journal article·2022-12Open access

Infiltration of molten fluoride salts in graphite: Phenomenology and engineering considerations for reactor operations and waste disposal

Lorenzo Vergari, Malachi Nelson, Alex Droster, Cristian Contescu, Nidia Gallego, Raluca O. Scarlat

Abstract

The possibility and consequences of salt-infiltration in graphite must be evaluated for graphite used in molten salt reactors (MSRs) and fluoride-salt-cooled high-temperature reactors (FHRs), which can be subjected to salt pressures as high as 500 kPa. The volume of graphite porosity infiltrated by salt can be measured by direct infiltration and it can be predicted from the graphite pore size distribution, the surface tension of the salt, and the contact angle between the graphite and the salt. While these three properties are believed to be insensitive to irradiation, the former can be impacted by chronic or acute oxidation, and the latter two are highly sensitive to the chemistry of the salt and to events such as air ingress. For MSRs, predictions based on nominal properties of salt and graphite reveal that few graphite grades would satisfy the 4 vol% limit set in the Molten Salt Reactor Experiment, and even fewer would satisfy the 0.5 vol% design target. For FHRs, infiltration limits have not been defined and depend on the effect of infiltration on graphite properties, which are discussed. A hypothesis is presented for properties that may be impacted by infiltration and for which future studies are needed.
Source: openalex_inverted_index · Quality: baseline

Research context

OpenAlex topics: Graphite, nuclear technology, radiation studies · Nuclear and radioactivity studies · Radiation Shielding Materials Analysis

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (100+)

