L‘—.._"‘\2N0C|‘UC|4
47 370 %5 Eutectic L— 2Nc:lC|°UCl4 + unidentified compound
57 41515 Peritectic L+ UCI4 #unidenfified 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

900 T T

8OO P>

700 \

\ : 1
600 y

500 o

TEMPERATURE (°C}

o @ SR SIS S 5 PR, S ——

400
| __ D N

300

:
/
‘?\\

ENOCI-UCI4

200
NaCl 10 20

i

|

i

!

|
40 50 &0 70 80 90 ucCl
uci, {mole %)

oY)
(@]

Fig. 3.84, The System NaCI—UC|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.

Preliminary diagram.

Invariant Equilibria

Invariant
Mole % UCI . Phase Reaction at
4 Temperature Type of Equilibrium
in Liquid (°C) Invariant Temperature
25 550 Eutectic L == KClI +2KC|'UC|4
33.3 630 Congruent melting point L"*-(_.‘__—“.'ZKCI'UCI4
44 330 Eutectic L &= 2KCI'UCI  + KCI-UCI
. . . .
49 345 Peritectic L + KClI 3UC14<——-.—"'\‘KCI UC|4
. . _ .
61 395 Peritectic I+ UC|4‘__ KClI 3UC|4

A phose 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).

TEMPERATURE (°C)

UNCLASSIFIED
ORNL-LR-DWG 1532R

700 \'
600 4
____J)O_o_l)lj___ — X /fl)
oo
| \& X
a00 | TrTIrePtoettres E A =
o e
’/
< o] _=
300 O _ o
] [ 2
- 2 M
g o S
o ¥ ¥
KCl 10 20 30 40 50 &0 70 80 Q0 UCI4

UCI4 {mole )

Fig. 385, The System KCI—UC|4.

135
3.86. The System RbCl—UCl3
C. J. Barton, R. J. Sheil, A. B. Wilkerson, and W. R. Grimes, unpublished work performed
at the Oak Ridge National Laboratory, 1954.

Preliminary diagram.

Invariant Equilibria

Mole % UCI Invariant Phase Reaction at
ST Temperature Type of Equilibrium .
in Liquid o Invariant Temperature
(C)
15 610 Eutectic L ;_{RbCI + 3RbCl'UC|3
25 745 110 Congruent melting point L #3RbCI'UC|3
40 560 £ 10 Peritectic L+ 3RbC|'UC|3"‘; 2RbCI°UC|3
i — . .
45.5 5135 Eutectic L +—=2RbClI UCI3 + RbClI UC|3
- . L]
49 550 £ 10 Peritectic L+ UCI3—\\_—R!:CI UCI3
UNCLASSIFIED
ORNL-LR-DWG 340
900 JL B T
o
-~
800 =
/’
~
//
9 o -7
N 700 ¢ ‘//,
D
g o
G :
& 600
-
o I S E———
e}
o _ ? © 0 ¢ T
500
o O
o+ ? ° oo
400 st—13& -
2 2 3]
S S 2
x z 2
> o a
300 . B

40 50 [5le; 70 80 90 UGl
UCly (mole %)

|
o
o
o
N
(@]
[81]
o

Fig. 3.86. The System RLCI-UCI

136
3.87. The System CsCI-UCI,
C. J. Barton, A. B. Wilkerson, and W. R. Grimes, unpublished work performed at the Oak
Ridge National Laboratory, 1953.

Preliminary diagram.

Invariant Equilibria

Invariant
Mole % UCI Phase Reaction at
4 Temperature Type of Equilibrium .
in Liquid o Invariant Temperature
(7C)
20 50515 Eutectic L &= CsCl + 2CsClUCI
33.3 65715 Congruent melting point L:—-2Cs CI-l..lCl4
58 370 £ 5 Eutectic LF7=2CsCkUCI, + CsCl-2uCl
63 3825 Peritectic L + UCl,7==CsCl2ucl,
) UNCL ASSIFIED
DWG 22253R
8C0
700 — —— .
N
600 f\( A S [ S
e d
lfil:J /_-O
=
2 /©/
& 500 . ®o0a e
= C \c / ®
i 0 ® \ /
400 ©
(OO 2O ORGS o U'(A)‘- = e ComC 1O T A Bt
300 o =
- S
(] o
& S
200 ©
CsCl 10 20 30 40 50 60 70 80 S0 UCl4

)
UCI4 (mole %)

Fig. 3.87. The System CsCI-uCl,

137
3.88. The System K,CrF ,—Na,CrF —Li,CrF,
B. J. Sturm, L. G. Overholser, and W. R. Grimes, unpublished work performed at the Oak
Ridge National Laboratory, 1951-52.

Preliminary diagram.

UNCLASSIFIED
NO3CFF6 DWG 17407

O X-RAY PATTERN OBTAINED AT THESE

COMPOSITIONS
SOLID SOLUTION

K3N03(CrF6)2 o 0O

SOLID SOLUTION

VARV~ V A VAR VAR Gk

‘o; L S N ‘r;

K3Crfg K LICrFg L1, KCrFy L|3CrF6

Fig. 3.88. The System K3CrF6—N03CrF6—Li3CrF6.

138
4.1. The System $i0,~ThO,

(*C)

TEMPERATURE

4. OXIDE AND HYDROXIDE SYSTEMS

L. A. Harris, ‘A Preliminary Study of the Phase Equilibria Diagram of ThO,-Si0,,"” J. Am.
Ceram. Soc. 42, 74-77 (1959).

UNCL ASSIFIED

PHOTO 31087
2300 T Ll l\ T T T T T T
N
AN
2200} \ .
ThO, + LIQUID \
21004 \ LIQUID 7
2000} \ .
. 1975 * 50°
BN
~
~
19001 \ —
ThO,+ ThO, - Si0, ~
ThO, - Si0, + LIQUID AN
1800} AN SI0,+ -
AN LIQUID
S N
u—) + o \
1700} ol — — — — 700~ 10 —_— e N
o
,f Th02 . Si02 + SiOZ
1600 1 1 1 1 i 1 i 1 1
0 10 20 30 40 50 60 70 80 90 100
ThO, $10, (WT %) S0,

Fig. 4 1. The System 5i0,~ThO,.

139
4.2, The System LiOH-NaOH
C. J. Barton, J. P. Blakely, K, A, Allen, W. C, Davis, and B. S. Weaver, unpublished work
petformed at the Oak Ridge National Laboratory, 1951.

Preliminary diagram.

A phase diagram of the system LiOH=NaOH has been reported more

recently by N. A, Reshetnikov and G, M. Oonzhakov, Zbur. Neorg. Khim. 3, 1433 (1958),

Invariant Equilibria

Mole % LiOH Invariant Temperature T . Phase Reaction at
o ype of Equilibrium
in Liquid (*C) Invariant Temperature
27 219 Eutectic L == NaoOH + a-NaOH.LiOH
40 250 Peritectic L+ LiOH = a-L.iOH«NaOH
- 180 Inversion a-LiOH+NaOH == 5-LiOH«NaOH
UNCLASSIFIED
ORNL-LR-DOWG 20463R
500 T
|
|
450 o ——t
400
°
350
o
D
&
o
i
o
E 300‘
= '
. l
M — — e s—
250 Py T
a-NeOH LiOH |
L o }
v % !
200 ————
A
B-NaOH LiOH
150 L
NaOH 10 20 30 40 50 6C 70 80 S0 LiOH
L1CH [mole %)

140

Fig. 42. The System LiOH-NaOH.
4,3, The System LiOH~KOH
C. J. Barton, J. P. Blakely, L. M, Bratcher, and W. R, Grimes, unpublished work performed
at the Oak Ridge National Laboratory, 1951,

Preliminary diagram.

Invariant Equilibria

Mole % KOH Invariant Temperature T f Eauilibri Phase Reaction at
ilibrium
in Liquid (°C) ype of =qu Invariant Temperature
40 315 Incongruent melting point of L+ LiOH —3LiOH.2KOH
3LiOH.2KOH
70 245 Eutectic L ==3LiOH+2KOH + [5-KOH

UNCLASSIFIED

ORNL-LR-DWG 20460R
600

5 399
e 400 BN
ul /
o
p (4]
}.—
<I
a
B.J S
= 300 — |
o B-KOH
|
B-KOH 2
I 1] J 0 e L o ] o
200 Q
o
I
(]
3
M
100 L
LiOH 10 20 30 40 50 60 70 80 90 KOH
KOH (mole %)

Fig. 43 The System LIOH-KOH.

