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ORNL-2548 Chemistry — General TID-4500 (15th ed.)

PHASE DIAGRAMS OF NUCLEAR REACTOR MATERIALS

R. E. Thoma, Editor

OAK RIDGE NATIONAL LABORATORY operated by

U N I O N CARBIDE CORPORATION

for the

U.S. A T O M I C ENERGY C O M M I S S I O N

Printed in USA. Price j O . J U . Available from the

Office of Technical Services

Department of Commerce

Washington 25, D. C.

LEGAL NOTICE

This report was prepared os an account of Government sponsored work. Neither the United States,

nor the Commission, nor any person acting on behalf of the Commission

A. Makes any worranty or representation, expressed or implied, with respect to the accuracy,

completeness, or usefulness of the information contained in this report, or that the use of

any information, apporotus, method, or process disclosed in this report moy not infringe

privately owned rights, or

B. Assumes any liabilities with respect to the use of, or for damages resulting from the use of

any information, apparatus, method, or process disclosed in this report.

As used in the above, "person acting on behalf of the Commission" includes any employee or

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

provides access to, any information pursuant to his employment or contract with the Commission,

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DISCLAIMER

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ORNL-2548 Chemistry — General TID-4500 (15th ed.)

Contract N o . W-7405-eng-26

R E A C T O R C H E M I S T R Y D I V I S I O N


R. E. Thoma, Editor

D A T E ISSUED

OAK RIDGE NATIONAL LABORATORY Oak Ridge, Tennessee

operated by UNION CARBIDE CORPORATION

for the U.S. ATOMIC ENERGY COMMISSION

CONTENTS

INTRODUCTION 1

1. METAL SYSTEMS 2

1.1. The System Silver-Zirconium 2 1.2. The System Indium—Zirconium 4 1.3. The System Antimony—Zirconium 6 1.4. The System Lead—Zirconium 8

2. METAL-FUSED-SALT SYSTEMS 9

2.1. The Sodium Metal-Sodium Halide Systems 9 2.2. The Potassium Metal—Potassium Halide Systems 10 2.3. The Rubidium Metal-Rubidium Halide Systems 11 2.4. The Cesium Metal—Cesium Halide Systems 12 2.5. The Alkal i Metal-Alkali Metal Fluoride Systems 13

3. FUSED-SALT SYSTEMS 14

3.1. The System L iF-NaF 14 3.2. The System L i F - K F 15 3.3. The System L iF -RbF 16 3.4. The System L iF -CsF 17 3.5. The System NaF-KF 18 3.6. The System NaF-RbF 19 3.7. The System KF-RbF 20 3.8. The System L i F - N a F - K F 21 3.9. The System L iF -NaF-RbF 22 3.10. The System L i F - K F - R b F 23 3.11. The System NaF-KF-RbF 24 3.12. The System NaBF^-KBF^ 25 3.13. The System NaF-FeF j 26 3.14. The System NaF-N iF j 27 3.15. The System RbF-CaFj 28 3.16. The System L i F - N a F - C a F j 29 3.17. The System NaF-MgF j -CaF j 30 3.18. The System NaF-KF-AIFg 32 3.19. The System L i F - B e F j 33 3.20. The System NaF-BeF^ 34 3.21. The System K F - B e F j 36 3.22. The System RbF-BeFj 38 3.23. The System CsF-BeF j 40 3.24. The System L i F - N a F - B e F j 42 3.25. The System L i F - R b F - B e F j 44 3.26. The System N a F - K F - B e F j 46 3.27. The System NaF-RbF-BeF j 47 3.28. The System NaF-ZnF j 48 3.29. The System K F - Z n F j 49 3.30. The System RbF-ZnF j 50 3.31. The System L i F - Y F j 51 3.32. The System L i F - Z r F ^ 52 3.33. The System NaF-ZrF^ 54

3.34. The System K F - Z r F ^ 56

3.35. The System R b F - Z r F ^ 57

3.36. The System C s F - Z r F ^ 58

3.37. The System L i F - N a F - Z r F ^ 60

3.38. The System N a F - K F - Z r F ^ 62

3.39. The System N a F - R b F - Z r F ^ 64

3.40. The System N a F - C r F j - Z r F ^ : The Section N a F - C r F j - Z r F ^ 66

3 .41 . The System N a F - C e F 3 - Z r F 4 67

3.42. The System L i F - C e F j 68

3.43. The System N a F - H f F ^ 70

3.44. The System L i F - T h F ^ 72

3.45. The System N a F - T h F ^ 73

3.46. The System K F - T h F ^ 74

3.47. The System R b F - T h F ^ 76

3.48. The System B e F j - T h F ^ 77

3.49. The System B e F j - U F ^ 78

3.50. The System M g F ^ - T h F ^ 79

3 .51 . The System L i F - B e F j - T h F ^ 80

3.52. The System N a F - Z r F ^ - T h F ^ 82

3.53. The System L i F - U F g 84

3.54. The System L i F - U F ^ 85

3.55. The System N a F - U F j 86

3.56. The System N a F - U F ^ 88

3.57. The System K F - U F ^ 90

3.58. The System R b F - U F ^ 91

3.59. The System C s F - U F ^ 92

3.60. The System Z r F ^ - U F ^ 93

3 .61 . The System S n F j - U F ^ 94

3.62. The System P b F j - U F ^ 95

3.63. The System ThF - U F ^ 96

3.64. The System L i F l N a F - U F ^ 98

3.65. The System L i F - K F - U F ^ 101

3.66. The System L i F - R b F - U F ^ 102

3.67. The System N a F - K F - U F ^ 103

3.68. The System N a F - R b F - U F ^ 104

3.69. The System L i F - B e F j - U F ^ 108

3.70. The System N a F - B e F 2 - U F 4 110

3 .71 . The System N a F - P b F j - U F ^ 113

3.72. The System K F - P b F j - U F ^ 114

3.73. The System N a F - Z r F ^ - U F ^ 116

3.74. The System L i F - T h F ^ - U F ^ 119

3.75. The System N a F - T h F ^ - U F ^ : The Section 2 N a F . T h F 4 - 2 N a F . U F 4 124

3.76. The System L i F - P u F j 125

3.77. The System L i C I - F e C l j 126

3.78. The System K C I - F e C l j 127

3.79. The System N a C I - Z r C I ^ 128

3.80. The System K C I - Z r C I ^ 130

3 .81 . The System L i C I - U C l 3 131

3.82. The System L i C I - U C I ^ 132

3.83. The System NaCI -UCIg 133

3.84. The System N a C i - U C I ^ 134

http://2NaF.ThF4-2NaF.UF4

3.85. The System K C I - U C I ^ 135

3.86. The System RbCI -UCIg 136

3.87. The System C s C I - U C I ^ 137

3.88. The System K 3 C r F g - N a 3 C r F ^ - L i 3 C r F g 138

4 . OXIDE AND HYDROXIDE SYSTEMS 139

4 . 1 . The System S i O j - T h O j 139

4 .2 . The System L i O H - N a O H 140

4.3 . The System L i O H - K O H 141

4 .4 . The System N a O H - K O H 142

4.5. The System NaOH-RbOH 143

4.6. The System Ba(OH)2-Sr(OH)2 144

5. AQUEOUS SYSTEMS 145

5 . 1 . The System U O j - P j O ^ - H j O , 25°C Isotherm 145

5.2. The System U O j - H j P O ^ - H j O , 25°C Isotherm 146

5.3. The System U ( H P 0 4 ) 2 - C l 2 0 7 - H 2 0 , 25°C Isotherm 147

5.4. The System U 0 3 - N a 2 0 - C 0 2 - H 2 0 , 26°C Isotherm 148

5.5. Port ions of the System T h 0 2 - N a 2 0 - C 0 2 - H 2 0 , 25°C Isotherm 150

5.6. The System N a 2 0 - C 0 2 - H 2 0 , 25°C Isotherm 153

5.7. So lub i l i t y of Uranyl Sulfate in Water 156

5.8. Two-L iqu id -Phase Region of UO jSO, in Ordinary and Heavy Water 158

5.9. The System UO3-SO3-H2O 160

5.10. Coexistence Curves for Two L i q u i d Phases in the System

UO2SO4-H2SO4-H2O 164

5 .11 . Two-L iqu id -Phase Region of the System UO2SO4-H2SO4-H2O 166

5.12. Two-L iqu id -Phase Coexis tence Curves for UO,—Rich Solut ions in

the System U O 3 - S O 3 - H 2 O With and Without HNO3 167

5.13. So lub i l i ty of UO3 in H2SO4-H2O Mixtures 168

5.14. Ef fect of Excess H.SO. on the Phase Equ i l ib r ia in Very D i lu te

UO2SO4 Solut ions 169

5.15. Second-Liquid-Phase Temperatures of U O j S O . - L i j S O . Solut ions 170

5.16. Second-Liquid-Phase Temperatures for UO.SO. Solut ions Conta in ing

L i . ,SO, or BeSO, 171

5.17. Second-Liquid-Phase Temperatures for BeSO^ Solut ions Conta in ing UO3 172

5.18. The System N i S 0 4 - U 0 2 S 0 4 - H 2 0 at 25°C 173

5.19. Phase-Trans i t ion Temperatures in Solut ions Conta in ing CuSO. ,

UO2SO4, a n d H j S O ^ 174

5.20. The Ef fect of CuSO, and NiSO, on Phase-Trans i t ion Temperatures:

0.04 m UOjSO^; 0.01 m H jSO^ 175

5 .21 . The System U 0 3 ^ C u O - N i O - S 0 3 - D 2 0 at 300°C; 0.06 m SO3 176

5.22. So lub i l i ty of Nd2(S04)3 in 0.02 m UO2SO4 Solut ion Conta in ing 0.005 m

H2SO4 (180-300°C) 177

5.23. So lub i l i ty of La2(S04)3 in UOjSO^ Solut ions 178

5.24. So lub i l i ty of CdSO^ in UO2SO4 Solut ions 179

5.25. Solub i l i ty of C s S O ^ in UOjSO^ Solutions 180

5.26. So lub i l i ty of Y2(S04)3 in UO2SO4 Solut ions 181

5.27. So lub i l i ty of Ag2S04 in UOjSO^ Solut ions 182

5.28. So lub i l i ty at 250°C of BaSO^ in UO2SO4-H2O Solut ions 183

5.29. Solub i l i ty of H2WO4 in 0.126 and 1.26 M UOjSO^ 184

5.30. Phase Stab i l i t y of H2WO4 in 1.26 M UO2F2 186

v

5 .31 . The System U 0 2 ( N 0 3 ) 2 - H 2 0 188

5.32. Phase Equ i l i b r ia of UO and HF in Stoichiometr ic Concentrat ions

(Aqueous System) 190

5.33. So lub i l i t y of Uranium Tr iox ide in Orthophosphoric A c i d Solut ions 191

5.34. So lub i l i t y of Uranium Tr iox ide in Phosphoric A c i d at 250°C 192

5.35. So lub i l i t y of UO3 in H3PO4 Solution 193

5.36. The System U 0 2 C r 0 4 - H 2 0 194

5.37. Var ia t ion of L i 2 C 0 3 Solub i l i ty wi th UO2CO3 Concentrat ion at Constant

CO Pressure (250°C) 195

5.38. The System L i O - U O 3 - C O 2 - H 2 O at 250°C and 1500 psi 196

5.39. The System T h ( N 0 3 ) 4 - H 2 0 197

5.40. Hydro ly t ic Stab i l i ty of Thorium N i t r a t e - N i t r i c A c i d and Uranyl

N i t ra te Solut ions 198

5 .41 . The System T h 0 2 - C r 0 3 - H 2 0 at 25°C 199

5.42. Phase Stab i l i t y of T h 0 2 - H 3 P 0 4 - H 2 0 Solut ions at High Concentrat ions

of T h O j 200

vi


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

recent publication by Ricci. Nor has any attempt been made to assemble the phase equilibrium

data on reactor materials available from many other sources. For such information the reader is

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

works dealing specifically with nuclear reactor materials.

