Development of the fluorine potential model for

understanding materials corrosion on molten FLiBe

Brian Kelleher, Kumar Sridharan, Mark Anderson, Guiqui Zheng,

Guoping Cao

University of Wisconsin-Madison

October 30th , 2014

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 Outline

1 Fluoride Salt Cooled Reactor (FHR) Materials and Chemistry

Research

2 Equilibrium Chemistry Review

Fluorine Potential

3 Example: Hydrofluorination

4 Example: The Redox Potential of the MSRE

5 Calculating Beryllium Additions

6 Measurement and Validation

7 Conclusions

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 FHR vs. MSRE

Figure : Fluoride Salt Cooled Reactor

(FHR) Core Figure : MSRE core and plumbing.

Coolant Fuel Material Temperature

FHR Li2 BeF4 TRISO 316SS 700 C
MSRE LiF-BeF2 -ZrF4 -UF4 UF4 Hastelloy-N 650 C
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FHR Materials and Chemistry

• FHR program is a integrated research project between MIT

UC-Berkeley, and UW-Madison.
• UW-Madison supports FHR Materials and Chemistry.
• Where to start? Follow the MSRE salt program.

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Salt Purification

Figure : UW Salt Processing

Figure : ORNL Salt Processing
• ORNL made 57153 kg of salt for their research. UW has
re-purified roughly 18 kg.
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Flibe

Figure : Purified flibe. The crystals indicate the presence of L2B or the
Li2 BeF4 molecule. This flibe was used to test FHR materials.
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 Corrosion Tests

Figure : Stainless steel and Figure : In and out of core testing.

Hastelloy-N coupons after 3000 hours
in 700 C flibe.

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What does the FHR need next?

• Precision control of corrosion tests.

• Predict and quantify salt chemistry.
• Create an optimal salt environment for next generation materials.
• Figure out how to control chemistry in an FHR.
• All require deeper chemistry knowledge.
• How to gain a deeper knowledge of the chemistry?

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 Outline

1 Fluoride Salt Cooled Reactor (FHR) Materials and Chemistry

Research

2 Equilibrium Chemistry Review

Fluorine Potential

3 Example: Hydrofluorination

4 Example: The Redox Potential of the MSRE

5 Calculating Beryllium Additions

6 Measurement and Validation

7 Conclusions

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Review: Reaction Equilibrium
The reaction
aA + bB ⌦ cC + dD (1)
has an equilibrium constant, K which can be defined as

[C ]c [D]d
K= . (2)
[A]a [B]b

Bracketed constants are activities, a, or partial pressures, p. The

activities of each species which are defined as

a= . (3)

The equilibrium constant can be related to the concept of Gibbs free

energy through the relation

G= RT ln(K ). (4)

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Fluorine Potential
• In the case of fluoride salts the anion is F . Olander, calling on
previous work done with UO2 fuels, created the ‘fluorine
potential’.1
GF2 = RT ln pF2 . (5)

• However, a partial pressure of fluorine will never exist in the salt

anywhere close to measurable quantities.2
• Fluoride ions in the salt in great quantity. Therefore better to say:
GF = RT ln aF , (6)

• Akin to hydrogen potential (pH).

pH = log10 (aH+ ) (7)
1
D. Olander, Redox condition in molten fluoride salts: Definition and control,
Journal of Nuclear Materials, Volume 300, Issues 23, Feb 2002, Pg. 270-272.
2
Unless performing electrolysis.
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Fluoride Potential Issues

• The amount of F in a fluoride salt cannot change as dramatically

as pH in an aqueous solution.
• Claim: While pH relies on a change in hydrogen ion concentration,
fluoride potential relies on the activity coefficient, , to create
chemical changes.