141
4.4, The System NaOH-KOH

TEMPERATURE {°C)

142

G.

400
350 \\
300 \ /
= —+LIQUIDUS DIAGRAM /
250 /
200 \\ \ A
———— o -3 PHASE
TRANSITION DIAGRAM
150
100
KOH 10 20 30 40 50 60 70 80 90

von Hevesy, ‘‘The Binary Systems NaOH-KOH, KOH-RbOH, and RbOH-NaOH," Z.
pbysik. Chem. 13, 667-84 (1910).

UNCLASSIFIED
ORNL-LR-DWG 20458

NaOH {(mole %)

Fig. 4.4. The System NaOH-KOH.

NaOH
4.5. The System NaOH-~RbLOH

G. von Hevesy, ‘‘The Binary Systems NaOH-KOH, KOH~RbOH, and RbOH-NaOH,' Z,
pbysik. Chem. 13, 667-84 (1910).

320

UNCLASSIFIED

ORNL-LR-OWG 20459

300

280

260

240

TEMPERATURE (°C)

RbOH {NaCH},

220

200

180

RbOH

10

20

30 40 50 60
NaOH {mote %}

Fig. 45. The System NaOH-RbLOH.

70

80

20

NaOH

143
4,6. The System Bu(ol'l)z—Sr(Qi'i)2
K. A. Allen, W. C. Davis, and B. S. Weaver, unpublished work performed at the Oak Ridge

National Laboratory, 1951.

Preliminary diagram.

The system Ba(OH),-3r(OH), contains a single eutectic at 37

Sr(OH),—63 Ba(OH), (mole %), m.p. 360°C.

550

UNCLASSIFIED
ORNL-1LR-DWG 204 62R

500

T T

450

400

TEMPERATURE {°C)

350

U

RIS

300
Slr(OH)2

144

10

20

30 40 50 60 70 80 I=1¢] BCJ(OH)2
ch(OH)2 {mole %)

Fig. 4.6. The System Ba(OH)z-—-Sr(OH)T
5. AQUEOUS SYSTEMS

5.1. The System UO,~P ,0.-H,0, 25°C Isotherm

J. M. Schreyer, ‘“The Solubility of Uranium(lV) Orthophosphates in Phosphoric Acid So-
lutions,”’ J. Am. Chem. Soc. 77, 2972 (1955).

The transition point between U(HPO,),6H,0 and U(HPO4)2-H3PO4-H20 as stable solids
was at 0,62 + 0,02 M U (10.3 wt % UQ,) and 9.8 £ 0.1 M PO, (42.6 wt % P205), density
1.63 £ 0.03 g/ml. The compound U(HPO,),-H;POH,0 is incongruently soluble in water,

100

~ ® ©
o O O

o))
@)

N
(@)

GRAMS OF UOQ, PER 100 GRAMS OF MIXTURE
ol o
O O

[ UHPO)y 6H0
/ UH PO,)sHz PO, HO

)

O MOTHER LIQUORS
@ CALCULATED VALUE
@ SLURRIES

UNCLASSIFIED
ORNL-LR-DWG 1915

10)

e

20 30

40 50

80 90 100

GRAMS OF P,05 PER 100 GRAMS OF MIXTURE

Fig. 5.1. The System uo,-p 205-H,0, 25°C Isotherm,

145
5.2. The System UO,~H,PO,~H,0, 25°C Isotherm

J. M. Schreyer and C, F, Baes, Jr., "“The Solubility of Uranium{VI) Orthophosphates in
Phosphoric Acid Solution,’’ J. Am, Chem. Soc. 76, 354 (1954).

The normal phosphate (UOZ)S(PO4)2-6H20 is stable below 0.025 mole % H3P04. The

stability ranges are as follows:

Compound Total Phosphate Molarity
UO2HPO4-4H20 0.014-6.1
UO,(H,PO,),+3H,0 >6.1
UNCLASSIFIED
DWG 20233
60

O SATURATED SOLUTIONS
® SLURRIES

Y
UOgHPQ 4 H,0 1/ UO.(HPOY3H,O

N
\

He0O © 50 60

mole % H,PO,

Fig. 5.2 The System UO ,—H,PO —H,0, 25°C Isotherm, 0-60 mole % UDj, 0-60 mole % HaPO,.

146
5.3. The System U(HPO,),-ClI ,0,-H,0, 25°C Isotherm

J. M., Schreyer and L. R. Phillips, ‘““The Solubility of Uranium(VI) Orthophosphates in
Perchloric Acid Solutions,”’ J. Phys. Chem. 60, 588 (1956).

The stable solids in this system are U(HPO,),.2H,0, U(H,P0,),(CIO,),-4H,0, and
U(H2PO4)2(CIO4)2-6H20. Metastable anhydrous U(HPO4)2 formed readily in all solution compo-

sitions tested. X-ray diffraction patterns indicated the existence of three polymorphic forms

of U(H,P0,),(CIO,),6H,0.

UNCLASSIFIED
ORNL-LR-DWG. 6845

ot

_U(HzP04)2 (ClO4)2" 4H20 —
D __ U{H2PO04)2 (ClOa)2* 6H20

‘_ o
. i) \}
2 _
¥ Y-
A . ).
g% "'
A R NS
*,«_Ti iy
b= o AN
AL .(
.. e
QCTh
\ T B \
ke
%
\

1 \J \\L \ \I\V\\l
25 30 3

H20 5 10 15 20

‘ wt.%
— ' e e Cl207
5 40 45 50 55 60 66 70

Fig. 5.3. Schreinemakers’ Projection of the System U0 ,~P ,0.,-Cl,0,-H,0 at 25°C. A projection on
the UOz—C|207—H20 face, plotted in rectangulor coordinates.

147
5.4. The System UO,-Na,0-CO,-H 0, 26°C Isotherm

C. A, Blake, C. F. Coleman, K, B. Brown, D. G, Hijll, R. S. Lowrie, and J, M. Schmitt,
**Studies in the Carbonate—Uranium System,’’ ], Am. Chem. Soc. 78, 5978 (1956).

UNCLASSIFIED
ORNL-LR—-DWG 39480

COMPOSITION wt %,

No,O

Fig. 5.4a. The System UO ;—Na ,0-C0 ,—H ,0 at 26°C. Compositions are
plotted in weight per cent. |, solutions in equilibrium with sodium uranates;
I, solutions in equilibrium with sodium wranyl tricarbonate; Ill, solutions
in equilibrium with uranyl carbonate. A, N02C03; B, N02C03-H20; C,
N02C03-7H.20; D, N02C03-]0H20; E, N02C030N0HC03-2H20 (trona); F,
NaHCO3, G, U02C03; H, Na4UO2(CO3)3. The entire upper face of the tri-

angular prism represents pure water.

148
The stable uranium—carbonate solids found were U02C03 and Na ,U0,(CO,};. The solution
composition at the transition point (not determined exactly) was at least 26 wt % UO,, 5.6 wt %
Nazo, and 7.2 wt % CO2 (mole ratio UOB:N020:C02 = 1:1.0:1.8).

Further data on this system are available from the American Documentation Institute
(document No. 5079). These include compositions, pH's, and densities at points in and near the
planes Na,0-CO,~-H,0, U0,-Na,0-H,0, UO,CO,~Na,CO,-H,0, Na,U0,(CO,),-NaHCO,-
H,0, UO;-Na,C0,~H,0, UO,-NaHCO,-H,0, and UO,CO;~Na,0-H,0.

Related phase equilibria in the system Na,0-UO;-H,0 at 50 and 75°C are reported by
J. E. Ricci and F. J, Loprest, J. Am. Chem. Soc. 77, 2119 (1955),

UNCLASSIFIED
PHOTO 24714

H20

A, Na, 10, (CO, ),

B. Na, U0, (C0,),

COMPOSITION wt % C. Na,C0, " 10H,0

Na,CO4

U0,CO,4

Fig. 5.4b. The Section UO ,C0 ;—-Na,C04—-H,0 at 26°C,

149
5.5. Portions of the System ThO,-Na,0-C0O,~H 0, 25°C Isotherm

F. A. Schimmel, unpublished work performed at the Oak Ridge National Laboratory, 1955,
The stable thorium~carbonate solids found were ThOCO,:8H,0 and NuéTh(COB)S-quO.