While some of the diagrams presented below are the result of fundamental researches, most

were obtained in support of the ORNL programs in development of fluid-fueled reactors. Others

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

reactor metallurgy, production of uranium and thorium from raw materials, and studies of

mechanisms of corrosion.

Much of the research effort was devoted to searches for systems of direct use as fluid fuels

or blanket materials; unpromising systems were often given only casual attention. The diagrams

in this collection, accordingly, vary widely in the degree of completeness of examination. A

brief description of the status of the work is presented in each case; in a few cases, where no

detailed description of the system has been published, the available data have been included

with the diagram.

J. E. Ricci , Guide to the Phase Diagrams of the Fluoride Systems, ORNL-2396 (Nov. 19, 1958).

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

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

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

1958).

E. M. Levin, H. F . McMurdie, and F . P . Hall , Phase Diagrams for Ceramists, The American Ceramic

Society, Columbus, Ohio, 1956.

E. M. Levin, H. F . McMurdie, and F . P . Hall , Supplement to Phase Diagrams for Ceramists, The

American Ceramic Society, Columbus, Ohio, 1959.

B. Yates , Materials for Use m Nuclear Reactors, Information Bibliography, IGRL-IB/R-15 (2nd ed . ) ,

1958. o

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

New York, 1955. O

B, Kopelman (ed.)# Materials for Nuclear Reactors, McGraw-Hill Book Co. , New York, 1959.

1

1. METAL SYSTEMS

1.1. The System Silver—Zirconium

J . 0 . Betterton, Jr., and D. S. Easton, "The Silver-Zirconium System," Trans, Met. Soc,

A/ME 212, 470-75(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, Zr2Ag and ZrAg, and a eutectoid reaction in which the /S-zirconium solid solution de-

composes into a-zirconium and Zr jAg. 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.

2

UNCLASSIFIED

ORNL-LR-DWG 18989

u S huLE PHASE a- S NGLE PHASE WITH A TRACE OF SECOND PHASE

DAV TWO PHASE THREE PHASE FILLED SYMBOLS NDICATE METALLOGRAPHIC SAMPLES

WHICH WERE CHEMICALLY ANALYZED FOR SILVER CONTENT

-O-O • ' V V

SILVER (at %)

at.

F ig . 1.1a. The System Si lver-Zirconium in the Eutectoid Region ( 0 - 6

% Ag).

1400

1300 -

1200

o 1100

a:, 1000

900

8 0 0

7 0 0

/ a + >

/3 + LIQ

/ 8 + y

UNCLASSIFIED

ORNL-LR-DWG 18988A

""^ \ M, • \ LIQ

_v \

\ \

' + LIQ,

o SINGLE PHASE

DAV TWO PHASE

FILLED SYMBOLS INDICATE METALLOGRAPHIC SAMPLES

WHICH WERE CHEMICALLY ANALYZED FOR SILVER CONTENT

y+S

10 15 20

SILVER (at %)

25 3 0 35

F ig . l . lfe. The System Silver—Zirconium in the Region 0—36 at. % Ag .

1.2. The System Indium—Zirconium

J . 0 . Bet ter ton, Jr . , and W. K. Noyce, " T h e Equi l ib r ium Diagram of Indium—Zirconium in the

Region 0 - 2 6 at. pet I n , " Trans. Met. Soc. AlME 212, 3 4 0 - 4 2 (1958).

The z i rconium-r ich port ion of the ind ium-z i rcon ium phase diagram was determined as a

study of the ef fect of a l l oy ing a t r i va len t B-subgroup element, indium, wi th zirconium in group

IVA. The temperature of the a l lo t rop ic t ransi t ion was found to r ise w i th indium, terminat ing in a

per i tec to id react ion, |S(9.3% In) + y{22.4% In) ; ^ : : ^ - a ( 1 0 . 1 % In) at 1003°C. In th is respect the

ef fect of indium is analogous to that of aluminum in z i rconium and t i tanium a l l oys .

1300

1200

1100

1000

UNCLASSIFIED ORNL-LR-DWG 18987

LiJ Q.

9 0 0

8 0 0

700

6 0 0

5 0 0 6 8

INDIUM (at 7o)

F ig . 1.2a. The System Indium—Zirconium in the Peritectoid Region (0—13

at . % In) .

4

millercText BoxBLANK

1400

1300

1200

u UJ

ID

cr u Q.

1100

1000

900

800

700


Fig. 1.3fe. The System Antimony-Zirconium in the Peritectoid Region (0-6 at. % Sb).

7

1.4. The System Lead—Zirconium

G. D. Kneip, Jr., and J . 0 . 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

LU

2. M E T A L - F U S E D - S A L T SYSTEMS

2 . 1 . The Sodium Metal—Sodium Halide Systems

M. A . Bredig and J . E. Sutherland, "H igh-Tempera ture Region of the Sodium—Sodium Hal ide

Sys tems , " Chem. Ann, Prog, Rep. June 20, 1957, ORNL-2386, p 119. Subsequent report on these

systems to be publ ished.

UNCLASSIFIED ORNL-LR-DWG. 21894A

1200

1100

l O O O i i

< - MOLE FRACTION MX .9 .8 .7 .6 .5 .4 .3 .2 .1

^ MOLE FRACTION MX .9 .8 .7 .6 .5 .4 .3 .2 .1

°C

9 0 0

8 0 0

7 0 0

6 0 0

1100

7 0 0

6 0 0

iTson \ \ I \ r

®

® ONE LIQUID

TWO LIQUIDS

NaBr - Na

740°

\

SOLID SALT+ LIQUID METAL \

I I I I I I I I I

"1 \ o COOLING CURVESJHIS WORK X EQUILIBRATION, MAB,JWJ,WTS A EQUILIBRATION, HRB, MB

1080°

SOLID SALT + LIQUID METAL

® ONE LIQUID

1033°

SOLID SALT + LIQUID METAL J L J \ \ \ L J L

1200

1100

1000

°C

9 0 0

8 0 0

7 0 0

6 0 0

- 1 1 0 0

1000

°C

9 0 0

8 0 0

700

.1 .2 .3 .4 .5 .6 7 .8 .9 MOLE FRACTION OF METALS

.1 .2 .3 .4 .5 .6 7 ,8 .9 MOLE FRACTION OF METALH

>600

Fig. 2 ,1 . The Sodium Metal—Sodium Halide Systems.

2.2. The Potassium Metal—Potassium Halide Systems

J. W. Johnson and M. A. Bredig, "Miscib i l i ty of Metals with Salts in the Molten State. I I I . The

Potassium-Potassium Halide Systems," / . Phys. Chem. 62, 604 (1958).

Complete miscibil i ty of metal and salt exists in the KX—K systems, X = F, CI, 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.

UNCLASSIFIED ORNL-LR-DWG 2(481B

I I I I I I I I \ I W t

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

Fig . 2 .2 . The Potassium Metal—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 Equi l ibr ia," Chem. Ann, Prog, Rep, June 20, 1958,

ORNL-2584, p 73. Subsequent report on these systems to be published.


800

750

700 °c

650

600

550

790°

\ / RbF-Rb \ . — ^ X — X - ^ .

773° \ \

scr^xRb-qizRb 696°

R b B r - R b

\

\

25 50 75

MOLE % Rb METAL

Fig. 2.3. The Rubidium Metal—Rubidium Halide Systems.

n

2.4. The Cesium Metal—Cesium Halide Systems

M. A . Bredig, H. R. Bronste in , and W. T . Smith, J r . , " M i s c i b i l i t y of L iqu id Metals w i th

Sal ts . I I . The Potassium—Potassium Fluor ide and Cesium—Cesium Hal ide Sys tems , " / . Am,

Chem, Soc. 77, 1454 (1955).

M i s c i b i l i t y in a l l proport ions of cesium metal w i th cesium hal ides at and above the mel t ing

points of the pure sa l t s , and of potassium metal w i th potassium f luor ide 50° above the mel t ing

point of the sa l t , occurs. The temperature-concentrat ion range of coexistence of two l iqu id

phases decreases in going from sodium to potassium systems and disappears al together for the

cesium systems. The so lub i l i t y of the sol id ha l ides in the corresponding l iqu id a l ka l i metals,

at a given temperature, increases great ly wi th increase of atomic number of the metal .

UNCLASSIFIED ORNL-LR-DWG. 37011

0 25 50 75 ^00

MOLE % METAL

Fig. 2.4. The Cesium Metal—Cesium Halide Systems.

12

2.5. The Alkal i Metal—Alkali Metal Fluoride Systems

M. A . Bredig, J . E. Sutherland, and A . S. Dwork in , " M o l t e n Salt—Metal Solu

E q u i l i b r i a , " Chem, Ann. Prog. Rep, June 20, 1958, ORNL-2584, p 73,

1300 —

1200

1100

1000

9 0 0

800.—


700

600 25 50 75

MOLE % METAL 100

Fig. Z5 . The Alkal i Metal -Alkal i Metal Fluoride Systems.

3. FUSED-SALT SYSTEMS

3.1. The System LiF-NaF

A. G. Bergman and E. P. Dergunov, "Fusion Diagram of L iF -KF—NaF, " Compt. rend. acad.

sci. U.R.S.S. 31, 753-54 (1941).