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 Outline

1 Fluoride Salt Cooled Reactor (FHR) Materials and Chemistry

Research

2 Equilibrium Chemistry Review

Fluorine Potential

3 Example: Hydrofluorination

4 Example: The Redox Potential of the MSRE

5 Calculating Beryllium Additions

6 Measurement and Validation

7 Conclusions

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Example: Fluoride Potential Set by Hydrofluorination

The fluoride ion can be created by the competition between hydrogen

and hydrogen fluoride in the reaction
1
H2 + F ⌦ HF + e . (8)
2
Therefore, the fluoride potential model can be used to establish an
equilibrium as ✓ ◆
pHF GHF
K=p = exp . (9)
p H2 a F RT
Solving for the fluoride potential yields
p
G F = RT ln aF = RT ln pHF / pH2 + GHF (10)

Typical conditions of purification T = 550 C, HF:H2 =1:10,

GF = 68 kcal mol 1

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 Graphical Hydrofluorination

-65

Metal
NiF2
G F - (kcal/mol)

FeF2

Metal Fluoride
-70
CrF2
HF
-75
Hydrofluorination

-80
500 550 600 650
Temperature (o C)

Figure : Hydrofluorination sets a fluoride potential in the salt. Anything less

negative stays metallic, anything more negative is fluorinated.

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 Outline

1 Fluoride Salt Cooled Reactor (FHR) Materials and Chemistry

Research

2 Equilibrium Chemistry Review

Fluorine Potential

3 Example: Hydrofluorination

4 Example: The Redox Potential of the MSRE

5 Calculating Beryllium Additions

6 Measurement and Validation

7 Conclusions

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Example: Fluoride Potential of the MSRE

The MSRE salt was constantly monitored by the couple

UF4 + e ⌦ UF3 + F . (11)

Which can be expressed as

✓ ◆
aUF3 aF GUF3 GUF4
= exp . (12)
aUF4 RT

Which shows that the ratio of U(III,IV) was the determining factor.
✓ ◆
aUF4
G F = RT ln + ( GUF4 GUF3 ) . (13)
aUF3

Allows the comparison of the MSRE to any salt system.

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Historical MSRE Potential

- 80

First Beryllium Addition

- 81
GF - (kcal/mol)

- 82

- 83

Fission Product Oxidation

- 84

0 2000 4000 6000 8000

Full Power Hours

Figure : As the MSRE’s primary loop transmuted UF4 into fission product
fluorides, it oxidized the salt. Beryllium was used to counteract this.
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Fluoride Potential vs. Redox Potential

MSRE literature always uses redox potential because it was

experimentally measurable.

GF = mnF (ERedox + EF2 ) (14)

Fluoride potential has a few advantages over redox potential.

1 Bases the system on a reaction possible in all salts.
2 Tabulated Gibbs free energies.
3 Exploration of complex reactions.
4 For the mathematically inclined: shows trends with equations.
What is the disadvantage of fluoride potential?
1 Not directly measurable.
2 What does it physically describe?

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Historical MSRE Potential: Revisted

-80 -0.60

Redox Potential (HF|H2 ) = 0V

-81
GF- (kcal/mol)

-0.65

-82
-0.70

-83
-0.75
-84

0 2000 4000 6000 8000

Full Power Hours 19 / 35
 Outline

1 Fluoride Salt Cooled Reactor (FHR) Materials and Chemistry

Research

2 Equilibrium Chemistry Review

Fluorine Potential

3 Example: Hydrofluorination

4 Example: The Redox Potential of the MSRE

5 Calculating Beryllium Additions

6 Measurement and Validation

7 Conclusions

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 MSRE Beryllium Additions

Cr
200 Fe

Analyte Concentration (PPM)

Ni

150

100

50

0
0 2000 4000 6000 8000
Full Power Hours

Figure : The MSRE shows only a few
graphs, dependent on metal
concentrations, to reduce the salt.
Sha↵er, J. H. (1971). Preparation and
Handling of Salt Mixtures for the
Molten Salt Reactor Experiment.
Figure : Metal ion concentration in the
MSRE does not follow the redox
voltage. Not reliable for beryllium
additions.
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Example: ICE Table for Beryllium Addition