Ternary Points

Solid Phases Present

Composition of Solution (wt %)

N06 Th(C03)5-12H20, NqHCOs, and
N02C03-N0HC03-2H20 {trona)

NaéTh(C03)5°12H20, N02C03-'|0H20, and trona

Tho, Na,0 co,
0.62 12.0 9.96
0.48 14.1 10.86

EQUILIBRIUM SOLID PHASES

a-b z+ NaHCO4

b z + NaHCO, + TRONA

b-c NCIHCO3 + TRONA

b-d z+ TRONA

d 2 + TRONA + Nc12CO3 10H,0
d-e TRONA +Na,COz 10H,0
d-f z+Na,CO5 10H,0
g-h z+ThOCO5 8H,0

{z=3Na,0 ThO, 5CO, 12H,0
(TRONA =Na,CO, NoHCO; 2H,0}

N02C03 40H20 0

NagTh(COslg 12H,0

UNCLASSIFIED
ORNL-LR-DWG 38010

COMPOSITION wt %

(ThOCO, BH,0

\ \

\
oo, \
~

J)/ . (Th, CO,)
1 trona | e
" R ™~
— & \\
o NGHCO, N
- /" N3Na,0 Tho, 5C0,) ~
-
oo L7 - d > co
0 2
¢ (Na,0 CO,)  (3Ng,0 4C0,)  (Na,0 2C0,)

Fig. 5.5a. Perspective Representation of the System ThOz—Nuzo—COZ—H 20 as a Tetrahedron.

150
The highest thorium solubility found was 3.35 wt % ThO, (3.06 wt % Na,0, 3.60 wt % CO,)
in equilibrium with solid N06Th(CO3)5-]2H2O and ThOCO;-8H,0. (The terminal points of this
binary line were not established.) The maximum thorium solubility in equilibrium with
Na,Th(CO,) 4-12H,0 and Na,CO,4-10H,0 was 1.25 wt % ThO, (12.5 wt % Na,0, 9.4 wt % CO,);
with Na,Th(CO,)4-12H,0 and trona, the highest solubility was 0.7 wt % ThO, (12.6 wt % Na,0,
10.4 wt % COZ). The highest found with NabTh(CO3)5-12H20 and NaHCO, was 1.2 wt % ThO2
(5.0 wt % Na,0, 6.0 wt % CO,), which was the most dilute NaHCO, solution tested.

UNCLASSIFIED
ORNL- LR~ DWG 38043

ThO,

EQUILIBRIUM SOLID PHASES

i
o

z+ Nr_qHCO3

Z + NaHCO5 + TRONA
NaHCO3 + TRONA

z + TRONA

z+ TRONA + N02C03-4OH20
TRONA + chco3-aoH20
z+ N02C03A10H20

z+ ThOCO, 8H20

1]
a o

ThOCO,

[}
1]

\

1
=Y

COMPQSITION wi T

GO QO a a o o dJo

{z= Na ThiCO4)5 12H,0}
(TRONA = Na,CO5NaHCOy 2H,0)

VARV, R

Na,CO; ec TRONA NaoHCO,

Na,0

Fig. 555, The System ThOZ—NGZO—COZ-—Hzo at 25°C, Projection to the Th02-N020—C02 face

along radii from the H,0 vertex,

151
UNCLASSIFIED
ORNL- LR-DWG 38014

EQUILIBRIUM SOLID PHASES

0-b z+ NaHCO,

b Z+ NaHCO, + TRONA

b-c  N@HCO;+TRONA

b-d z+ TRONA

d  z+ TRONA+No,CO5 $OH,0
d-e TRONA +Na,COy 10H,0
d-t  z4+No,CO3 10H,0

g-h z+ ThOCC; 8H0 COMPQSITION wt %
{z = 3Na,0-ThO, 5C0, 12,0}

{TRONA = Na,CO5 NaHCO, 2H,0l

80

75

\/ \/ \/ {ThO, CO,)

(3Na,0 4C0,)
o 5 10 45 20 25 30

Fig. 55c, The System ThO 2—N020—C02—H 20 at 25°C. Projection to the Th02-C02—3N020-4C02—H20
internal plane, represented as an equivolent triangle, along radii from the C02 vertex, Portion from 70 to

100 wt % H,0,

152
4

5.6. The System Na,0-CO,~H,0, 25°C Isotherm

F. A, Schimmel, unpublished work performed at the Oak Ridge National Laboratory, 1955,
Significant 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 Hill and Bacon [J. Am. Chem. Soc. 49, 2487 (1927)].

Transition Points

Composition of Solution

Solid Phases Present (wt %)

Na, 0 co,
NaOH:H,0 and Na,CO, 40.5 0.85
Na,CO, and Na,CO4+H,0 31.4 0.72

Na,CO,H,0 and Na,CO,+7H,0 18.7 6.9

Na,CO4+7H,0 and Na,CO,+10H,0 17.85 7.8

. Na,CO5:10H,0 and Na,CO4:NaHCO4+2H, 0 (trona) 13.7 10.35
Trona and NaHCO, 11.9 9.5

153
The System N020—C02—H20, 25°C Isotherm

Composition of Saturated Solution

(wt %) Equilibrium Sclid Phase

N020 C02

41,3 0 NaOH-H20
40.5 0.85 N02C03
40.45 0.8 N02C03

3.6 0.67 N<12CC)3

31.4 0.72 N02C03 and Na2C03-H2O
31.1 0.78 N02C03-H20

29.9 0.5 N02C03-H20

26.6 0.4 N02C03-H2O

25.2 0.55 N02C03-H20

23.2 0.9 N02C03-H20

23.15 1.0 N02C03-H20

21,15 2.3 NOZCOS-H2O

19.3 4.3 N02C03-H2O

18.95 6.0 N02C03-H2O

18.57 7.5 N02C03-H20 (metastable)
18.6 7.8 Na2C03-H20 {metastable)
18.7 6.9 N02CO3-H20 and N02C03°7H20
18.5 6.75 N02C03'7H20 {metastable)
17.7 7.95 N02C03-7H20 (metastable)
18.3 7.3 N02C03-7H20

17.85 7.8 N02C03'7H20 and N02C03'70H20
17.3 7.88 N02C03- ]0H20

16.1 7.9 Na2CO3~10H20

15.6 7.92 Na2C03-10H20

15.1 8.1 N02C03-10H20

13.7 8.85 Nu2C03-'|0H20

13.28 9.4 N02C03-'|0H20

13.55 10.15 N02C03-70H20

14.1 1.0 N02C03-10H20 (metastable)
13.7 10.35 N02C03-]0H20 and trona*
17.0 13.0 Trona {metastable)

16.7 12,7 Trona (metastabie)

13.8 10.35 Trona

1.9 9.5 Trona and NqHCO3

11.55 9.3 NqHC03

10.5 8.8 NuHC03

9.4 8.0 NaHCO3

8.1 7.5 NcHCO3

6.4 6.5 chHCO3

5.4 5.75 NoHCO:‘l

3.9 5.0 NeHCO,

3.56 4,95 NaHCO,

3.47 4.93 NuHC03

*The formula of trona is N02C03-N0HC03'2H20.

154
Na,COy TRONA

VAl V.

UNCLASSIFIED

ORNL~LR-DWG 38014

H0
95
90
85
80
75
70
65
No,CO3- 10H,0
60
55
NaHCO,

\ vV N NN

COMPOSITION wt %o
20
25 A
30 A4
35 4
40
; g4
NG,CO5H,0
Na,COy4 ‘
50 A\VA T VARV
Na,C 5 10 15
Fig. 5.6.

45 Cco

The System Nu20—C02—H20, 25°C Isotherm. 0-50 wt % Na,0, 0-50 wt % Co.,.