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

1000

900

800

700

600

500 LiF 10 20 30 40 50 60

NaF (mole%)

70


^ ^

" ^

^ ^ - ^

/

/ 6 5 2 ° C

^

9 0 NaF

Fig. 3.1. The System LiF—NoF.

14

3.2. The System L i F - K F

A. G. Bergman and E. P. Dergunov, "Fusion Diagram of L i F - K F - N a F , " Compt. rend. acad.

sci. U.R.S.S. 31, 753-54 (1941).

The system L i F - K F contains a single eutectic at 50 LiF—50 KF (mole %), m.p. 492°C.


40 50 60

KF(mole%)

Fig. 3,2. The System L i F - K F .

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

Mole % L iF

in Liquid

Invariant

Temperature

(°C) Type of Equilibrlun Phase Reaction

at Invariant Temperature

44

47

470

475

Eutectic

Perltectic

L ^ ^ ^ R b F -I- LIF-RbF

L + L I F ; ^ ^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.S.S.R. 58, 1369-72 (1947).


9 0 0

6 0 0

5 0 0

~-.^ I ' '

, , J II a \ ^ ' Ji • • — < »

1 u_ -Q

cr

u.

4 0 50 60 LiF (mole %)

Fig. 3.3, The System L iF -RbF.

16

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.



Mole % CsF

In Liquid

Invariant

Temperature

(°C) Type of Equilibrium Phase Reaction


55

63

495 ± 5

475 ± 5

Perltectic

Eutectic

LIF +L ^=^LIF-CsF

L V 'LIF-CsF + CsF

900

800

700

600

500

400


3 0 0

\

x̂ \

V)

O l i -_ l

\ .^ ^^

X ^ ^

LiF 10 2 0 3 0 40 50 60 CsF (mole %)

70 80 90 CsF

Fig, 3,4. The System LiF—CsF.

17

3.5. The System NaF-KF


sci. U.R.S.S. 31, 753-54 (1941).

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


5 0 6 0

KF(mole7o)

Fig, 3,5. The System NaF-KF.

18

3.6. The System NaF.RbF

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

at the Oak Ridge National Laboratory, 1951.

Preliminary diagram. The system NaF-RbF contains a single eutectic at 27 NaF-73 RbF

(mole %), m.p. 675 + 10°C.




1000 1

9 5 0

9 0 0

o - 850 LJ a:

a: 0-5 800 u

750

700

• \ \

\ • S .

•

"^ \

\ c N,

X X

i 1

L ^

\ \

\ ^ \

•

/•:

\A» • •'

/


3.7. The System KF-RbF



Preliminary diagram. The system KF-RbF contains a solid solution minimum at 28 K F -

72 RbF (mole %), m.p. 770 + 10°C.

— — IT^^^ ^_^__^ . *•

(0 20 40 50 60 RbF (mole %)

Fig, 3.7. The System KF-RbF.

20

3.8. The System L i F - N a F - K F


sci. U.R.S.S. 31, 753-54 (1941).

The system L i F - N a F - K F contains a single eutectic at 46.5 L iF -11 .5 NaF-42.0 KF

(mole %), m.p. 454°C.

UNCLASSIFIED ORNL-LR-DWG 1!99A

NaF 990

Fig. 3,8, The System L i F - N a F - K F .

21

3.9. The System LiF-NoF-RbF

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


Preliminary diagram. The system L iF -NaF-RbF contains a single eutectic at 42 L i F - 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.


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). Dergunov lists the composition and tempera-

ture of the ternary eutectic as 46.5 L iF -6 .5 NaF-47 RbF (mole %), m.p. 426°C.

Fig. 3.9. The System L iF -NaF -RbF .

22

3.10. The System L i F - K F - R b F



Preliminary diagram. The system L i F - K F - R b F contains a single eutectic at 40 L iF -32 .5

KF-27.5 RbF (mole %), m.p. 440 ± 10°C.




856 f 4 8 5 845

Fig. 3.10. The System L i F - K F - R b F .

23

3.11. The System NaF-KF-RbF

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


Preliminary diagram. The system NaF—KF—RbF contains a single eutectic at 21 NaF-5

KF-74 RbF (mole %), m.p. 621 + 10°C.

990 £ 710 856

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

24

3.12. The System NoBF^-KBF^

R. E. Moore, J. G. Surak, and W. R. Grimes, unpublished work performed at the Oak Ridge

National Laboratory, 1957.

Preliminary diagram. The system NoBF . -KBF^ contains a single eutectic at 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

600

500

5 400

300

200

100

UNCLASSIFIED ORNL-LR-DWG35487

10 20 30 40 50 60 NoBF. (mole7o)

70 80 90

Fig. 3.1Z The System NoBF^-KBF^.

25

3.13. The System N a F - F e F j

R. E. Thoma, H. A. Fr iedman, B. S. Landau, and W. R. Gr imes, unpubl ished work performed

at the Oak Ridge Nat ional Laboratory, 1957.

Pre l iminary diagram.


Mole % FeF,

in Liquid

Invariant

Temperature

(°C) Type of Equilibriun Phase Reaction


30

50

63

680

783

745

Eutectic

Congruent melting point

Eutectic

L ^ = ^ N a F + NaF-FeF2

L ^ = ? NaF-FeFj

L ; = ^ NaF-FeF, + FeF,

UNCLASSIFIED ORNL-LR-DWG 2 2 3 4 5

900

HJ 8 0 0

5 0 0 30 40 50 60

FeFj (mole %) 70

1

\

\

1

I

'

\ ! > - ^

\ \

y^ v ^

U-o •z.

~~-^

/

y

/

y

/

X' /

i

80

Fig. 3.13. The System NaF-FeF_.

26

3.14. The System N o F - N i F j

R. E. Thoma, H. A . Fr iedman, B. S. Landau, and W. R. Grimes, unpubl ished work performed

at the Oak Ridge Nat iona l Laboratory, 1957.

Pre l im inary diagram.

invariant Equilibria

Mole % N i F ,

in Liquid

Invariant

Temperature

{°C)

Type of Equilibrium Phase Reaction


23

50

57

795

1045

1040

Eutectic


Eutectic

L

L

- N a F H-NaF-NiF,

::̂ NaF-NiF,

L ^ ^ ^ N o F - N i F j + N i F j

(300

noo

900

6 0 0

NoF to 30 40 50 60 NiF2(mole %)

70


u.

li-o 2

80 9 0

Fig. 3.14. The System NaF-N iF - .

27

3.15. The System RbF-CoFj

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

the Oak Ridge National Laboratory, 1956.


Invariant Equil ibria

Mole % C a F ,

in Liquid

Invariant

Temperature

(°C) Type of Equilibrium Phase Reaction


9

50

57

760

1110

1090

Eutectic


Eutectic

L ^ = i R b F -I- R b F - C a F ,

L ^ ^ R b F - C a F ,

L ^ ^ ^ R b F - C a F j + C a F j

UNCLASSIFIED O R N L - L R - D W G 17668R

1500

(300

(200

700

o THERMAL ANALYSIS DATA

• VISUAL OBSERVATION DATA

20 40 50 60 CaFj (mole7o)

90 CaF,

Fig. 3.15. The System R b F - C a F j .

28

3.16. The System L lF -NaF-CaF2

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 L i F - N a F - C a F j contains a single eutectic at 53 L i F -

36 NaF-11 CaFj (mole %), m.p. 616°C.

- 1350 -

UNCLASSIFIED ORNL-LR-DWG (2779R

TEMPERATURES ARE IN °C COMPOSITION IN mole7o

' 730^ 6(2

"625

5 A DV T T ^ >»\ 6 6 0 . * ^ >, 663,620

—^zpr

3.17. The System NaF-MgF2-CaF2

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




Com

NaF

65

35

position of L

(mole %)

C a F j

23

28

quid

M g F j

12

37

Te mperature

(°C)

745

905

Type of

Equilibrium

Eutectic

Eutectic

Solids Present


NaF , N a F - M g F j , and C a F j

C a F j , M g F j , and N o F - M g F j

UNCLASSIFIED ORNL-LR-DWG 17575R

COIVIPOSITION IN mole 7o

TEMPERATURE IN °C

Fig. 3.17a. The System N a F — M g F , — C a F ~

30

The minimum temperature along the quasi-binary section N a F - M g F 2 - C a F 2 occurs at the

composition 36 N a F - 3 6 M g F 2 - 2 8 C a F j (mole %) , at 910°C.

The existence of the compound N a r - M g F j was previously reported by A. G. Bergman and

E. P. Dergunov, Compt. rend. acad. sci. U.R.S.S. 3 1 , 755 (1941).

Ternary systems of alkali fluorides with MgF2 have been reported by Bergman et al. as

follows: the system L i F - N a F - M g F j by A. G. Bergman and E. P. Dergunov, Compt. rend. acad.

sci. U.R.S.S. 3 1 , 755 (1941); the system L i F - K F - M g F 2 by A. G. Bergman and S. P. Parlenko,

Compt. rend.acad. sci. U.R.S.S. 3 1 , 818 -19 (1941); the system N a F - K F - M g F 2 by A. G. Bergman

and E. P. Dergunov, Compt. rend. acad. sci. U.R.S.S. 48, 330 (1945).


O

1500

1400

1300

LU Q: 1200

< u 1100 Q.

•- 1000

9 0 0

"^•--

• ^ T . .

1

1 1

y y' •

y

y y

y y

y y

y

y

^^ y

y y

1 y y

y

X y

800 NaMgFj 10 20 30 4 0 5 0 60 70 80 90 CoFg

CoFg (mole 7o)

Fig. 3.17fc. The Subsystem N a F ' M g F j - C a F j .

31

3.18. The System NaF-KF-AIF3



Preliminary diagram. No study has been made at the Oak Ridge National Laboratory of the

phase relationships occurring within the system NaF—KF—AlF,. Phase diagrams have been

reported for the AIF^ binary systems, N a F - A I F j [P. P. Fediotieff and W. P. I l j insky, Z. anorg.

Chem. 80, 121 (1913); also N. A. Pushin and A. V. Baskow, ibid. 81, 350 (1913)] and KF-AIF3

[P. P. Fediotieff and K. Timofeef, Z. anorg. u. allgem. Chem. 206, 265 (1932)].

71000

Fig. 3.18. The System N a F - K F - A I F j .

32

3.19. The System L i F - B e F j

This phase diagram is a composite from several published sources and from unpublished

data derived at the Oak Ridge National Laboratory (R. E. Moore, C. J. Barton, R. E. Thoma,

and T. N. McVay) and at the Mound Laboratory (J. F. Eichelberger, C. R. Hudgens, L. V. Jones,

and T. B. Rhinehammer). Thermal gradient quenching data (ORNL) and differential thermal

analysis data (Mound Laboratory) have served to corroborate this composite diagram.