Beryllium usually avoided as a reductant for flibe. We can take

advantage of old MSRE data and ICE tables.
• Beryllium additions to a salt work by shifting the equilibrium.
• When equilibrium is shifted, components must rearrange towards
equilibrium.

aBeF2
K= . (15)
aBe aF2
aBeF2 (aBeF2 *)
Q= !K = ⇣ ⌘ (16)
(aBe *) aF2 (aBe +) aF2 +

• In what ratio does beryllium, fluoride, and beryllium fluoride shift

in order to reach equilibrium?

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Beryllium Additions: equilibrium change ratios

• Check the original equation stoichiometry.

Be + 2F ⌦ BeF2
Stoichiometry 1 2 1
Reactant Biased x 2x x
Product Biased x 2x x

• Require activities or partial pressures.

• Convert x ! ; moles!mole fraction. Convert ! a; mole
fraction!activity

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Beryllium Additions: quantifying setup

• Subtract or add converted activities into the equilibrium Eq. 15

GBeF
2 (aBeF2 + BeF2 x)
e RT = ⇣ ⌘ (17)
2 2
(aBe Be x) a F
( F x)

• In the case of the addition of beryllium, the activity is the

equilibrium activity at a redox plus the activity of the added
beryllium, in mole fraction.

GBeF
2 (aBeF2 + BeF2 x)
e RT = ⇣⇣ ⌘ ⌘⇣ ⌘ (18)
aBe0 + nBe
Be nSalt Be x aF2 ( F x)2

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Activities by Hitch and Baes

1.00

0.70

0.50 BeF2
LiF
g

0.30

0.20

0.15

0.10
0.3 0.4 0.5 0.6 0.7 0.8 0.9
cBeF2

Figure : Measured activity coefficients in flibe from “Electromotive force

study of molten lithium fluoride-beryllium fluoride solutions.” B. F. Hitch
and Charles F. Baes Jr., Inorganic Chemistry 1969 8 (2), 201-207

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Beryllium Additions: MSRE Data

Equivalent Beryllium Beryllium GF GFa

b
Full Power Addition Addition After Before
(hr) (g) (mol) (kcal/mol) (kcal/mol)
1870 3 0.333 -80.4 -79.7
1920 1 0.111 -80.6 -80.4
1948 1.63 0.181 -80.8 -80.6
2247 10.65 1.182 -81.9 -80.6
2663 11.66 1.294 -82.7 -81.7
3856 8.4 0.932 -82.8 -82.1
4513 7.933 0.880 -83.0 -82.5
4558 9.84 1.092 -83.4 -83.0
4739 8.33 0.925 -83.7 -83.4
4811 11.677 1.296 -84.1 -83.7
5492 9.71 1.078 -84.2 -84.0

• T = 650 C; nSalt = 112702 mols; LiF-BeF2 -ZrF4 -UF4 (65.0-29.1-5.0-0.9

mol%)
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Beryllium Additions: Calculated F and x

Avg. GF x ⇥ 106
Addition F ⇥ 1016
(kcal/mol) (mol %)
1 -80.1 2.96 331.17
2 -80.5 0.99 411.92
3 -80.7 1.61 226.09
4 -81.3 10.5 68.04
5 -82.2 11.5 31.93
6 -82.4 8.27 32.06
7 -82.7 7.81 24.14
8 -83.2 9.69 13.69
9 -83.6 8.20 11.57
10 -83.9 11.5 7.82
11 -84.1 9.56 5.94

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Beryllium Additions: GF vs. F

5. × 10-14

1. × 10-14

5. × 10-15
F

1. × 10-15

5. × 10-16
-84 -83 -82 -81 -80
GF (kcal/mol)