155
5.7. Solubility of Uranyl Sulfate in Water

1. C. H. Secoy, J. Am. Chem. Soc. 72, 3343 (1950) (data above 300°C).

2, C. H. Secoy, J. Am. Chem. Soc. 70, 3450 (1948) (data up to 300°C).

3. L. Helmholtz aond G. Friedlander, Physical Properties of Uranyl Sulfate Solutions,
MDDC-808 (1943) (room temperature data),

4. C, Dittrich, Z. pbysik, Chem. 29, 449 (1899).

5. E. V. Jones and W. L. Marshall, HRP Quar. Prog. Rep. Marck 15, 1952, ORNL.-1280,
p 180-83,

6. E. V. Jones and W. L. Marshall, HRP Quar. Prog. Rep. Jan. 31, 1959, ORNL-2696,
p 210-11,

The two-liquid-phase region of this system in actuality must be represented by the three
components UO,, 50,, and H,0, The curve representing the boundary of liquid-liquid immisci-
bility is correct for stoichiometric solutions. However, the tie lines within the region of immisci-
bility do not connect two solutions containing stoichiometric U0,50, but rather connect solu-
tions containing varying concentrations and ratios of UO; and SO, (Fig. 5.10). At low concen-
trations and high temperatures, that is, below 0.02 m UQ,50, and above 250°C, hydrolysis
occurs to produce a nonstoichiometric solution phase. The point of hydrolysis is dependent on
concentration and temperature (see Sec 5,13),

Note: Revised data (ref 5) are used to construct the immiscibility boundary in the figure.
Earlier data (ref 1) showed higher temperatures in this region and a possible likelihood of acid

impurity in the solutions.

156
TEMPERATURE (°C)

400

350

300

250

200

130

100

50

-50

ORNL-LR-DWG 844A

UNCLASSIFIED

— UNSATURATED SOLUTION

ICE + SOLUTION

U0,50,+ 3 Hy0 + SOLUTION

T T T T T T T
UNSATURATED SOLUTION (/.2) + VAPOR U02504'H20
7. +
¢ SOLUTION
TWO-LIQUID PHASES Lg
\ -
7;4

— ICE + U0,50,-3H,0

0 ! 2 3 4 5 S

m, moles /1000 g HZO

Fig. 5.7. The System U02504—H 20-

157
5.8. TwosLiquid-Phase Region of UO,S0, in Ordinary and Heavy Water

E. V. Jones and W, L, Marshall, HRP Quar. Prog. Rep. March 15, 1952, ORNL-1280, p 180--83.

The two curves shown are boundary curves for liquid-liquid immiscibility obtained by ob-
serving the phase-transitional behavior of known U0,30,-H,0 (D20) solutions in sealed tubes
as a function of temperature. For later reference, this procedure is designated the visual-
synthetic method. As was described in Sec 5.7, the concentrations and compositions of the two
phases within the boundary region at equilibrium cannot be obtained from this figure. Mixtures
which are solutions at lower temperatures separate into two liquid phases as the temperature is

raised, according to the boundary curves,

158
TEMPERATURE (°C)

300

290

280

UNCLASSIFIED
ORNL-—LR-DWG 29314

m, moies UO,50, /1000 gm H,0, D50

Fig. 5.8 Two-Liquid-Phase Region of U0,50, in Ordinary and Heavy

Water.

159
5.9. The System U0,-30,~H,0

1. A, Colani, Bull. soc. chim. France [4] 43, 754-62 (1928).

2. J. S. Gill, E. V, Jones, and C. H. Secoy, HRP Quar. Prog. Rep. Oct. 31, 1953,
ORNL-1658, p 87.

The 25° data on the SO,~rich side are those of Colani. The higher temperature data are
those of Gill, Jones, and Secoy, obtained by filtration techniques at temperature. The number
and identity of the solid phases in the UO;—rich regions at 25, 100, and 175°C 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-tzO, 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 some-

what lower concentrations than those indicated.

UNCLASSIFIED
DWG 21234

F=U0z-H,0

K= URANOPILITE
6U03-S0318 (?)H,0
G=G BASIC SALT
(5U05- 2505~ yH,0)?

E=U0,S0, - 3H,0
D=U0,S0, - 2H,0
C=U05- 2505 6H,0
B=UO5- 2505 3H,0
A=UOy- 2505 1.5H,0

SO : U0

Fig. 5.9a. The System UO 330 3—H,0 at 25°C,

160
UNCLASSIFIED

HZO DWG 21835
\
\ F=U05H,0
\ G=G BASIC SALT
\ E =U0,S50," 3H,0
\
\
\
\
\\ 2

Fig. 5.95. The System UO 3—503—H 20 at 100°C,

161
UNCLASSIFIED
DWG 21936

F = U0 H,0
G=G BASIC SALT

SO

162
UNCLASSIFIED

HZO DWG 21937

. SOLID PHASE : B UO3-H,0

99.75 \

99.50 \

99.25 /\ X
SO U053
({? @) ‘OO O

© O
. K -
7 o o

‘A
o S o) O

Fig. 5.94. The System U0 ;~50,-H,0 at 250°C,

163
5.10. Coexistence Curves for Two Liquid Phases in the System U0,50,-H,50 ,-H, 0

H. W, Wright, W. L. Marshall, and C. H., Secoy, HRP Quar. Prog. Rep. Oct. 1, 1952,
ORNL-1424, p 108.

All curves in this figure must extrapolate to the critical temperature of water (374,2°C)
at zero concentration of uranium., These are boundary curves which were determined by
observing sealed tubes in which immiscibility occurred in UO,-50,~H,0 solutions upon varying
the temperature. As was explained in Sec 5.7, they do not represent concentrations and compo-
sitions of the two liquid phases within the temperature-concentration region of immiscibility

but are lower solution boundary curves,

164
TEMPERATURE (°C)

UNCLASSIFIED
ORNL-LR OWG 6586

450 9) [
ONE PHASE ONE PHASE
AT 525°C AT 530°C
1
I
425 ‘
400 -

955

350 x
50,
\ | 5 =148
|
[
\
f
325 — \\ I
!
|
S04
\\ e
300 —— g T a
SO,
94 _
\'\ S =1 000
I—
[
275 !
e} 5 10 15 20 25

URANIUM (wt =)

Fig. 5.10. Coexistence Curves for Two Liquid Phases in the System U0 ,50 ,-H,50 ,-H 0.

165
5.11, Two-Liquid-Phase Region of the System UO,50,-H,50,-H,0

R, E. Leed and C. H. Secoy, Chem. Quar, Prog. Rep. Sept. 30, 1950, ORNL-870, p 29-30;
C. H. Secoy, Chem. Quar. Prog. Rep. Dec. 31, 1949, ORNL-607, p 33--38,

In contrast with the immiscibility curves shown in Fig. 5.10, each of these curves must
extrapolate to a critical temperature curve for SO,—H,0 in which a small or negligible amount of
UQ, is dissolved. Since SO, dissolved in H,0 (neglecting any dissolved UO,) will elevate the
critical temperature, the curves obtained from solutions containing a constant amount of free

H,S0, will all extrapolate to critical temperatures higher than that (374.2°C) for H,O alone.

UNCLASSIFIED
DWG. 10085

410 /| T T T T l \I
/ \
400F / \ .
/ \
[ |
390 f| _
’l
\ / [
380 X T} B
AN \\ l/ , Ill
Y 7

370

360

?.. \ \ \\.O/ / /
Z s
2 350 // / -
E 0.480 M ACID / /
W 340 |
/
\o 0.365M ACID/
330 B

0.248 M ACID

320

310
0.099 M ACID

300
NO ACID

290 | | | | | l |
0 10 20 30 40 50 60 70 80
WEIGHT PERCENT U050,

Fig. 5.11. Two-Liquid-Phase Region of the System U0 ,50 ,—H 50 ,—H,0.

166
5.12, Two-LiquidsPhase Coexistence Curves for UO,—Rich Solutions in the System Uo,-S0 -
H,0 With and Without HNO,

E. V. Jones and W. L. Marshall, HRP Quar. Prog. Rep. July 1, 1952, ORNL-1318, p 147-48,
These curves have been obtained by the visual-synthetic method mentioned in Sec 5.8. They
are therefore boundary curves and do not describe compositions and concentrations within the

liquid-liquid immiscibility region.

