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Outline
Motivation
Innovation
Goals and Objectives
Background
Molten Salt and Material Selection
Molten Salt Corrosion Review
Current status
Corrosion measurements/Inhibitor studies
Thermodynamic modeling
Electrochemical Kinetics and CFD Corrosion Modeling
Future plans
April
1st
, 2013
Salt Selection
DOE has invested considerable effort in determining ideal salt candidates for heat
transfer candidates for nuclear applications (no exposure to radiation)
Corrosion inhibitors that could not be used for nuclear application may have solar
applications
Need High Boiling Point and Low Vapor Pressure
[1]: Williams, D., Assessment of Candidate Molten Salt Coolants for the NGNP/NHI Heat-Transfer Loop, ORNL/TM-2006/69.
Salt Selection:
[1]: Williams, D., Assessment of Candidate Molten Salt Coolants for the NGNP/NHI Heat-Transfer Loop, ORNL/TM-2006/69.
Materials Selection
Goal is to look at a wide range of materials and alloy systems for the most
widespread characterization of corrosion inhibitors possible
Alloys
Capable of being formed into piping
Reasonable strength between 800-1000 C
Compatibility with salt
Single alloys must be oxidation resistant on outside, salt compatible on inside,
or:
Plating or bilayer piping for salt compatibility, oxidation resistant coatings
Ceramics and Composites
Less affected by heat
SiC has proven fluoride/chloride compatibility
SiC/SiC composites can be tailored to a range of physical properties such as
thermal expansion and tensile strength
Material Selection:
Physical Property Considerations
Hours to Rupture
760C/103 MPa
871C/31 MPa
982C/14 MPa
Haynes-230
8 200
6 500
5 000
Incoloy-800H
130
1 200
920
10
100
72
35
800H in
FLiNaK
30
25
20
15
800H in
MgCl2-KCl
10
10
Corrosion test #1
Corrosion test #2
Thermodynamic Modeling
Calculations were performed based on the method of Gibbs
energy minimization under the condition of mass balance:
G ni ( gio RT ln Pi )
gas
ni gio
pure
condensed
phase
ni (gio RT ln Xi RT ln i )
solution1
o
n
(
g
i i RT ln Xi RT ln i ) ...
solution2
Where G - total Gibbs energy of the system; gio - standard molar Gibbs
energy of species i at T and P; ni - number of mole of species i; Pi - partial
pressure of species i=(ni/nt)Ptotal; Xi - mole fraction of species i; and , activity coefficient of species iWe will find ni which minimize G subject to
mass balance constraints.
N.A. Gokcen and R.G. Reddy, Thermodynamics, Plenum Press, 1996
April 1st , 2013
Composition of corrosion
product/(mol%)
70
60
50
Cr2O3
40
Cr2FeO4
30
KCrO2
20
K3AlF6
10
LiCrO2
0
700
750
800
850
900
Temperature/(degree C)
950
1,000
As shown in Fig.2, when in contact with N2 or Ar gas, the corrosion effect will be
minimized. K3AlF6 will be most stable corrosion product.
Corrosion Products (moles)
Phases
800
900
1000
100%
100%
100%
100%
100%
100%
Composition of corrosion
product/(mol%)
700
800
900
100
90
80
70
60
50
40
30
20
10
0
1000
700
K3AlF6
700
750
800
850
900
950
1000
Temperature/(degree C)
15
Activity Gradient
Metal
Cr
3e-
Metal Oxide/
Protective Film
With Vacancies
Solution
Cr+3
Solubility/Complexes
Cr+3 + 3 Cl- = CrCl3
or
+3
Cr + 3 F- = CrF3
ForCl
or
Contaminants:
Fe2+
Important
Activity ratios
Cr(II)/C(III)
Fe(II)/Fe(III)
Cr3C/Fe3C
Cr(II)/Ni(II)
16
Fig. from Incropera et al., 5th Ed. John Wiley & Sons, Inc., NJ, Chapter 8, 2007.
17
Geometry affects
Figures from Incropera et al., 5th Ed. John Wiley & Sons, Inc., NJ, Chapter 11, 2007.
18
Temperature profiles from Incropera et al., 5th Ed. John Wiley & Sons, Inc., NJ, Chapter 8, 2007.
April
1st
, 2013
19
20
Future Work
Characterize corrosion in FLiNaK and KCl-MgCl2
Identify novel materials and salts that enable long service
life based on mechanisms
Advanced Ni-Fe-Cr Alloys
Refractory Alloys & Composites
High fluoribasicity salts to reduce corrosion
21
Project Plan
Task/Milestone
PlaceSubcontracts&ProjectPlanning
T1.1ElectrochemicalCorrosionTesting
M1.1.1ExperimentalSetup&SetupVerification
M1.1.2CorrosionResultsComparison
T1.2CorrosionKineticsModeling&CFD
M1.2.1CorrosionMechanismModeling
M1.2.2CFDModelingPlatformDevelopment
T1.3ThermodynamicModeling
M1.3.1SpeciesSolubilityPrediction
M1.3.2StableCorrosionProductPrediction
M1.3.3MoltenSaltStabilityPrediction
T1.4LongTermCorrosionTesting
M1.4.1LongTermCharacterization
April 1st , 2013
22
Thank You
QUESTIONS?