• A clear trend between the fluoride potential and the activity

coefficient–as there should be.
• Fits with an exponential line.
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Beryllium Additions: In practice

-70

mgBe /kgFlibe
12.5
G F- b (kcal/mol)

-75
10.0

7.5

5.0

-80 2.5

-85
-85 -80 -75 -70
GF - a (kcal/mol)
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 Outline

1 Fluoride Salt Cooled Reactor (FHR) Materials and Chemistry

Research

2 Equilibrium Chemistry Review

Fluorine Potential

3 Example: Hydrofluorination

4 Example: The Redox Potential of the MSRE

5 Calculating Beryllium Additions

6 Measurement and Validation

7 Conclusions

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Electrochemical Probe

Figure : Electrochemical probe for measuring flibe redox potential.

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Measuring Redox Potential

-0.44
-76.4

-0.45 -76.6
Redox Potential (HF|H2 =0)

GF- (kcal/mol)
-0.46 -76.8

-77.0
-0.47

-77.2
-0.48
-77.4
-0.49
-77.6
-0.50
0 5 10 15 20 25
Time (s)

Figure : Measured redox/fluoride potential of the UW-Madison salt.

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 Outline

1 Fluoride Salt Cooled Reactor (FHR) Materials and Chemistry

Research

2 Equilibrium Chemistry Review

Fluorine Potential

3 Example: Hydrofluorination

4 Example: The Redox Potential of the MSRE

5 Calculating Beryllium Additions

6 Measurement and Validation

7 Conclusions

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Conclusion

• The University of Wisconsin - Madison is able to safely handle and

purify flibe to perform research which supports the FHR
development.
• The fluoride potential model has been expanded upon to guide
corrosion tests and predict FHR chemistry.
• MSRE data has been been used with the fluoride potential model
to show what redox to operate a reactor at without uranium, and
how much beryllium to add to shift the redox.
• Work is being done at the moment to validate these claims.
• Measure flibe redox before, after, and during beryllium addition.
• Measure flibe redox after purification.
• Create tables or graphs of beryllium additions which put salt in
‘redox window’.
• Compare to theory.

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Questions

Thank You For Your Attention

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 Outline

8 Backup Slides

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Beryllium Additions: making an assumption

• Assume (for now) that beryllium is not in solution with the salt
and behaves ideally. Be = 1.
GBeF
2 (aBeF2 + BeF2 x)
e RT = ⇣⇣ ⌘ ⌘⇣ ⌘ (19)
Be0 + nnSalt
Be
x aF2 ( F x)2

• If you add in this activity coefficient and solve for it later, it turns
out to be ⇠ 1.0003.

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Beryllium Additions: replacing unknowns

• a2 can be changed to a fluoride potential through the definition

F
of fluoride potential, GF = RT ln aF .
✓ ◆
2 2 GF
aF = exp (20)
RT

• Be0 can be found from the equilibrium equation.

✓ ◆
GBeF2 2 GF
Be = a BeF2 exp (21)
RT RT

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Beryllium Additions: change after equilibrium

• The initial fluoride potential,GFa , minus the change from the

Be addition, makes the new fluoride potential GF :
b
2 G 2 G
!
F Fa
b
e RT = e RT ( F x)2 (22)

• Include before and after fluoride potentials in new equations.

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Beryllium Additions: solving for x and F

• Three equations
GBeF
2 (aBeF2 + BeF2 x)
e RT = 0 2 G ! 1 (23)
⇣⇣ ⌘ ⌘ Fa
B RT C
Be0
nBe
+ nSalt x @e ( F x)2 A

2 G 2 G
!
F Fa
b 2
e RT = e RT ( F x) (24)

✓ ◆
GBeF2 2 GFa
Be0 = aBeF2 exp (25)
RT RT

• Unknowns: GF , GFa , nSalt , nBe , T , x

b
• Givens: GBeF2 , R
• MSRE data provides the missing pieces.
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