UNCLASSIFIED
DWG 15625

I ! |18 I

300

290

280} %o ._./. / ]
o—"

270 -

300} —
-0~ L - 120 AND CONTAINING
290 SG, A
002 M UO,(NO,),

280 o o © g/ -

TEMPERATURE (°C)

! 1 | i
0 {0 20 30 40

TOTAL URANIUM (wt %)

Fig. 5.12. Two-Liquid-Phase Coexistence Curves for UO ,—Rich Solutions
in the System U03—503—H20 With and Without HN03.

167
5.13. Solubility of UO, in H,50 ,-H,0 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. The solid phase is a-U0,-H,0 below 205°C
and B-UQ0,:H,0 above 205°C. These curves represent hydrolysis equilibria.

UNCLASSIFIED
ORNL-LR-DWG. 1840AR

1.0 = .0 0000
— TWO-LIQUID PHASE
— REGION =~/ 3
S o E o DIRECT UO3 AND SO, it =
Z - ANALYSES =
= - * ANALYSES BASED ON -
< = pH AT ROOM TEMPERATURE .
- | *® & o ® © * ]
g
S
2 0.01 =— —
Q — 3
Q f— -]
Od' - —
w — -]
N
I — -
0.001 — —
e
0.0001 | | |
03 04 05 06 07 08 09 40 44 42 413 44

SOLUBILITY MOLE RATIO UOB/ HZSO4

Fig. 5.13. Solubility of U0, in H,50 ,—H,0 Mixtures,

168
5.14. Effect of Excess H,S0, on the Phase Equilibria in Very Dilute U0 ,SO, 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. I, 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 1
3
i
350 [\
N\
\\\\
AN 9
\\\ 05 = 1454
_ ~ \ SO3
£ 325 ™SS ~ U5, =142
~, 3 1
Lid
o
=
L 300
S+L+V 9
) ®
/ L+V
275 -
| /| s=soup
' 1 4 L = LIQUID
/ / V = VAPOR
250 =/

O 0.5 10
URANIUM (wt %)

Fig. 5.14. Effect of Excess H2504 on the Phase Equilibria in Very Dilute

uo 2504 Solutions.

1.5

169
5.15. SecondsLiquidsPhase Temperatures of U0,50,-Li,S0, Solutions

R. S. Greeley, S. R, Buxton, and J, C. Griess, ‘‘High Temperature Behavior of Aqueous
U0,S0,~Li,50, and UO,SO,~BeSO,,"”" paper presented at American Nuclear Society 2nd Winter
Meeting, New York City (Oct, 1957). Also R. S. Greeley and J. C. Griess, HRP Dynamic So-
lution Corrosion Studies for Quarter Ending July 31, 1956, ORNL CF-56.7.52, p 30-31.

These data were obtained by the visual-synthetic method mentioned in Sec 5.8,

UNCLASSIFIED
ORNL-LR-DWG 19101

400
/
380 //

~

340 / /

& / {
i { vl
2 /. ’e
843 320 —
.
LIEJ g //// '—-—/
~ 300 i —
-/
—

A 0.42-0.45 m U0,50, PLUS Li»S504 ]
280 © 4.3 m U0,50, PLUS LS04 | |

® 2.2 mU0,50, PLUS LizSOq4
CONCENTRATIONS ARE UNCORRECTED
260 FOR LOSS OF WATER TO VAPOR PHASE -
AT ELEVATED TEMPERATURES

240 R
0] 0.02 0.05 0.1 0.2 0.5 1.0 2.0 5.0
Li2504 (rn)

Fig. 5.15. Second-Liquid-Phase Temperatures of U0,50 ,-Li, SO, So-

lutions.

170
5.16. Second-Liquid«Phase Temperatures for U0,S0, Solutions Containing Li,SO, 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.

Liquid-liquid immiscibility occurs at the boundary curves as the temperature is raised.

UNCLASSIFIED
ORNL-LR-DWG 15803

400 }
| SUPERCRITICAL
U0,504 + 100 MOLE % L12504 7 LIGHT PHASE
~ ’
)/
/ U0,S04 + 70 MOLE %
\0— / /A/ 112504
— | |
350 / /{02504 + 50 MOLE % Li,50, |
-
g” S -— -
< — e —— — U0,50, + 100 MOLE % BeSO,
uJ ~ T
/

"' ‘/
; g ~ | U0250; + 25MOLE % L1504
2
L) _/-
[ ~t3&0--'

300 \D. —

-...________D_________._-_——-D/m)2504
250
0 05 1o 15 20 25 30 35

MOLALITY OF UO,S0,

Fig. 5.16. Second-Liquid-Phase Temperatures for UO,50, Solutions Con-
taining Li 2.‘304 or BeS0 ,.

171
5.17. SecondsLiquid-Phase Temperatures for BeSO, Solutions Containing UO,
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.

UNCL ASSIFIED
ORNL-LR-DWG 15804
400

—

TEMPERATURE (°C)

300

250
0 0.5 t.0 1.5 2.0 2.5 3.0

MOLALITY OF BeSOa

Fig. 5.17. Second-Liquid-Phase Temperatures for BeSO, Solutions Con-
taining U0,

172
5.18. The System NiSO,-U0,$0,~H 0 at 25°C

E. V. Jones, J. S. Gill, and C. H. Secoy, HRP Quar. Prog. Rep. Oct. 31, 1954, ORNL-1813,

p 166-67.

Also included in the reference are solubility data for this system at 175 and 250°C, The

data at high temperature are not in sufficient quantity for a diagram to be presented.

UNCLASSIFIED
ORNL~LR-DWG 3713A

Fig, 5.18. The System NiSO4—U02504—H20 at 25°C. Compositions are
plotted in weight per cent,

173
5.19. PhasesTransition Temperatures in Solutions Containing Cu$0,, UO,SO,, and H,50,
F. E. Clark, J. S. Gill, R. Slusher, and C. H, Secoy, J. Chem. Eng. Data 4, 12 (1959).

All data were obtained by the visual-synthetic method mentioned in Sec 5.8 and represent

temperatures at which immiscibility occurred upon raising the temperature,

No deductions can

be made regarding compositions within the two-liquid-phase region.

UNCLASSIFIED
ORNL-LR-DWG 24422B

3 94 mole % EXCESS
SULFURIC ACID

305°C,
300-\._\
i
i5 20
U02$O4(w'r Do) uo, 504(wt T}
15 - 15 —
/340 Cc—~— 29 11 mole % EXCESS /355“C 3875 mole Ta EXCESS

SULFURIC ACID

335 v
~ 10 3N
B~
<
Q
0 320

10
U0, S0, (wi %)

SULFURIC ACID

5 10
UOZ SO4 (w1 a]fl)

—325°C~

19 25 mole 7 EXCESS
BULFURIC ACID

Cuso, {wi %)

5 10
U0, S04 (wt %)

15 20

=== TEMPERATURE CONTOUR LINES lisotherms)
FOR APPEARANCE OF TWO LIQUID PHASES

SR REGION OF BLUE-GREEN CRYSTALLINE S0LIDS
[ REGION OF RED SOLIDS

4 REFERENCE COMPOQOSITION OF
Q1 m CuSO4
Qim U02304
<~ REFERENCE COMPOSITION OF HRT FUEL.

0 005 m CuS0,
004 m U050,
(PLUS ca 0025 m Hy50,)(55%)

Fig. 5.19. Phase-Transition Temperatures in Solutions Containing CuSO4, U02504, and H2504.

174
5.20. The Effect of CuSO, and NiSO, on Phase:Transition Temperatures: 0.04 = UO,S0,;
0.01 = H,SO

C. H. Secoy et al., HRP Quar. Prog. Rep. July 31, 1957, ORNL.2379, p 163. Also additional
data: F,

F. Moseley, Core Solution Stability in the Homogeneous Aqueous Reactor; the Effect of
Corrosion Product and Copper Concentrations, HARD(C)/P-41 {May 1957)

The curves for liquid-liquid immiscibility were drawn from data obtained by the visual-

synthetic method mentioned in Sec 5.8. Saturation temperatures for solid-liquid equilibria were
obtained by measuring solution concentrations as a function of temperature and determining a
break in the curve.