Invar ian t E q u i l i b r i a

Mole % B e F j

in L i q u i d

33 .5 *

52

-

T

Invar iant

emperature

(°C)

454

355

280

Type of Equ i l i b r i um

P e r i t e c t i c

Eu tec t i c

Upper temperature of

s t a b i l i t y for L i F ' B e F j

Phase React ion

at Invar iant Temperoture

L - l - L i F ^ = ^ 2 L i F ' B e F ,

L ^ ^ 2 L i F . B e F 2 + B e F j

2 L i F . B e F 2 + BeF2 L i F - B e F ,

* R e f 3.

Roy, Roy, and Osborn have reported the presence of the compound LiF-2BeF2 in the system

L i F - B e F j although neither the Mound Laboratory nor the ORNL data have indicated the exist-

ence of this compound.

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

^ A . V . Novose lova , Y u . P. Simanov, and E. I. Yarembash, / . Phys. Chem. (U.S.S.R.) 26, 1244 (1952).

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

^

—— L\¥ +

L

\

F + 2L iF-BeF

\

^

2

\ \

- I

_ 2 L i F - 3 e F o \ _

LIQUID

2L iF-BeF2 i ^

+ f be^g -

^ y ^

2 L i F - B e F

^

2 + BeFg(HI

E

GH QUARTZ

eFg -t- L IQU

TYPE)

1 U F ' B e F 2 - l - BeFg (HIGH QUARTZ

. . 1 1

D

YPE)

L (F -BeF2+BeF2 (LOW QUARTZ TYPE;

10 20 30 40 50 60 70 80 90 BeFj

BeFj (mole 7o)

F i g . 3.19. The System L i F - B e F ,

33

3.20. The System N a F - B e F 2

D. M. Roy, R. Roy, and E. F. Osborn, " F l u o r i d e Model Systems: I I I . The System NaF-

B e F j and the Polymorphism of Na2BeF4 and B e F j , " / . Am. Ceram. Soc. 36, 185 (1953).

Invariant Equilibria*

Mole % BeF j

in Liquid

31

33.3

-

-

43

50

55

T

Invariant

emperature

(°C)

570

600

320

225

340

376 + 5

365

Type of Equilibrium

Eutectic


Inversion

Inversion

Eutectic


Eutectic

Phase Reaction


L ^=i NaF + a-2NaF-BeF2

L ^==^ a-2NaF-BeF2

a-2NaF-BeF2 ^ a '2NaF-BeF2

a'-2NaF-BeF2 ^ = ^ 7-2NaF-BeF2

L I ' a-2NaF-BeF2 + /S-NaF-BeFj

L ; ' ^'•-NaF-BeF2

L ^ = i ^ ' -NaF-BeF j + BeF2

*Roy, Roy, and Osborn did not list invariant equil ibria; those shown are estimates made from the reportec work and from experiments performed at the Oak Ridge National Laboratory.

34

^

N

1-

= ORNL DAT

= HIGH QUA

= LOW QUAF

S ?

o U-o •z.

3

O

+

CD

U

. O

1

^

' 1

: \ \

»

» »

Q (HQ) + LIQU

CD

O

U-

-»-

\ "̂

\ 5 =1 J

li \

^

Li_ O

+ •s U

-o

z. O

J 1

V.

u ^ 1 jj c C

L C

L C

/ / Q

OJ

z + L D

L L 3 0 3

5 2 J I 0." u. LL m

u_ o

Z

1

+

X

OJ

CO

°

+ o

-1

m

u_ D

OJ

"7 / u5^ CD Li_ D U

. O

J O

1

OJ

^

•b i.

. LJ_ o Z + C

D

Li_ D

Z

O

J

OJ

3yniva3dW3i

to 00

UL

0)

m

u. o Z

E 0)

CM

3.21. The System K F - B e F j

R. E. Moore, C. J. Barton, L. M. Bratcher, T. N. McVay, G. D. White, R. J. Sheil, W. R.

Grimes, R. E. Meadows, and L. A. Harris, unpublished work performed at the Oak Ridge National

Laboratory, 1955-56.



Mole % BeF2

In Liquid

19

25

27

33.3

-

52

59

66.7

-

72.5

Invariant

Temperature

(°C)

720

740

730

787

685

390

330

358

334

323

Type of Equilibrium

Eutectic


Eutectic


Inversion

Peritectic

Eutectic


Inversion

Eutectic

L

L

L

L

a-

A L

L

a -

L

Phase Reaction


F = ^ K F + 3KF-BeF2

F=^3KF-BeF2

F = ^ 3KF-BeF2 + a-2KF-BeF2

^ = ^ a - 2 K F - B e F 2

2KF-BeF2 ^ ^ / S - 2 K F - B e F 2

2KF-BeF2 + L ^ = ^ K F - B e F 2

^ ^ KF-BeF2 + /3.KF-2BeF2

^ = ^ a-KF-2BeF2

KF-2BeF2 ?=^^ -KF-2BeF2

^ ^ - K F - 2 B e F 2 + BeF2

This system has been reported by M. P. Borzenkova, A. V. Novoselova, Yu. P. Simanov,

V. I. Chernikh, and E. I. Yarembash, "Thermal and X-Ray Analysis of the K F - B e F j System,"

Zhur. Neorg. Khim. 1, 2071-82 (1956).

36

UNCLASSIFIED ORNL-LR-DWG (7574R

800

700

600

500

400

300

^ s

\

OJ

CD Lu

ro

y y^

\^°

C\J Q .

OJ

03,

- 2 K F BeFj

\

\ CM

L_

GO

^

,a-KF -•2B

u^ CD (M

^

i

/

^

^^ >̂ ^^

20 40 50 60 BeFj (mole %)

9 0 BeF,

Fig. 3.21. The System KF-BeF2.

37

3.22. The System RbF-BeFj

R. E. Moore, C. J. Barton, L. M. Bratcher, T. N. McVay, G. D. White, R. J. Sheil, W. R.

Grimes, and R. E. Meadows, unpublished work performed at the Oak Ridge National Laboratory,

1955-56.



Phase Reaction


L ̂ ^ RbF-I- 3RbF-BeF2

L ^=^3RbF-BeF2

L ̂ =i3RbF-BeF2 + 2RbF.BeF2

L ^^2RbF-BeF2

L + 2RbF-BeF2 ̂ =^RbF.BeF2

L ^ ^ RbF-BeF2 + RbF.2BeF2

L ^=^RbF-2BeF2

L ^ = ^ RbF-2BeF + BeF

This system has also been reported by R. G. Grebenshchikov, "Investigation of the Phase

Diagram of the RbF-BeF2 System and of Its Relationship to the BaO-Si02 System," Do^/aJy

Akad. Nauk S.S.S.R. 114,316(1957).

Mole % BeF j

in Liquid

16

25

27

33.3

50.5

61

66.7

81

Ti

Invariant

emperature

(°C)

675

725

720

800

442

383

464

397

Type of Equilibrium

Eutectic


Eutectic


Peritectic

Eutectic


Eutectic

90 BeF,

Fig. 3.22. The System RbF-BeF2.

39

3.23. The System CsF-BeFj

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

of the System CsF—BeF2 and its Interrelationships with MeF and BeF2 Systems," Doklady

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


Mole % BeFj

in Liquid

14

23.5

-

33.3

-

48

50

-

-

58.4

66.7

-

77.5

Invariant

Temperature

(°C)

598

659

617

793

404

449

475

360

140

393

480

450

367

Type of Eqi

Eutectic

Peritectic

Inversion

Congruent

Inversion

Eutectic

Congruent

Inversion

Inversion

Eutectic

Congruent

Inversion

Eutectic

me

me

me

j i l ibrium

Iting

Iting

Iting

point

point

point

Phase Reaction


L F = ^ CsF -F/e.3CsF-BeF2

a-2CsF-BeF + L ; = ^ a-3CsF-BeF2

a-3CsF-BeF2 F = ^ /3-3CsF-BeF2

L F = ^ a-2CsF-BeF2

a-2CsF-BeF2 F=^/3-2CsF-BeF2

L F = ^ a-2CsF-BeF2 - i -a-CsF-BeFj

L f = ^ a-CsF-BeF2

a-CsF-BeF2 F ^ /S-CsF-BeF2

/3-CsF-BeF2 F = ^ y -CsF-BeF j

L F = ^ a-CsF-BeF2-t-/3-CsF-2BeF2

L ; ' a-CsF-2BeF2

a-CsF-2BeF2 F=^/3-CsF-2BeF2

L f = i /3-CsF-2BeF2 + BeF2

40

900

800

700

600

500

400

300

200

UNCLASSIFIED ORNL-LR-DWG 3 5 4 8 1

3.24. The System L i F - N a F - B e F j

R. E. Moore, C. J. Barton, W. R. Grimes, R. E. Meadows, L. M. Bratcher, G. D. White, T. N.

McVay, and L. A. Harris, unpublished work performed at the Oak Ridge National Laboratory,

1951-58.



Composition of Liquid

(mole %)

L i F NaF BeF,

Invariant

Temperature

;°c)

480

328

355

318

Type of Equilibrium

Eutectic

Eutectic


Eutectic

Solids Present

at Invariant Point

15

23

20

5

58

41

40

53

27

36

40

42

NaF, L iF , and 2NaF-BeF2

L i F , 2NaF-BeF2, and

2NaF-LiF-2BeF2

2NaF-LiF-2BeF^

NaF-BeF2, 2NaF-BeF2, and 2NaF-LiF-2BeF^

31.5 31 37.5 315 Eutectic 2LiF-BeF2, L i F , and 2NaF-LiF-2BeF^

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

Minimum Temperature on Alkemade Lines

Composition of Liquid (mole %)

L i F NaF BeF,

Temperature

(°C) Alkemade Line

16

26

11

16

30.5

56 28

37 37

44 45

45 39

31 38.5

485

340

332

343

316

2NaF-BeF2-LiF

2NaF-L iF-2BeF2-L iF

NaF-BeF2-2NaF-LiF-2BeF2

2NaF-BeF2-2NaF-LiF-2BeF2

2LiF-BeF2-2KaF-LiF-2BeF2

Phase relationships of two of the ternary compounds in this system have been reported by

W. John ["Si l icate Models. V. NaLi(BeF4), a Model Substance for Monticellite, CaMg(Si04),"

Z. anorg. u. allgem. Chem. 276, 113-27 (1954); "Si l icate Models. V I . Na3Li(BeF4)2, a New

Compound in the Ternary System N a F - L i F - B e F 2 , and Its Relation to Merwinite, Ca3Mg(SiO^)2,"

Z. anorg. u. allgem. Chem. Ill, 274-86 (1954)].

42

CO

(r Q

tr

. ^ C/) U

J R

< ^ X

J

: D

. <

U. »

CO 1

u. D z I iil

3.25. The System LiF-RbF-BeF2

T. B. Rhinehammer, D. E. Etter, C. R. Hudgens, N. E. Rogers, and P. A. Tucker, unpublished

work performed at the Mound Laboratory.