23
Extra Slides
24
Thermally stable
Cheap
Easy to handle
Water
(PWR)
Sodium
(LMR)
Helium
Molten Salt
Pressure (MPa)
15.5
0.69
7.07
0.69
320
540
1000
1000
75
Slide Source: Charles W. Forsberg, (June 7, 2006) High-Temperature Reactors for In Situ Recovery of Oil from Oil Shale, Presentation for ICAPP06; Paper 6104
25
Salt Selection
Nitrates, sulfates, carbonates (oxygen containing salts) [1]:
Lack high temperature thermal stability
e.g. Nitrates decompose into nitrites with usable temperature
range of <95 - 600 C [2, 3]
Carbonates decompose into oxides (calcination)
Release oxygen during decomposition can rely on mature
oxide passivation layer paradigm
Fluorides, chlorides, alkali fluoroborates:
Chemical stability above 800 C, melt below 525 C and not
volatile, compatible with high temp alloys and ceramics [1]
Appear to have suitable traits, but corrosion mitigation via oxide
passivation layers likely not possible
[1]: Williams, D., Assessment of Candidate Molten Salt Coolants for the NGNP/NHI Heat-Transfer Loop, ORNL/TM-2006/69.
[2]: Bradshaw et al., Patent No.: US 7,588,694 Bl
[3]: Bradshaw et al., High-temperature stability of ternary nitrate molten salts for solar thermal energy systems, Solar Energy Materials 21 (1990) 51-60.
26
Salt Selection
[1]: Williams, D., Assessment of Candidate Molten Salt Coolants for the NGNP/NHI Heat-Transfer Loop, ORNL/TM-2006/69.
27
Cr
Mo
Al
Ti
Fe
Co
Ni
Mn
.02
.05
.02
.02
99.4
.19
0.5
0.6
42.3
.07
31.6
0.8
<.01
4.03
.03
.15
72.2
0.53
1.8
0.1
0.3
59
0.5
Ni-201*
Incoloy-800H*
20.4
Hastelloy-N*
6.31
16.1
0.06
<.01
Haynes-230*
22.5
1.2
14.1
0.3
Haynes-NS-163*
28
0.5
TZM*
99.37
Mo-30W*
70
1.3
0.5
21
0.1
40
Zr
Nb
0.5
<.01
0.5
0.03
Si
0.1
30
SiC/SiC Composites
*New heat compositions need to be input, these compositions are from previous work
28
Material Selection:
Chemical/Morphology Considerations
Ni-201<Hastelloy-N<Haynes-230
29
Sources: [1] D. Wilson, Corrosion Issues In Molten Fluoride Salts, 2006 ANS Annual Meeting Reno, Nevada, June 8, 2006
30
Corrosion Mechanisms
April
1st
, 2013
Slide copied from: Williams, D., Molten Fluorides as High Temperature Coolants for Nuclear Reactors, January 21, 2003 Nuclear Engineering Design, University of
Tennessee , Knoxville 308 Pasqua Hall.
31
Alloy Selection:
Chemical Considerations
32
April
1st
, 2013
[1] L. Olson, J. Ambrosek, K. Sridharan, M. Anderson, T. Allen, "Materials corrosion in molten Lif-NaF-KF salt," Journal of Fluorine Chemistry, Vol. 130, No. 1, pp.
67-73, Jan. 2009.
33
Weight-loss/area shown to
correlate with C content in
alloys with ~20% Cr [1]
Cr is concentrated in
carbides in GB leading to
GB attack
55
45
R =0.95
P=0.02
40
35
30
25
20
15
3. Incoloy-800H
4. Hastelloy-X
5. Inconel-617
6. Haynes-230
10
0.06
0.07
0.08
0.09
0.10
Cross-section
Cross-section
Surface
Cr
Carbides
April
1st
[1] "Intergranular Corrosion of High Temperature Alloys in Molten Fluoride Salts", L. Olson, K. Sridharan, M. Anderson, T. Allen,
, 2013Materials at High Temperatures, vol. 27, No. 2, pp. 145-149, (2010).
34
[1] Del Cul, et al., Redox Potential of Novel Electrochemical Buffers Useful for Corrosion Prevention in Molten Fluorides, http://www.ornl.gov/~webworks/cppr/y2001/pres/112728.pdf
[2] J. Plambeck, Electromotive Force Series in Molten Salts, in Journal of Chemical and Engineering Data, Vol. 12, No. 1, January 1967, pg. 77-82.
[3] Williams, D., Molten Fluorides as High Temperature Coolants for Nuclear Reactors, January 21, 2003 Nuclear Engineering Design, University of Tennessee , Knoxville 308 Pasqua Hall.
35
CrF2
Gibbs Free Energy of Formation
(J/mol) l
40
-2.0E+05
-3.0E+05
-4.0E+05
-5.0E+05
-6.0E+05
-7.0E+05
R =0.64
P=0.06
400
30
20
200
100
0
10
15
, 2013
R =0.91
P=0.003
April
300
1. Ni-201
2. Hastelloy-N
3. Incoloy-800H
4. Hastelloy-X
5. Inconel-617
6. Haynes-230
10
1st
NiF2
Fluorides
50
1. Ni-201
2. Hastelloy-N
3. Incoloy-800H
4. Hastelloy-X
5. Inconel-617
6. Haynes-230
CoF2
-1.0E+05
Weight-loss/area results
60
FeF2
0.0E+00
20
25
10
15
20
25
Weight % Chromium
[1] L. Olson, J. Ambrosek, K. Sridharan, M. Anderson, T. Allen, "Materials corrosion in molten Lif-NaF-KF salt," Journal of Fluorine Chemistry, Vol. 130, No. 1,
pp. 67-73, Jan. 2009.
36