The numbers in parentheses are temperatures at which the indicated solid

phase appeared upon raising the temperature. Solid phases indicated in parentheses were found
in small quantity,

UNCLASSIFIED

ORNL-LR-DWG 23014 A
OO4H L Z L d
(249) <249 T<249 Z T 200 (186) (175)
-282 Z (245)
7 220
Z
Z
Z
Z
(261) 7
003e— e ° Z —@
( 249) ( 249) 2 (215 *(197) (185)
-282) \-282 7 \229
Z
% 3CuO 303 2H2
~ (+NiSO4-H,0) 7
Soo2 47 % 0 ° -
P %, (240) (211) (186)
= Z 216
%
A 7Y, Aéé
/
Z
001 — 7 ® — @
%, (215) (189)
SECOND LIQUID PHASE %,
%,
%,
\
330 320 310 %,
| \} “
0 001 002 003 004
CuSQy (m)
Fig. 5,20,

atures:

The Effect of CuSO4 and NiSOA on Phase-Transition Temper-
0.04 U02504; 0.01 m» H,SO

175
5.21. The System UO;~Cu0-Ni0-S0,-D,0 ot 300°C; 0.06 = SO,

J. S. Gill, R. Slusher, and W. L. Marshall, HRP Quar. Prog. Rep. Jan. 31, 1959, ORNL-2696,
p 20513,

The variation in solution composition in the presence of one, two, and three solid phases was
determined at 300°C from 0.04 to 0.2 m 503. Solubility relationships at 0.06 m .‘303 were ob-
tained from these separate solubility curves, and the skeletal volume figure for the five-compo-
nent system was drawn. Other skeletal figures can be drawn at various SO, concentrations.

This investigation is still in progress, and the data are subject to revision.

UNCLASSIFIED
ORNL- LR -DWG. 35714A

7
Ternary Composition
0.014 m NiO
0.010 m CuO

0.025 m U0,

!
|
|
|
|
|
!
|
|
|
T
I
I
I

.05

0.04
UO3- UO,504 SOLID
QUESTIONABLE

m
UOy

0.03

0.02

0.01

Fig. 5.21. The System U0Q ;~Cu0-Ni0-50,-D,0 at 300°C; 0.06 m 50,.

176
UNCLASSIFIED

ORNL-LR-DWG 925A

10.0

5.0

<

ISUAL OBSERVATION METHOD

2.0

0.5

Ndp(SOg)3 IN SOLUTION (g/liter)
o

0.2

0.1

Fig. 5.22. Solubility of Nd2(504)3 in 0.02 U02504 Solution Containing
0.005 m H,50, (180-300°C),

N
\ /— TRACER-FILTRATION METHOD
e
\\~
<]
Te—o
180 200 220 240 260 280 300

TEMPERATURE (°C)

5.22. Solubility of Nd2(504)3 in 0,02 » UO S0, Solution Containing 0.005 H2$04('|80—300°C)
R. E. Leuvze 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 Cee2(504)3 and Lc:2(504)3 in 0,02 m U02504, 0.005 m H2504.

177
5.23. Solubility of La,(80,), in U0, 50, Solutions

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

Experimental data for Figs. 5.23-5.27 were obtained by the visual-synthetic method
described in Sec 5.8. The very large effect of UO,S0O, must be noted and indicates consider-

able solvation of other species by aqueous UO,S0,.

UNCEL ASSIFIED

300 o DWG. 14640A
] l | | I
A
|
| A TWO LIQUID PHASES
\ A MUTHMANN AND ROLIQ
250 — \ —
\
\
\
®
® \
°
W 200 ° /IN .35 m U0, SO, —
o
-
— \
~ °
Ll
a
=
- .\..‘
150 ®-0-g—0 —_
100 —
°
\.\
1.0 2.0 3.0 4.0

La,(S0,)5 (Wt %)

Fig. 5.23. Solubility of L02(504)3 in U0 ,50 , Solutions.

178
5.24. Solubility of CdS0, in U050, Solutions

E. V. Jones, M, H. Lietzke, and W. L. Marshall, J. Am. Chem. Soc. 79, 267 (1957); also
Tne Solubility of Several Metal Sulfates at High Temperatures and Pressures in Water and in
Aqueous Uranyl Sulfate Solution, ORNL CF-55-7-69 (declassified Aug. 23, 1955),

See comments in Sec 5.23.

UNCLASSIFIED

DWG. 14613A
| | | | |
250 -
5 IN 1.35 m U0,S0, N
IN 0.427 m U0,S0, .
200 T
o
e
W 150 -
o
-
—
<
0- ~
Ll ~
= P
L 100 — &
—
® BENRATH
50— —
0 | | | | | |
O 5 10 15 20 25 30 35

CdSO, (WT %)

Fig. 5.24. Solubility of CdSO4 in U02S°4 Solutions,

179
5.25. Solubility of Cs,50, in UO,50, Solutions
E. V. Jones, M. H, Lietzke, and W, L. Marshall, J. Am. Chem. Soc. 79, 267 (1957); also

The Solubility of Several Metal Sulfates at High Temperatures and Pressures in Water and in

Aqueous Uranyl Sulfate Solution, ORNL CF-55.7.69 (declassified Aug. 23, 1955).

TEMPERATURE (°C)

180

See comments in Sec 5.23.

UNCLASSIFIED
DWG. 146174

300 |

200—

IN 1,35 m U0,50,

{00

® BERKELEY

IN 0.427 m U0,5S0,

70
Cs, S0, (WT %)

Fig. 5.25. Solubility of Cs,50, in UO ,S0 , Solutions,

75
. 5.26. Solubility of \’2(504)3 in V0,50, Solutions
E. V. Jones, M. H, Lietzke, and W, L, Marshall, J. Am. Chem. Soc. 79, 267 (1957); also
The Solubility of Several Metal Sulfates at High Temperatures and Pressures in Water and in
Agqueous Uranyl Sulfate Solution, ORNL CF-55-7-69 (declassified Aug. 23, 1955),

See comments in Sec 5.23.

TEMPERATURE (°C)

350

300

250

200

150

{00

UNCLASSIFIED
DWG 146354

TWO LIQUID PHASES

IN 114 m U02504

IN 0427 m U02804

| | | | l |

10 20 30 40

Y,(80,); (wt %)
Fig. 5.26. Solubility of Y2(504)3 in UO,50, Solutions.

181
5.27. Solubility of Ag,50, in U0,S0, Solutions

E. V. Jones, M. H. Lietzke, and W. L. Marshall, J. Am. Chem. Soc. 79, 267 (1957); also
The Solubility of Several Metal Sulfates at High Temperatures and Pressures in Water and in
Agueous Uranyl Sulfate Solution, ORNL CF-55-7-69 (declassified Aug. 23, 1955).

See comments in Sec 5.23.

UNCLASSIFIED

DWG. 14645A
o l.,
250 —
/.
200|— ]
__ /o _
e ®
d
T 50— |
’;C_x IN 0427 m U050,
b
=
- _ IN 1.35 m UO_SO _
2°Va
IN H o
100 / -
'S
B — BARRE ]
50— —
R TN A A N A O M A I I O O
205 5 10 15 18

AgZSO4 (WT %)

Fig. 5.27. Solubility of Ag,50 , in UD,50, Solutions.

182
5.28. Solubility ot 250°C of BaSO in U0 ,50,~H,0 Solutions

E. V. Jones, M. H. Lietzke, and W. L. Marshall, J. Am. Chem. Soc. 79, 267 {1957); also
The Solubility of Several Metal Sulfdtes at High Temperatures and Pressures in Water and in
Aqueous Uranyl Sulfate Solutions, ORNL CF-55-7-69 (declassified Aug, 23, 1955).

Solutions were filtered from solids at 250°C to obtain the solubility of BaSO, in H,0.
Counting of radioactive barium was used to determine the solubility concentration. The very
large effect of UO,S0, must be noted and indicates considerable solvation of other species by

aqueous UO,S0,.

UNCLASSIFIED

DWG. 15330 A
100 1 T — 1 T 1 ' 4
- / ay
L
= /./ -
10 — o —
@

BaSO4{mx10°) SOLUBILITY

0.2 0.4 06 0.8 1.0 1.2 1.4
VMOLALITY UO,S0,

Fig. 5.28. Solubility at 250°C of BuSO4 in UO 2504—H20 Solutions.