Invariant Equil ibria and Singular Points

Solid Phases Present

2 L i F . R b F - 2 B e F 2

2 L i F - B e F 2 , 2 L i F - R b F - 2 B e F 2 , and BeF2

2 L i F - R b F . 2 B e F 2 , R b F . 2 B e F 2 , and BeF2

2 L i F - R b F . 2 B e F 2 and RbF-2BeF2

2 L i F - R b F . 2 B e F 2 , R b F . B e F 2 , and RbF.2BeF 2

2 L i F - R b F - 2 B e F 2 , L i F - R b F - B e F 2 , and RbF .BeF2

L 1 F . R b F . B e F 2 , 2 R b F . B e F 2 , a n d R b F . B e F j

L i F , 2 L i F - R b F . 2 B e F 2 , and 2 L i F . B e F 2

L.F and 2 L i F . R b F . 2 B e F 2

L r F , 2 L i F . R b F . 2 B e F 2 , and L i F - R b F - B e F j

L i F , 2 R b F . B e F 2 , and L1F .RbF .BeF2

L i F and L i F . R b F - B e F . ,

L i F and 2RbF-BeF2

Corr iposition of

Liquid (mol

L i F RbF

40.0

33.3

33.0

26.0

12.0

11.0

11.5

9.0

50.0

41.5

35.0

23.0

30.0

41.0

43.0

43.0

43.0

20.0

33.3

8.0

12.0

29.0

34.0

35.5

40.0

8.0

19.5

25.5

40.0

35.0

39.5

50.0

54.0

55.0

le %)

BeF2

40.0

33.3

59.0

62.0

59.0

55.0

53.0

51.0

42.0

39.0

39.5

37.0

35.0

19.5

7.0

3.0

2.0

Temperature

(°C)

485

544

295

305-

334

+

±

±

5

5

5

- 3 2 0

± 5

300 ± 5

335

380

426

473

470

530

544

640

527

470

462

+ + + ±

± + +

+

+

± ±

5

5

5

5

5

5

5

5

5

5

5

Type of

Equilibrium


Incongruent melting point of L1F .RbF.BeF2

Eutectic

Peritectic

Quasi-binary eutectic

Eutectic

Peritectic

Peritectic

Peritectic

Quasi-fainary eutectic

Peritectic

Peritectic

Maximum on the boundary

Quasi-binary eutectic

Peritectic

Peritectic

Eutectic

L i F , 3RbF .BeF2 , and 2RbF .BeF2

L i F , L i F - R b F , and 3RbF-BeF2

L i F - R b F , RbF, and 3RbF-BeF2

44

http://L1F.RbF.BeF2http://L1F.RbF.BeF2http://L1F.RbF.BeF2

UNCLASSIFIED ORNL-LR-DWG 38H3

BeF2

TEMPERATURE °C COMPOSITION mole 7o

LigBeF^

RbjBeFg

LiRbFj P E RbF

Fig. 3.25. The System Li F -RbF-BeF,

45

3.26. The System NaF-KF-BeF2

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 NaF-KF—BeF2 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 l isted.

2 \548

^ Q O -

a^2-

UNCLASSIFIED O R N L - L R - D W G 3S114

TEMPERATURE IN °C COMPOSITION IN mole %

y^ KF 2 BeF,

NaF^ 9 9 0

£"-365 ,

NaF BeF,

i f - 3 4 0 ,

3 5 0 ^

- 4 5 0 -

4 0 0 ,

- 5 0 0 -

^ - 3 9 0 KF 2 BeFj

750^

'oS^

— ^

535^^ ,

v\

A 2KF BeFj

TA^JKF BeFj

A__Af-720

• ^ O Q

s950_^

\L \J_

~g50

V V

^50N

\ / /

fE-GZQ

A ^

750

M.

' 8 0 0

KF " 8 5 6

Fig. 3.26. The System N a F - K F - B e P ,

46

3.27. The System NoF-RbF-BeFj

R. E. Moore, C. J. Barton, L. M. Bratcher, and W. R. Grimes, unpublished work performed



Invariant Equil ibria and Singular Points

Con-

L iq i

NaF

20.5

50

46

45

37

52

33

51.7

iposition

lid (mole

RbF

68.5

37.5

38

37

33

15

33.7

15

of

%) BeF j

11.0

12.5

16

18

30

33

33.3

33.3

Temperature

(°C)

610

640

635

650

570

477

580

480

Type of Equilibrium Solids Present at Invariant Temperature

Eutectic RbF , N a F , and 3 R b F . B e F 2

Quasi-binary eutectic 3 R b F ' B e F _ and NaF

Eutectic 3 R b F - B e F 2 , 2 R b F - B e F 2 , and NaF

Quasi-binary eutectic 2 R b F ' B e F _ and NaF

Peritectic 2 R b F - B e F 2 , N a F , and 2 N a F . 4 R b F . 3 B e F 2

Eutectic 2 N a F ' 4 R b F . 3 B e F 2 , N a F , and 2 N a F ' B e F 2

Peritectic

Quasi-binary eutectic 2 N a F - 4 R b F ' 3 B e F 2 and 2NaF«BeF_

2RbF-BeF2 and 2 N a F . 4 R b F . 3 B e F 2

UNCLASSIFIED ORNL-LR-DWG 22343R2

BE BINARY EUTECTIC BP BINARY PERITECTIC CM CONGRUENT MELTING POINT IM INCONGRUENT MELTING POINT TE TERNARY EUTECTIC TP TERNARY PERITECTIC

TEMPERATURES BeFg

ARE IN °C CM 543

COMPOSITION IN mole 7o

BE 395

BE 375

B P 4 4 0 RbF BeF,

BE 375

I M 4 4 0

2RbF BeFp CM 8 0 0

BE 720 3RbF BeFp CM 725 •

BE 675,

BE 335

2NaFBeF2 • CM 595

BE 570

Fig. 3.27. The System N a F - R b P - B e F j .

3.28. The System N o F - Z n P j


Ridge National Laboratory, 1952.



Mole % Z n F j

in L i q u i d

Invar ian t

Temperature

(°C) Type of Equ i l i b r i um Phase React ion

at Invar iant Temperature

33

50

69

635

748 + 10

685

Eutec t i c

Congruent mel t ing po in t

Eu tec t i c

L

L

L

, NaF - H N a F - Z n F j

? = i N o F - Z n F j

^ = i N a F - Z n F j + Z n F j

tOGO

900 —

UNCLASSIFIED DWG 14627 R

6 00

5 00 —

4001- 20 30 40 50 60 Zn Fp (mole %)

Fig. 3.28. The System N a F — Z n F j .

48

3.29. The System KF-ZnF2





Mole % ZnF„

in Liquid

Invariant

Temperature

(°C)



21

30

50

80

670 Eutectic

720 + 10 Peritectic

850 + 10 Congruent melting point

740 ± 5 Eutectic

L ? = ^ K F + 2KF.ZnF2

L - f K F - Z n F j ; = ^ 2 K F - Z n F 2

L ^ = ^ K F - Z n F 2

L ^ = ^ K F - Z n F 2 + ZnF2

1000

900

800

700

lij 6 0 0

500

400

UNCLASSIFIED DWG (4625R

300 40 50 60

ZnFj (mole7o)

ZnF,

Fig. 3.29. The System K F - Z n F - .

49

3.30. The System RbF-ZnFj





Mole % Z n F j

in Liquid

21

32

50

70

Invariant

Temperature

{°C)

595 ± 10

620 ± 10

730 ± 10

650

Type of Equilibrium

Eutectic

Peritectic


Eutectic

Phase Reaction


L ;̂ ' R b F + 2RbF.ZnF2

L + RbF-ZnFj F = ^ 2RbF-ZnF2

L f = ^ R b F . Z n F 2

L I ' RbF.ZnF2 + Z n F j

1000

900

8 0 0

7 0 0

600

500

4 0 0

UNCLASSIFIED DWG 15349R

® ® ^ ^ ®

C

Nl

b_ Q: C\J

^ j ^ ^ ^ ® ^

C

Nl

U-Q:

® /

(J, y B T ^ O U U

1

RbF 10 20 30 50 70 90 ZnF,

Fig. 3.30. The System RbF-ZnFjp

50

3.31. The System L i F - Y F j

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




Mol

i n

e %

L i q

19

49

YF3 u i d

T

I n v a r i a n t

e m p e r a t u r e

(°C)

695

815



Eutectic

Peritectic

L ^ ^ L i F + L iF-YFg

L + Y F g ^ ^ ^ L1F.YF3

1400

1300

1200

1100

1000

900

UNCLASSIFIED ORNL LR-DWG 38116

8 0 0 -

700

5 0 0

Fig. 3.31. The System L i F - Y F 3 .

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.



Mole % ZrF^

in Liquid

21

25

-

-

29.5

33.3

49

51.5

-

Invariant

Temperature

(°C)

598

662

475

470

570

596

507

520

466

Type of Equilibrium

Eutectic


Inversion

Decomposition

Eutectic


Eutectic

Peritectic

Decomposition

L ^

L ^ -

a-3L

/^-3L

L ^

L f =

L^=

Phase Reaction


=i L iF + a - 3 L i F - Z r F ^

— a -3L iF 'Z rF^

iP.ZrF^ ^=^ p.3UF-ZrF^

iF 'Z rP^ ^ = ^ L iF + 2LiF-ZrF4

=^a-3LiF.ZrF . + 2 L i F . Z r F . 4 4

=^2LiF-ZrF4

: ^2L iF -Z rF4 + 3LiF-4ZrF4

L + ZrF4 ^ = ^ 3 L i F . 4 Z r F 4

3L iF.4ZrF^ f = ^ 2LiF.ZrF4 + ZrF^

52

UNCLASSIFIED ORNL-LR-DWG (6951

! 1 1 1 1

1 >

. 1

—

\ j - d -JL iF ZrF^ + LIOUID ' Ji

LiF+ LIQUID \ 1 V

t !-3LiF ZrF^ + 2LiF ZrF^^^

LiF+ a -3L iF ZrF^

^ ^ Vi X

, . , i . . _ ' / - L i r 1-p oLir- irr-^

2L;F ZrF^+/3-3LiF ZrF^^

LiF+ 2LiF ZrF^

/

^2LiF ZrF^+LIQUID /

1 ^ / 2LiF + LIQt in \ / * ^

\ ^ ' 2LiF ZrF^+ 3L(F 4ZrF^

^

' ZrF^+LIQUID

1 ! F 4ZrF,+LIQUID

\

M

-J CM

1

3LiF 4ZrF4+ZrF^

^ 3 L i F 4ZrF,

2LiF ZrF,+ ZrF^

LiF 10 20 30 40 50 ZrF. (mole%)

60 70 80 90

Fig. 3.32. The System L iF -Z rF^ .