183
5.29. Solubility of H, WO, in 0.126 and 1.26 M UO,SO,

C. E. Coffey, W. L. Marshall, and G. H. Cartledge, HRP Quar. Prog. Rep. Oct. 31, 1953,
ORNL-1658, p 96-99.

The data shown in the figures were obtained by direct sampling of equilibrated solutions, by
the filter bomb method, and by the synthetic method described previously in Sec 5.8. In 0,126 M
UQ,S0, the solubility of H2WO4 first shows a positive temperature coefficient of solubility and
then, above 100°C, a negative coefficient of solubility. In 1.26 M UO,50, the temperature
coefficient of solubility is positive up to 285° the temperature at which two liquid phases

form — a characteristic of U02$O4—H20 solutions.

UNCLASSIFIED

DWG. 21760B
300
®
°
000 o
5200 R o
E (
) b /
3 . *
L SOLUTION\ |,/ SOLID + SOLUTION
= 1
= 100 1)
/.
0
0 1.0 2.0 3.0

SOLUBILITY (MOLARITY OF H,WO, x 10°)

Fig. 5.29a. Solubility of H2W04 in 0.126 M U02504.

184
TEMPERATURE (°C)

300

200

100

UNGLASSIFIED

DWG. 24757 B
|
TWO LIQUID PHASES
/b
o]
SOLUTION
QO
(o]
O
SOLID + SOLUTICN
C
10 20

40

SOLUBILITY ( MOLARITY OF H,WO0, x10°)

Fig. 5.295. Solubility of H,WO , in 1.26 M U0 ,50,.

185
5.30. Phase Stability of |'|2WO4 in 1.26 M UOF,

C. E. Coffey, W. L. Marshall, and G, H, Cartledge, HRP Quar, Prog. Rep. Oct. 31, 1953,
ORNL-1658, p 96-99.

The methods of solubility and stability determination were the same as for analogous studies
of H,WO, in UO,S0, (Sec 5.29). The data on the figure as drawn show temperatures at which

hydrolytic precipitation of an unidentified solid phase occurs from solutions stable at lower

temperatures,

186
TEMPERATURE (°C)

300

200

100

UNGLASSIFIED

SOLUBILITY (MOLARITY OF H,WO, x 10%)

DWG, 21761 B
°
/
SOLID + SOLUTION //
oo /"
y SOLUTION
10 2.0 3.0 4.0 50

Fig. 5.30. Phase Stability of H,W0 , in 1.26 M UO,F,,

187
5.31. The System UO,(NO,),~H,0
1. Reported in full by W, L., Marshall, J. S, Gill, 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. Gill, and C, H. Secoy, J. Am. Chem. Soc. 73,
1867 (1951).

As in the case of the system UO,50,-H,0, hydrolysis occurs at high temperatures and low
concentrations, resulting in precipitation of UO;:H,0 from stoichiometric UO,(NO,), solutions,
In addition, decomposition of NO,™ 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 visval-synthetic method described in Sec 5.8.

188
TEMPERATURE (°C)

400

350

300

250

200

150

100

50

UNCLASSIFIED
DWG. 10868

O = PRECIPITATION LIMITS
e = VAPOR PHASE COLORATION

T

10 20 30 40 50 60
U02 (N03)2 (wt °/°)

Fig. 5.31. The System U02(N03)2—H20.

189
5.32. Phase Equilibria of U0, and HF in Stoichiometric Concentrations (Aqueous System)

W. L. Marshall, J. S. Gill, and C, H. Secoy, J. Am. Chem. Soc. 76, 4279 (1954),

The two-liquid-phase region and the region of ‘‘basic’’ solid solution + saturated solution
are in actuality segments of the three-component system UOa—HF—HzO, in which the equilibrium
phases are nonstoichiometric with regard to UO,F,. This system is somewhat analogous to the

system UO,~H,50,-H,0 (see Sec 5.7).

UNCLASSIFIED
ORNL—LR—DWG 19098

400 f 1 | I T \ T
T T T T soLipksuper crimical FLuo | 11 1]
| —A—A— A A—A—A——A— A ]
350 | y UO,F, - 2H,0+LIQUID I
b U . -
- —— . i
BASIC SOLID © y UO,F, - 2H,0
300 |—SOLUTION+ ¢~ F + SATURATED
SATURATED SOLUTION
| SOLUTION °
/ \
®
250 — / L)
@ ’ + 2
— — 7 oo
(] [ J A —
o [ &2
200 — e
&J K e u_x(f’
= - UNSATURATED SOLUTION S'S
& 150 — Ceo |
= /
L
— - /.
100} o
/6
~ Oe@ N A OUR DATA g'
50 | © DATA OF DEAN & @ 2 UOF, - 2H0
® DATA OF KUNIN /@  + SATURATED
| @ SOLUTION
§
0 - O3
ICE + SATURATED SOLN. O-0-0—000 ¢ ©
SO TN T N S O N I S N S S
0 10 20 20 40 50 60 70 80 90

WEIGHT PERCENT AS UOQ,F,

Fig. 5.32. Phase Equilibric of UO , and HF in Stoichiometric Concentrations (Aqueous System).

190
5.33. Solubility of Uranium Trioxide in Orthophosphoric Acid Selutions

W. L. Marshail, J.S. Gill, and H. W, Wright, HRP Quar. Prog. Rep. May 15, 1951, ORNL-1057,
p 112-15,

The data were obtained for the most part by equilibrating solutions of known concentration in

sealed tubes for various times at different temperatures. Phase changes were observed visuvally,

UNGLASSIFIED

350 DWG 1232
| [ ! ] | | i ]
— — —
300 -
250}— -8
-— -
//
a—
- 200}— |
(&)
s A
[T ]
1
|
=
1 w |50_ -
[/
=
w
l-
100 b L\° CURVE A | MOLAR Hy PO, _
\ CURVE B 2 MOLAR Hy PO,
/B/ CURVE G 3 MOLAR Hy PO,
7 O®m OUR DATA
50— 84 KUHN AND RYON —
o LOS ALAMOS
U MORSE
o | | | | | | I
0] | 2 3 4 5 6 7 8 9

UO3 MOLARITY

Fig. 5.33. Solubility of Uranium Trioxide in Orthophosphoric Acid Solutions.

191
5.34, Solubility of Uranium Trioxide in Phosphoric Acid ot 250°C

J. S. Gill, W. L. Marshail, and H. W, Wright, HRP Quar, Prog. Rep. Aug. 15, 1951, ORNL-1121,
p 119-21,

Solution and solid mixtures were equated at 250°C in sealed glass tubes. The tubes were
cooled rapidly to room temperature, and the solution and solid phases were analyzed, The slow

reversibility of equilibrium conditions made this procedure possible.

UNCLASSIFIED
DWG. 13000

O ANALYTICAL
® PREVIOUS SYNTHETIC ?

0.8

/
o
B

SOLUBILITY OF UD, (M)

0 1 2 3 4 5 6 7 8

CONCENTRATION OF H,PO, (M)

Fig. 5.34. Solubility of Uranium Trioxide in Phosphoric Acid at 250°C.

192
5.35. Solubility of UO, in H,PO, Solution

B. J. Thamer et al., The Properties of Phosphoric Acid Solutions of Uranium as Fuels for
Homogeneous Reactors, LA-2043 (March 6, 1956); W. L. Marshall, J. S. Gili, and H. W. Wright,
HRP Quar. Prog. Rep. May 15, 1951, ORNL-1057, p 112-15; and J. S. Gill, W. L. Marshall, and
H. W. Wright, HRP Quar. Prog, Rep. Aug. 15, 1951, ORNL-1121, p 119-21,

This figure represents a compilation from the data of B. J. Thamer et al. of Los Alamos and
W. L. Marshall et al. of Oak Ridge National Laboratory.

UNCLASSIFIED
ORNL-LR-DWG 29316

N

—SOLID PHASE IS

/ uoz( H2P04)2-3H20
{ / (25°C) —
- SOLID PHASE IS / \\
U0, HPO," 4H,0 // /

r (25°-400°C ;=
7/

505 /1 f(250°C)| \

: N
yAY/ERRIEN
2 / N

/
02 / !
0.4

10 2 5 10 20
PO, MOLARITY

Fig. 5.35. Solubility of UD, in H;PO , Solution.