53

3 .33 . The System NcF-ZrF^

C. J. Barton, W. R. Grimes, H. Insley, R. E. Moore, and R. E. Thoma, "Phase Equilibria

in the Systems NaF-ZrF^ , UF^ -Z rF^ , and N a F - Z r F ^ - U F ^ , " / . Phys. Chem. 62, 665-76 (1958).


Phase Reaction


L f = ^ N a F + 3NaF-ZrF, 4

L F=^3NaF .Z rF *

a-5NaF.2ZrF^ ^ = i /S-5NaF.2ZrF^

a-5NaF-2ZrF^ss ^ ^ /3-5NaF.2ZrF^ +

+ 7-2NaF'ZrF^

34 640 Peritectic L + 3NaF.ZrF^(sj:, ca. 27.5 mole %

Z r F . ) ^ = ^ a - 5 N a F . 2 Z r F . 4 4

39.5 544 Peritectic L + a-5NaF.2ZrF^(ss, 30 mole %

ZrF. ) = = f a-2NaF.ZrF, 4 V 4

Mole % ZrF^

in Liquid

20

25

-

30.5

T.

Invariant

emperature

(°C)

747

850

523

500

Type of Equilibrium

Eutectic


Invers ion

Eutectoid

533 Inversion a-2NaF.ZrF, p= i / 3 -2NaF .Z rF 4 '

505

4

Inversion /3-2NaF.ZrF^ ^=^ -y .2NaF.Z rF^

40.5 500 Eutectic L '7 -2NaF.ZrF^ + 7NaF.6ZrF^s5

46.2 525 Congruent melting point L ^ 7NaF-6ZrF.

49.5 512 Eutectic L ^ = ^ 7NaF-6ZrF^ + 3NaF.4ZrF^

56.5 537 Peritectic L + Z r F . = = = : 3NaF.4ZrF.

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

Structures of No jZrF^ and NogHfF^," Acta Cryst. 12, 172 (1959).

54

TE

MP

ER

AT

UR

E

(°C

)

CO

Q •n

I N

"n

O

IV

O

O

-Ci

O

NJ 3

ui

1 o

59

en

0 0 0 0

3N

aF

Z

rF^

ZZ

rF^

2N

aF

Z

rF^

3N

aF

2

ZrF

^ ^

^

7N

aF

6

ZrF

^

3N

aF

4

ZrF

4

" r

J \ S

fc^ X

1

_——̂

-^

^

^ '—

—

\

X 9

J

\ 0

1

3.34. The System K F - Z r F ^

C. J . Bar ton, H. Ins ley, R. P. Metcal f , R. E. Thoma, and W. R. Grimes, unpubl ished work

performed at the Oak Ridge Nat ional Laboratory, 1951-55.



Mole % ZrF^j

in Liquid

14

25

36

40.5

42

50

55

Invariant

Temperature

{°C)

765

910

590

412

390

475

440

Type of Equilibrium

Eutectic


Peritectic

Eutectic


Eutectic

Phase Reaction


L f = ^ K F + 3KF-ZrF^

L ^ = ^ 3KF-ZrF^

3KF-ZrF4 + L ^ = ^ 2 K F - Z r F 4

?KF'ZrF + L ^3KF'27rF

L F = ^ 3KF-2ZrF4 + KF-ZrF^

L f = ^ KF 'ZrF^

L ?==i KF-ZrF^ + ZrF^

UNCLASSIFIED

O R N L - L R - D W G 1 8 9 6 5

1000

900

8 0 0

7 0 0

6 0 0

5 0 0

4 0 0

3 0 0

- f r

1 , ^

N

Li_

m

\

r i i 5

U-

:̂ CO

^

u5 U

M OJ

L L

I ^ J /

v Li5

N

U-

K /

Y —

—

20 30 40 50 ZrF, (mole 7o!

70 80

Fig. 3 . 34 The System K F - Z r F ^ .

56

3.35. The System R b F - Z r F ^

R. E. Moore, R. E. Thoma, C. J . Barton, W. R. Gr imes, H. Ins ley, B. S. Landau, and H. A.

Fr iedman, unpubl ished work performed at the Oak Ridge Nat iona l Laboratory, 1955—56.



Mole % ZrF^

in Liquid

Invariant

Temperature

(°C) Type of Equilibrium

Phase Reaction


10

25

34

42

44.4

48

50

54

57

710 Eutectic

897 Congruent melting point

620 Peritectic

460 Inversion

370 Lowered inversion and decomposition

410 Eutectic


390 Eutectic


391 Inversion

400 Eutectic

447 Peritectic

RbF + 3 R b F . Z r F ,

3 R b F . Z r F ,

L + 3 R b F . Z r F . s s 4

: a - 2 R b F . Z r F ,

a - 2 R b F . Z r F ^ ^ = : i / 3 . 2 R b F . Z r F _ j

a - 2 R b F . Z r F 4 S s F = ^ /3-2RhF-ZrF^SS

a - 2 R b F . Z r F .ss + 5 R b F . 4 Z r F . 4 4

5 R b F . 4 Z r F ,

L F = ^ 5 R b F . 4 Z r F ^ + /3 -RbF .ZrF^

L ^ = i a - R b F - Z r F . ^ 4

a-RbP-ZrF^ F = ^ /3-RbF.ZrF^

L ^ = i a-RbF-ZrF . + RbF.2ZrF . 4 4

L + Z rF^ ^ = ^ R b F . 2 Z r F ^

ZrF, lmol67.)

Fig . 3.35. The System R b F - Z r F 4 .

\ r

1

X

% a

^N

1 1 1 1 1 1

/ 1

i-

1

\

J 3

1 \ \ \ \ \ \ \ 1 \

—1—Y 1 \ 1

1 n t 1 1

V

V N

CC

"'

^--1^

, —

/

x~~

\r

az

-^ / N / N

°=

^

• — —

57

3.36. The System CsF-ZrF^





Mole % ZrF^

in Liquid

9

25

35

40

50

-

59

Invariant

Temperature

(°C)

640

775

520

420

515

320

470

Type of Equilibrium

Eutectic


Peritectic

Eutectic


Inversion

Eutectic

Phase Reaction


L ^ = ^ CsF + 3CsF.ZrF4

L ? = ^ 3CsF.ZrF^

L + SCsF-ZrF^ ^ = ^ 2CsF-ZrF4

L ^^=i 2CsF.ZrF^ + a-CsF-ZrF^

L ^ = ^ a-CsF-ZrF^

a - C s F - Z r F ^ ^ ^ ^ /3-CsF.ZrF^

L ? = ^ a-CsF.ZrF_^ + ZrF^

58

TE

MP

ER

AT

UR

E

(°C

)

w

Tl I N

3C

sF-Z

rF^

2CsF

CsF

-Zr

ZrF

^

^4

^ N y \ ) \

/

^

-^

I

N \ \

y ^

\

\ \

3.37. The System L iF-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.


invariant Equilibria

Composition of Liquid ^mol V) Temperature Type of Solids Present

Invariant at Invariant Temperature L i F

37

55

32

31

31

26

29

29

28

NaF

52

22

36

35

34.5

37

25.5

24.5

24

Z r F ,

11

23

32

34

34.5

37

45.5

46.5

48

604

590

450

448

445

425

449

453

475

Eutectic

Eutectic

Peritectic

Peritectic

Peritectic

Eutectic

Eutectic

Peritectic

Peritectic

NaF, L iF, and 3NaF.ZrF,

a -3L iF .ZrF , , 3NaF.ZrF,ss, and LiF

/S-SLiF-ZrF,, 3t^aF.ZrF^ss, and 2L iF .ZrF ,

3NaF.ZrF,, a-5NaF.2ZrF,ss, and 2LiF .ZrF ,

2NaF.ZrF, , a-5NaF.2ZrF4Ss, and 2LiF.ZrF4

2NaF.ZrF, , 7NaF.6ZrF,, and 2LiF.ZrF4

7NaF.6ZrF,, 2HaF.4ZrF^ss. and 2LiF.ZrF4

3NaF.4ZrF,S5, 3LiF.4ZrF,ss, and 2L iF .ZrF ,

3NaF.4ZrF,ss, 3LiF.4ZrF,ss, and Z r F ,

60

UNCLASSIFIED O R N L - L R - D W G 38115

TEMPERATURE IN C COMPOSITION IN mole %

II INDICATES SOLID SOLUTION

i N o F 4 Z r F ^ -

/ ° - 5 3 7

£ - 5 1 2

3L iF • 4 Z r F ,

-P-520 f-507

7 NaF- 6ZrF^

f -

P-544

/°-640,

2NaF-ZrF4-;;,

5NaF 2ZrF4~

3NaF-ZrF4

E- 747-

f -570

£-605

£-652 LiF 845

Fig. 3.37. The System L i F - N a F - Z r F , .

61

3.38. The System N o F - K F - Z r F ,

R. E. Thoma, C. J. Barton, H. Insley, H. A. Friedman, and W. R. Grimes, unpublished work

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



Composition of i • ^ Invariant

" " ' ° Temperature Type of Equilibrium Solids Present at Invariant Point

NaF KF Z r F , (°C)

695 Eutectic NaF, KF, and 3KF-ZrF ,

720 Eutectic NaF, SKF-ZrF,, and 3NaF.3KF.2ZrF,

710 Eutectic NaF, 3NaF-ZrF, , and 3NaF.3KF.2ZrF,

Peritectic 3NaF.ZrF, , 3NaF-3KF.2ZrF,, and

NaF.KF.ZrF,

Peritectic 3NaF.ZrF, , NaF-KF 'ZrF , , and

5NaF.2ZrF,

Peritectic 3NaF.3KF.2ZrF,, SKP.ZrF, , and

NaF-KF.ZrF,

12 51 37 Peritectic SKP.ZrF, , 2KF.ZrF , , and

NaF.KF.ZrF,

40 21 39 Peritectic 5NaF.2ZrF,, 2NaF.ZrF, , and

NaF.KF.ZrF. 4

Peritectic 2NaF.ZrF, , 7NaF.6ZrF,, and

NaF.KP.ZrF,

34

45

61

52

48

33

58

38

19

17

18

32

8

17

20

31

34

35

39

11

10

15

22

25

21

20

21

49

48

40

33

25

29

30

40

40

42

45

45

50

51

50

Peritectic 2KF.ZrF, , 3KF.2ZrF, , and 4

CF

NaF.KF-ZrF,

385 Eutectic 3KF.2ZrF, , KF-ZrF , , and 4

F

NaP.KP.ZrF, 4 Eutectic KF .Z rF , , NaP.KP.ZrF, , and

2NaF.3KF.5ZrF, 4

2NaF.3KF.5ZrF,

Peritectic NaF-KF.ZrF ., 7NaF.6ZrF. , and 4 4

4

Eutectic 7NaF.6ZrF,, 3NaF.4ZrF, , and

2NaF.3KF.5ZrF. 4

Eutectic 3NaF.4ZrF ., Z r F , , and 2NaF.3KF.5ZrF^

4

432 Congruent melting point 2NaF.3KF.5ZrF.

*Three solid phases have been observed routinely in the composition region 30—50 mole % ZrF . which

have not been identified as to composition. Whether these exhibit primary phases at the liquidus surface has

not yet been determined.

**Compositions of invariant points shown by the intersection of dotted boundary curves are approximate.

62

http://3NaF.3KF.2ZrFhttp://3NaF.3KF.2ZrFhttp://3NaF.3KF.2ZrFhttp://2NaF.3KF.5ZrFhttp://2NaF.3KF.5ZrFhttp://2NaF.3KF.5ZrFhttp://2NaF.3KF.5ZrF

UNCLASSIFIED ORNL-LR-DWG35480

TEMPERATURE IN°C

COMPOSITION IN mole7„ A 2NaF 3KF 5ZrF,

NoF KF ZrF̂

C 3NaF 3KF 2ZrF,

3NaF 4ZrF^ P 537

£512

7NaF 6ZrF,

£ 500 P54A

P 640 2NaF ZrF^ / — 7 5 0

5NaF 2ZrF 4

3NaF ZrE,

£ 747 A

3KF ZrF,

£ 7 6 5

F i g . 3 . 3 8 . T h e Sys tem N a F - K F - Z r F , . T h e i s o t h e r m s for the t e m p e r a t u r e s 6 0 0 , 6 5 0 , and 7 0 0 ° C

b e t w e e n the 30 and 40 m o l e % Z r F , c o m p o s i t i o n s h a v e been o m i t t e d in o rder not to o b s c u r e t h e p h a s e

r e l a t i o n s h i p s in t h i s p o l y t h e r m a l p r o j e c t i o n .

63

3.39. The System N a F - R b F - Z r F ,

R. E. Thoma, H. Insley, H. A. Friedman, and W. R. Grimes, unpubl ished work performed at

the Oak Ridge Nat ional Laboratory, 1951-56.

Prel iminary diagram.


Composi t ion of i • i "̂ Invar iant

L i qu i d (mole %) -r . ^ Temperature

NaF RbF Z r F , (°C) Type of Equi l ibr iun Sol ids Present at Invar iant Point

23 72 5 643

50 27 23 720

37 32 31 605

39 26 35

36.3 24.2 39.5

34.5 24 41.5

34 23.5 42.5

33 23.5 43.5

28.5 21.5 50

28 21.5 50.5

23.5 39.5 37

21 40 39

8 50 42

8.5 47 44.5

545

427

424

422

420

443

446

470

438

400

395

Eutec t ic

Eutec t ic

Eutec t ic

Per i tec t i c

Per i tec t i c

Per i tec t i c

Per i tec t i c

Eutect ic

Eutec t ic

Per i tec t i c

Per i tec t i c

Per i tec t i c

Eutec t ic

Eutec t ic

N a F , R b F , and 3 R b F . Z r F .

6.2

5

6.5

33.3

25

45.8

42

39

33.3

25

48

53

54.5

33.3

50

380

398

423

642

462

Eutectic

Eutectic

Peritectic

Congruent

Congruent

N a F , 3 R b F . Z r F , , and 3 N a F . Z r F ,

M a F . Z r F , , 3Rb

N a F . R b F . Z r F ,

3 N a F . Z r F , , 3 R b F . Z r F , , and

3 N a F . Z r F , , 5 N a F . 2 Z r F , , and

N a P . R b P . Z r F ^ 4

5 N a F . 2 Z r F , , 2 N a F . Z r F , , and

N a F - R b F . Z r F . 4

2 N a F . Z r F , , N a F - R b F . Z r F , , and

3 N a F . 3 R b F . 4 Z r F ,

2 N a F . Z r F , , 7 N a F . 6 Z r F , , and

3 N a F . 3 R b F . 4 Z r F ,

7 N a F . 6 Z r F , , 3 N a F . 3 R b F - 4 Z r F , , and

N a F - R b F . 2 Z r F . 4

3 N a F . 4 Z r F , , 7 N a F . 6 Z r F , , and

N a F . R b F . 2 Z r F . 4

3 N a F . 4 Z r F , , Z r F , , and

N a F . R b F . 2 Z r F . 4

N a F . R b F . Z r F , , 2 R b F . Z r F , , and 3 R b F . Z r F ,

4

N a F . R b F . Z r F , , 2 R b F - Z r F , , and

3 N a F - 3 R b F - 4 Z r F ,

3 N a F - 3 R b F - 4 Z r F , , 2 R b F - Z r F , , and

5 R b F . 4 Z r F , 4

3 N a F - 3 R b F - 4 Z r F , , 5 R b F - Z r F , , and

N a F - R b F - 2 Z r F ,

N a F - R b F - 2 Z r F , , 5 R b F - 4 Z r F , , and

R b F - Z r F ,

N a F - R b F - 2 Z r F , , R b F - Z r F , , and

R b F . 2 Z r F ,

Z r F , , N a F . R b F . 2 Z r F , , and

R b F . 2 Z r F ,

Congruent mel t ing point N a F . R b F - Z r F .

Congruent mel t ing point N a F . R b F - 2 Z r F .

64

http://3NaF.3RbF.4ZrFhttp://3NaF.3RbF.4ZrFhttp://NaF.RbF.2ZrFhttp://NaF.RbF.2ZrFhttp://NaF.RbF.2ZrF

Minimum Temperatures on Alkemade Lines

Composition of Liquid (mole %)

NaF RbF ZrF ,

Temperature (°C)

Alkemade Line

24.75

6

7.5

8.5

28

22

29

37

47

36

30

24.75

44

46.5

48.5

28

40

41.5

24.5

28

48

36.7

51.5

50

46

43

44

38

49.5

38.5

25

16

33.3

455

402

405

405

435

442

450

610

732

777

598

NaF.RbF.2ZrF , -Z rF ,

NaF.RbF-2ZrF. -RbF.ZrF. 4 4

NaF-RbF-2ZrF,-5RbF.4ZrF, 4 4

3NaF-RbF.4ZrF.-5RbF.4ZrF, 4 4

3NaF.RbF.4ZrF.-NaF.RbF.2ZrF, 4 4

3NaF.3RbF.4ZrF,-2RbF.ZrF, 4 4

NaF.RbF.2ZrF,-7NaF.6ZrF,

NaF.RbF.ZrF, -3NaF.ZrF, 4 4

3NaF-ZrF, -3RbF-ZrF,

NaF-3RbF.ZrF,

NaF-RbF.ZrF, -3RbF.ZrF, 4 4

COMPOSITION IN mole %

TEMPERATURE IN "C a NaF RbF 2ZrF^

* 3NaF 3RbF 4ZrF„

C NaF RbF ZrF.

RbF 2Zr^

P447 £ 4 0 0

RbF-ZrF, 423 f 390

5RbF 4ZrF,445

- / '620 2Rbi- ZrF.

3RbF ZrF. 897

Fig. 3.39. The System N a F - R b F - Z r F , .

65

http://NaF.RbF-2ZrF.-RbF.ZrFhttp://3NaF-RbF.4ZrF.-5RbF.4ZrFhttp://3NaF.RbF.4ZrF.-NaF.RbF.2ZrF

3.40. The System NaF-CrF j -Z rF , : The Section NoF-CrFj - ZrF,

R. E. Thoma, H. A. Friedman, B. 5. Landau, and W. R. Grimes, unpublished work performed


Preliminary diagram. No invariant equilibria occur for compositions lying on the section

NaF .CrF j -Z rF , .


9 0 0

600

500

4 0 0 NaF

\ \

\ \

NaF- CrFj

^ \

\ \

\ \

f LIQUID

NaF- CrFj +

NaF-CrFj-l

\ / a-NaF-CrFj

•/3-NaF-CrF

/ /

a-NaF- CrFj +• LIQU

•ZZrF^

2-2ZrF4

- ^

-2ZrF4

ID

^^^'^

CM

O 2

^

CrF^-Zr

cr-NoF-

/3-NaF

" ZrF4+LIQUID

F4 -F LIQUID

CrFj- 2ZrF4

CrF2-2ZrF4

+ ZrF4

-FZrF4

CrF2 10 20 30 40 50 60 ZrF4 (mole 7o)

ZrF.

Fig. 3.40. The Section N a F . C r F j - Z r F , .

66

3.41. The System NoF-CeFg-Z rF ,

W. T. Ward, R. A. Strehlow, W. R. Grimes, and G. M. Watson, "Solubil ity Relationships of

Rare Earth Fluorides and Yttrium Fluoride in Various Molten N a F - Z r F , and N a F - Z r F , - U F ,

Solvents," / . Chem. Eng. Data (in press).


CeF3(1387°C)

ZrF^(918°C)

Fig. 3.41a. The System N a F - C e F , - Z r F , .


PROBABLE NaF- ZrF^ PRIMARY PHASE FIELDS

A ZrF„ D 2NaF-ZrF, '4 " " " " ' " " 4 B 3NaF-4ZrF4 E5NaF-2ZrF4 C 7NaF-6ZrF^ F SNoF- ZrF^

20 . A 20

16

\ • "

%

; \ \ V

Fig. 3.416. The System N a F - C e F j - Z r F , in the Region 30-70 Mole % NaF, 0-20 Mole % CeFj , 30-70 Mole % ZrF , .

67

•

3.42. The System L iF -CeF j

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

the Oak Ridge National Laboratory, 1956-57.