193
5.36. The System U0,Cr0 ,~H 0

1. F. J. Loprest, W, L. Marshall, and C, H, Secoy, J. 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 U02Cr04-5]/2H20 (A) and UC,CrO,.xH,0 (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, U02Cr207, is stable to the critical temperatuyre

and apparently dissolves in the supercritical fluid (ref 2),

UNCLASSIFIED
ORNL-LR-DPWG 5144A

140 AN
NON-BINARY
{30 +—SOLID + LIQUID . —
}/%
120 — —
B /1/
0O — o

-
L//I ¥ B + LIQUID
100 |— T —]

90 — LIQUID ) ]

.

TEMPERATURE (°C)

A+ B

A + LIQUID

A +ICE

—10 | | R | —

0 {0 20 30 40 50 60 70 8O 9C 100
UO,CrO4 (wt %)

Fig. 5.36. The System U02Cr04--H20.

194
5.37. Variation of Li,CO, Solubility with UO,CO; Concentration at Constant CO, Pressure
(250°C)
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. [an. 31, 1956,
ORNL-2057, p 131-32,
The solubility relationships in the figure indicate strong complexing of U0,CO, with Li,CO,

under CO2 pressure. The formation of HCO,™ species in solution is indicated.

UNCLASSIFIED
ORNL-LR-DWG {1182A

g
7/

/
7/

1.000 I

0.800 QO}

\
SLOPES:
® 3. .37 moles of Li per mole of U
0.200 (LipCO5 IS SOLID PHASE)

A 4.44 moles of Li per mole of U |
AT ISOBARIC INVARIANT :
|

i
!
1

0 |
O 002 004 006 008 010 042 0144 016 048

U0,CO4 (m)

Fig. 5.37. Variation of Li,CO, Solubility with U02C03 Concentration at
Constant CO, Pressure (250°C).

195
5.38. The System Li,0-U0,~CO,~H,0 at 250°C 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,

ORNL-2057, p 131-32,

2. W. L. Marshall, F. J, Loprest, and C, H. Secoy, HRP Quar. Prog. Rep. [an, 31, 1956,

As CO, pressure is increased, the area of complete solution (indicated by the shading)
increases. As temperature is increased, the solution area decreases,

UNCLASSIFIED
ORNL-LR-DWG 113428B
H,50
100

{O

90

Fig. 5.38. The System Li20-—U03—C02—H20 ot 250°C and 1500 psi,

196
5.39. The System Th(NO,),-H,0

1. Reported in full by W. L. Marshall, J. S. Gill, and C. H. Secoy, HRP Quar. Prog. Rep.
Nov. 30, 1950, ORNL-925, p 279-90.

2. W. L. Marshall, J. S. Gill, and C. H, Secoy, . Am. Chem. Soc. 73, 4991 (1951),

Hydrolytic precipitation of ThO, and thermal decomposition of NO,™ in this system occur in
an analogous monner to the reactions occurring in the system UOZ(NOB)z-—-Hzo (see Sec 5.31).

At higher temperatures the two-component system in actuality must be considered in terms of the

three components ThO,, HNO,, and H,0.

UNCLASSIFIED
DWG. 9967

2501+

225

200

175

150

125
(@]
-]
i
T 100
'—-
!
& /
n O SOLUBILITY DATA I
= 75 ® DEGOMPOSITION PREGIPITATION I
- A  "MUSH" TEMPERATURES / |
O SUPER COOLING d /
50 n |
25—
A
o
_25 —
B
_50 }—
| | | 1 | | | | |
0 10 20 30 40 50 60 70 80 90 100

WEIGHT PERGENT Th{NO3)4

Fig. 5.39. The System Th(N03)4—H20.

197
5.40. Hydrolytic Stability of Thorium Nitrate~Nitric 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. Marshall, J. S. Gill, and C. H. Secoy, Chem. Quar. Prog. Rep. March 31, 1951,
ORNL-1053, p 22-25,

The data used to draw the individual curves were obtained by observations at various tem-
peratures of tubes that contained different solutions of known concentration. The procedure
was analogous to that used for obtaining data for Fig., 5.33. The curve for hydrolytic precipi-
tation of UG,(NO,), is taken from ref 2,

UNCLASSIFIED
ORNL-LR-DWG.21759B

380 | .
NO,/U =2.0
~ 300 }- -
O
) NOs/Th= 5.47
Lol
260 —
T NO,/Th=6.65
l_
=
i 220 —
=
W yan NO,/Th=4.0 |
140 |- -
100 | '
0 1,0 2.0

THORIUM, URANIUM (M)

Fig. 5.40. Hydrolytic Stability of Thorium Nitrate=Nitric Acid and Uranyl

Nitrate Solutions.

198
5.41. The System ThO,~Cr0,~H,0 ot 25°C

1. H. T. S. Britton, J. 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 1-7 indicate compositions
investigated at high temperature by Marshall, Loprest, and Secoy. These solution compositions

were phase stable up to 160°C for point 7 and 320°C for point 1.

UNCLASSIFIED
ORNL-LR-DWG 5020A

AA‘ A
JANAV 7 YATA
AVAVAV i ey
JAVAVAY 171 11
JAVAVAVAVA' .AV.

VAT AV R
Tho, »CrO

Fig. 5.41. The System ThOz-Cr03—H20 at 25°C. Compositions are in
weight per cent,

3

199
5.42, Phase Stability of ThO ,~H PO ~H,0 Solutions at High Concentrations of ThO,

W. L. Marshall, experimental data in ORNL research notebook 2881, p 35 (May 1953).

Solutions of appropriate concentrations were prepared and analyzed. These solutions were
sealed in glass tubes and shaken at various temperatures for times varying from 1 hr to several
days. In this manner the phase stability boundaries with respect to concentration and temper-
ature were established. At first inspection of the figure it is surprising that more ThO2 can be
dissolved per liter at the lower H,PO,/ThO, ratio than at the higher ratio. Actually, there
is a physical volume limitation due to the high fractional volumes occupied by ThO2 and H,PO,
at these concentrations. As any solution is diluted with H,O, hydrolysis of thorium in solution
occurs. At room temperature, solutions in which the H,PO,/ThO, ratio is 5:1 are gels, whereas

10:1 ratio solutions are still fluid.

UNGLASSIFIED
ORNL-LR-DWG 38529

400 I # I [ | \1] l
350+ \‘! —
\” \l,
: Y
= D
W 300 |- ™ /
= / P |
HYDROLYTIC HYDROLYTIC
< SOLUTION SOLUTION
PREGIPITATION PRECIPITATION
i CIPITATION ™ "ReGION Al REGION
a 250 — o / -
o 7 X
= BOUNDARY GURVE # BOUNDARY CURVE
FOR 40:1 MOLE " FOR 5: MOLE
200 — Y RATIO, HyPO,/ThO, 7 RATIO, —
N g Hy PO,/ ThO,
\/ y/o
150 I S N N i L1

0 100 200 300 400 500 600 700 80O 900 4000
GRAMS ThO» PER LITER OF SOLUTION (25°C)

Fig. 542. Phase Stability of ThO ,—H 3P0 ;~H,0 Solutions at High Concentrations of ThO »

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 and Engineering Data

Journal of Pbysical Chemistry

Journal of the American Chemical Society

U.S. Atomic Energy Commission

201
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104.
105.
106.
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159.
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162.
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164.

MR APE-AAAO - PAANEEC AT AIEE-PERA-AALATZIIACOPCZPIIZOOTE

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. Lee, Jr.

. Leed

. Leuze

. Lewis

. Lietzke

. Lincoln
Lind

. Lindauer

. Livingston
Long

. Lorenz

. Lowrie

T>»rPp=C 4 U0==0T

mr r—owDrITITmMmmmaoe

. 1. Lundin

Lyon

. McBride

. McDonald
McDuffie

. McLain

. McNees

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ZrMEOM-r IrmNO=E-7TITMrroAZer»> nwoZ

165.
166.
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222.
223.
224.
225.

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