Preliminary diagram. The system L i F - C e F j contains a single eutectic at 81 L iF -19 CeF

(mole %), m.p. 755 + 5°C.

68

#

TE

MP

ER

AT

UR

E

(°C

)

lO N

-I

3- a (/I

•<

H a 3 r Tl

« tp ) ) )

/ \

\ V

, K S-̂ \ \ \

"\

r̂P

ON

3.43. The System N a F - H f F ,

R. E. Thoma, C. F. Weaver, T. N. McVay, H. A . Fr iedman, and W. R. Grimes, unpubl ished

work performed at the Oak Ridge National Laboratory, 1956-58.

Prel iminary diagram.


Mole % HfF, in Liquid

18.5

25

34

-

35

-

43

45

50

53

Invariant

Temperature

(°C)

Be

Be

695

863

606

535

586

low 350

low 350

510

531

557

535

Type of Eq

Eutectic

Congruent

Peritectic

Inversion

Peritectic

Inversion

Eutectic

Peritectic

Congruent

Eutectic

me

me

ui

Iti

It

librium

ing

ing

poi

poi

nt

int

Phase Reaction


L F = ^ NaF-f 3NaF.HfF,

L f = ^ 3 N a F . H f F , *

L + 3NaF.HfF, ^ = ^ a.5NaF.2HfF,

a-5NaF.2HfF, ^==i:/3-5NaF.2HfF,

L + a-5NaF.2HfF, p = ^ ;S-2NaF.HfF,

/S.2NaF.HfF, ^ ^ 7-2NaF.HfF,

'V-2NaF.HfF : ^ ?-2NaF-HfF

L ^ = ^ /3-2NaF.HfF, + 7NaF.6HfF,

L + NaF.HfF, ^=^7NaF .6HfF ,

L F = ^ NoF.HfF,

L ^ NoF.HfF, + HfF,

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

Structures of NogZrF^ and NajHfF^," Acta Cryst. 12, 172 (1959).

70

1050

9 5 0 -

8 5 0

750

650

UNCLASSIFIED ORNL-LR-OWG 35488

450

350 NQF

V

\ , v A

(

l i ?

o

fN. \

I CM U.

z in

-

\

\

\ \

u ?

X

o z

N^ / " • ^ v̂

\g

o z 1^

I

D z

^

20 30 4 0 50 60 70 80 90

Fig. 143. 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^," / . Phys. Chem. 63, 1266-74 (1959).

Invariant E q u i l i b r i a

Mole % T h F ^

in L i qu i d

23

25

29

30.5

42

62

Invar iant

Temperature

(°C)

568

573

565

597

762

897

Type of Equ i l i b r i um

Eutec t i c

Congruent mel t ing point

Eutect ic

Per i tec t i c

Pe r i t ec t i c

Per i tec t i c

Phase React ion


L ^ ^ L i F + 3 L i F . T h F ^

L ^ 3 L i F . T h F ^

L ^ ^ S L i F ' T h F . + 7 L i F . 6 T h F 4 4

L i F . 2 T h F ^ + L ^ 7 L l F . 6 T h F ^

L i F . 4 T h F . + L F = ^ L i F . 2 T h F ^ 4 4

T h F . + L F = ^ L i F . 4 T h F . 4 4

1150

1050

950

cr 850

< cr ^ 750

650

550

450

1

^

1 \

31

^

. i F - T h F ^ -

r^ / /

7 L i F - 6 T h

/

/

\ -

^

UNCLASSIFIED ORNL-LR-DWG 26535A

/

/

U P 2ThF 4

—

-

l ^

\^

^ _ i "

1

—

LiF 10 20 30 40 50 60 70 80 90 ThF^ ThF^(mole7o)

Fig. 3.44. The System L i F - T h F ^ .

72

3.45. The System NoF-ThF ,

R. E. Thoma, H. Insley, B. S. Landau, H. A. Friedman, and W. R. Grimes, "Phase Equilibria

in the Fused Salt Systems L i F - T h F , and N a F - T h F , , " / . Phys. Chem. 63, 1266-74 (1959).

Invariant E q u i l i b r i a

Mole % T h F ^

in L i q u i d

Invar iant

Temperature

(°C)

Type of Equ i l i b r i um Phase React ion


21.5

22.5

33.3

37

40

41

45.5

58

645

618

604

558

705

690

712

705

683

730

831

Per i tec t i c

Eu tec t i c

Invers ion

Decompos i t ion

NaF + L ^ ^ a - 4 N a F . T h F ,

L ^=^ a - 4 N o F . T h F , + 2 N a F . T h F ,

a - 4 N a F . T h F , ^ = i / 3 . 4 N a F . T h F ,

/ S - 4 N a F . T h F , ; = ^ NaF -f 2 N a F . T h F ,

Congruent mel t ing point L ^ ^ 2 N a F . T h F ,

Eutec t ic

Congruent mel t ing point L ^ ^ 3 N a F . 2 T h F ,

Eutec t ic

Decompos i t ion 3 N a F . 2 T h F

Per i tec t i c

Pe r i t ec t i c

L ^ ^ 2 N a F . T h F , + 3 N a F . 2 T h F ,

L ^ = ^ 3 N a F . 2 T h F , 4- a - N o F - T h F ,

2 N a F . T h F , + a - N a F . T h F ,

N a F . 2 T h F , + L ? = ^ a - N a F . T h F ,

T h F , + L ? = : ^ N a F . 2 T h F ,

cc

< cr Q_

UJ

1150

1050

950

850

750

650

550

UNCLASSIFIED ORNL-LR-DWG 28528AR

450

N \

\

\ \ )

4NaF-ThF4-'

2NQ

L/ V r • ^•ThF^-—

^ » x

/ / ,^

f ^̂ 0

. ^

/

/

\;^

LL o

Y^ / I \ \ \

-7 /

/

\

NaF 10 20 30 40 50 60 70 80 90

T h i ^ (mole 7c,)

Fig. 3.45. The System N a F - T h F , .

ThF4

73

3.46. The System KF-ThF^

W. J. Asker, E. R. Segnit, and A. W. Wylie, "The Potassium Thorium Fluorides," / . Chem.

Soc. 1952,4470-79.

This system has also been reported by A. G. Bergman and E. P. Dergunov, Doklady Akad.

Nauk S.S.S.R. 53, 753 (1941) and by V. S. Emelyanov and A. J. Evstyukhin, " A n Investigation

of Fused-Salt Systems Based on Thorium Fluoride - I I . N a F - K F - T h F ^ , NaF-ThF^ , and K F -

T h F ^ , " / . Nuclear Energy 5, 108-14 (1957).


Mole % ThF^ in Liquid

14

-

-

25

-

31

-

5 0 *

56

66

75

78

Invariant

Temperature

(°C)

694

635

712

865

570

691

747

645

905

875

930

990

980

Type of Equilibrium

Eutectic

Inversion

Pentectic


Decomposition

Eutectic

Pentectic

Inversion


Eutectic

Pentectic


Eutectic

Phase Reaction at Invariant Temperature

L < = ^ K F + / 3 - 5 K F . T h F ^

a-SKF-ThF^ ;; ^/3-5KF.ThF^

L + 3KF.ThF^ ^ = ^ a-5KF.ThF^

L I '-SKF-ThF^

3KF.ThF^ ^=: i /3 .5KF.ThF^+/3.2KF.ThF^

L ^ = i 3 K F . T h F ^ + a-2KF.ThF^

L + KF-ThF^ ^ = ^ a-2KF.ThF4

n.9KF.ThF ^ /^.9KF.TIiF

L ^ = ^ K F . T h F ^

L ^ = i KF.ThF^ + KF-2ThF^

L + KF.3ThF^ ^=^KF.2ThF^

L ^=^KF.3ThF^

L ^ = ^ KF-SThF^ + ThF^ss

*lt has been shown that the compound labeled by Asker et al, has the actual formula 7KF'6ThF ., cf. R.

E. Thomo, Crystal Structures of Some Compounds of UF. and ThF, with Alkali Fluorides, ORNL CF-58-12-

40 (December 11, 1958).

74

TE

MP

ER

AT

UR

E (

°C)

3 7s

3 °

SK

F-T

hF^

ZK

F-T

hF

^

KF

-ThF

^

y ^ c ^

3K

F-T

::r;; \

KF

-ZT

hF^

KF

-3T

hF4

/ \ IF,

\

y ^ \ < --

\ / ^ \

N \ <

\

'-

"•

-.

^ \

3.47. The System RbF-ThF^

E. P. Dergunov and A. G. Bergman, "Complex Formation Betv/een Alkal i Metal Fluorides

and Fluorides of Metals of the Fourth Group," Doklady Akad. Nauk S.S.S.R. 60, 391-94 (1948).


Mole % ThF^

in Liquid

15

25

37

50

54

75

80

Invariant

Temperature

(°C)

664

974

762

852

848

1004

1000

Type of Equilibrium

Eutectic


Eutectic


Eutectic


Eutectic

Phase Reaction


L F = ^ RbF + 3 R b F . T h F , 4

L f = ^ SRbF-ThF^

L F = ^ 3RbF.ThF . + RbF-ThF. 4 4

L ^ = ^ RbF-ThF^

L ^= : ^ RbF-ThF^ + RbF.3ThF^

L ^ = ^ RbF.3ThF^

L ^ = ^ RbF-3ThF4 + ThF^

UNCLASSIFIED ORNL~LR-DWG 20461

o 900

E 800 u •^SO

6 6 4 °

1 1

9"

/

SI

L i .

rO

4 0

1

\

\

- ^

\

8;

762°

^ l i _ J 3 Q:

,.. / r~—/

^

848°

1004°

y

L i . X ) Q:

1114^

1000°

1

RbF \0 20 30 4 0 5 0 6 0 70 ThF. (mole % )

9 0 ThF.

Fig. 3.47. The System RbF-ThF^ .

76

3.48. The System BeFj-ThF^

R. E. Thoma, H. Insley, H. A. Friedman, and C. F. Weaver, "Phase Equilibria in the Sys-

tems BeF2-ThF4 and L i F - B e F 2 - T h F 4 , " paper to be presented at the 136th National Meeting

of the American Chemical Society, Atlantic City, N. J . , Sept. 13-18, 1959.

The system BeF2-ThF4 contains a single eutectic at 98.5 BeF2-1.5 ThF4 (mole %), m.p.

526 ± 3°C.


1200 I 1 1 1 ] , , 1 1 , 1

noo ^ ^ . — ^ =

„ 1000 ^ ^ ^ ^ ^ .,— 2— ^ ^ UJ . QL 9 0 0 -^-< y" S 800 y~

'" 700 y \ \

600 —J-

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