Show source-provided references
1. Kinetics of graphite oxidation10.1021/j150551a039 ↗
2. J.H.W. Simmons, B.T. Kelly, P.T. Nettley, W.N. Reynolds, The Irradiation Behavior of Graphite, Third United Nations International Conference on the Peaceful Uses of Atomic Energy, 1964. https://www.osti.gov/servlets/purl/4025669.
3. Dimensional change, irradiation creep and thermal/mechanical property changes in nuclear graphite full critical review10.1080/09506608.2015.1136460 ↗
4. Understanding the reaction of nuclear graphite with molecular oxygen: kinetics, transport, and structural evolution10.1016/j.jnucmat.2017.06.001 ↗
5. Solid fuel, Salt-Cooled Reactors
6. Liquid fuel, thermal neutron spectrum reactors
7. Molten salt reactor adventure10.13182/NSE90-374 ↗
8. Briggs · 1963
9. Protection of graphite from salt and gas permeation in molten salt reactors10.1016/j.jnucmat.2020.152119 ↗
10. Rosenthal · 1972
11. Briggs · 1964
12. The effect of molten FLiNaK salt infiltration on the strength of graphite10.1016/j.jnucmat.2018.09.051 ↗
13. Fluorine generation by gamma radiolysis of a fluoride salt mixture10.1080/10420159008213046 ↗
14. Spent nuclear fuel and graphite management for salt-cooled reactors: storage, safeguards, and repository disposal10.13182/NT14-88 ↗
15. Riley · 2018
16. Spent fuel management strategies for fluoride-cooled pebble bed reactors10.1016/j.nucengdes.2021.111189 ↗
17. Molten FLiNaK salt infiltration into degassed nuclear graphite under inert gas pressure10.1016/j.carbon.2014.12.044 ↗
18. Preparation of ultrafine-grain graphite by liquid dispersion technique for inhibiting the liquid fluoride salt infiltration10.1016/j.carbon.2016.02.018 ↗
19. Gallego · 2020
20. Mesocarbon microbead based graphite for spherical fuel element to inhibit the infiltration of liquid fluoride salt in molten salt reactor10.1016/j.jnucmat.2017.04.003 ↗
21. Phenomenology, methods and experimental program for fluoride-salt-cooled, high-temperature reactors (FHRs)10.1016/j.pnucene.2014.04.008 ↗
22. Graphite as a core material for generation IV nuclear reactors
23. Design summary of the mark-i pebble-bed, fluoride salt-cooled, high-temperature reactor commercial power plant10.13182/NT16-2 ↗
24. A new classification of pore sizes10.1016/S0167-2991(07)80009-7 ↗
25. Kelly · 1981
26. Microstructure and molten salt impregnation characteristics of a micro-fine grain graphite for use in molten salt reactors10.1016/S1872-5805(16)60034-3 ↗
27. SiC coating: an alternative for the protection of nuclear graphite from liquid fluoride salt10.1016/j.jnucmat.2014.01.034 ↗
28. Infiltration of graphite by molten 2LiF-BeF2 salt10.1007/s10853-017-1310-4 ↗
29. Wetting of Graphite by Molten Fluoride Salts: initial Experiments
30. Corrosion- and irradiation-induced porosity changes of a nuclear graphitic material10.1016/S0022-3115(86)80015-0 ↗
31. Grimes · 1964
32. Coefficient of thermal expansion of nuclear graphite with increasing thermal oxidation10.1088/0022-3727/33/8/316 ↗
33. Development of mesopores in superfine grain graphite neutron-irradiated at high fluence10.1016/j.carbon.2018.08.039 ↗
34. The effect of irradiation and radiolytic oxidation on the porous space of Gilsocarbon nuclear graphite measured with mercury porosimetry and helium pycnometry10.1016/j.carbon.2019.11.084 ↗
35. Improvement of stacking order in graphite by molten fluoride salt infiltration10.1016/j.carbon.2014.02.010 ↗
36. Preparation of binderless nanopore-isotropic graphite for inhibiting the liquid fluoride salt and Xe135 penetration for molten salt nuclear reactor10.1016/j.carbon.2014.07.022 ↗
37. Varma · 2012
38. The effect of neutron irradiation damage on the properties of grade NBG-10 graphite10.1016/j.jnucmat.2007.05.021 ↗
39. Williams · 2006 · 1
40. Compere · 1975
41. The dynamics of capillary flow10.1103/PhysRev.17.273 ↗
42. Understanding Tritium Transport Behavior in Fluoride-salt and Graphite System
43. The physics and chemistry of surfaces10.1021/ed008p2156 ↗
44. Measurement of contact angle and work of adhesion at high temperature10.1007/s10853-005-1945-4 ↗
45. Surface Tension and Its measurement
46. On pendent drops10.1098/rspl.1881.0032 ↗
47. The determination of surface tension by sessile drop measurements, with application to mercury10.1071/PH530086 ↗
48. A simple formula for the estimation of surface tension from two length measurements for a sessile or pendant drop10.1080/09500839.2018.1434320 ↗
49. The maximum bubble pressure method of measuring surface tension, revisited10.1016/0166-6622(90)80291-B ↗
50. A review of factors that affect contact angle and implications for flotation practice10.1016/j.cis.2009.07.003 ↗
51. II the Bakerian lecture On the theory of light and colours
52. Macpherson · 1958
53. Surface tension of lithium fluoride and beryllium fluoride binary melt10.1021/j100218a021 ↗
54. A multi-technique experimental and modelling study of the porous structure of IG-110 and IG-430 nuclear graphite10.1016/j.carbon.2017.11.076 ↗
55. Observations concerning the determination of porosities in graphites10.1016/0008-6223(68)90077-8 ↗
56. Structural damage in graphite occurring during pore size measurements by high pressure mercury10.1016/0008-6223(71)90092-3 ↗
57. 2016
58. Protecting nuclear graphite from liquid fluoride salt and oxidation by SiC coating derived from polycarbosilane10.1016/j.jeurceramsoc.2017.09.031 ↗
59. Current status of knowledge of the fluoride salt (FLiNaK) heat transfer10.13182/NT165-166 ↗
60. Williams · 2006
61. Absorption of molten fluoride salts in glassy carbon, pyrographite and Hastelloy B10.1016/S0022-3115(01)00419-6 ↗
62. Pore structure evolution of IG-110 graphite during argon ion irradiation at 600°C10.1007/s10853-019-03329-7 ↗
63. Mesocarbon microbead densified matrix graphite A3-3 for fuel elements in molten salt reactors10.1016/j.net.2020.10.018 ↗
64. Great structural stability of irradiated graphite after testing in molten Li2BeF4 salt10.1016/j.nimb.2018.08.049 ↗
65. Effect of temperature on graphite oxidation behavior10.1016/j.nucengdes.2003.11.004 ↗
66. Pore structure development in oxidized IG-110 nuclear graphite10.1016/j.jnucmat.2012.07.015 ↗
67. Comparison of oxidation behaviors of different grades of nuclear graphite10.13182/NSE05-A2534 ↗
68. Beyond the classical kinetic model for chronic graphite oxidation by moisture in high temperature gas-cooled reactors10.1016/j.carbon.2017.11.001 ↗
69. Oxidation of PCEA nuclear graphite by low water concentrations in helium10.1016/j.jnucmat.2014.07.009 ↗
70. Contescu · 2016
71. Protection of nuclear graphite toward liquid fluoride salt by isotropic pyrolytic carbon coating10.1016/j.jnucmat.2013.09.015 ↗
72. Dimensional change, irradiation creep and thermal/mechanical property changes in nuclear graphite10.1080/09506608.2015.1136460 ↗
73. Modeling the effects of oxidation-induced porosity on the elastic moduli of nuclear graphites10.1016/j.carbon.2018.09.051 ↗
74. Density Measurement Of Molten FLiBe
75. Engineering toolbox, Solids, liquids and gases - thermal conductivities, The Engineering Toolbox, 2003. https://www.engineeringtoolbox.com/thermal-conductivity-d_429.html (accessed August 4, 2022).
76. A novel effective medium theory for modelling the thermal conductivity of porous materials10.1016/j.ijheatmasstransfer.2013.09.043 ↗
77. The effect of porosity on the thermal conductivity of nuclear graphite10.1016/0022-3115(80)90003-3 ↗
78. Neutronic feasibility assessment of liquid salt-cooled pebble bed reactors10.13182/NSE10-38 ↗
79. Thermal analysis with contact resistance of packed bed by a homogenization method10.1016/j.powtec.2015.12.006 ↗
80. Overall heat transfer coefficient with considering thermal contact resistance in thermal recovery wells10.1016/j.ijheatmasstransfer.2016.07.050 ↗
81. Determination of thermal contact resistance from transient temperature measurements10.1016/j.ijheatmasstransfer.2007.05.004 ↗
82. Rosenthal · 1968
83. Interaction between nuclear graphite and molten fluoride salts: a synchrotron radiation study of the substitution of graphitic hydrogen by fluoride ion10.1021/jp208990y ↗
84. Fluorination of nuclear graphite IG-110 in molten 2LiF-BeF2 (FLiBe) salt at 700 oC10.1016/j.jfluchem.2018.04.001 ↗
85. Estimation of the tritium behavior in the pebble type gas cooled reactor for hydrogen production10.1080/18811248.2006.9711249 ↗
86. A.T. Cisneros, Pebble bed reactors design optimization methods and their application to the pebble bed fluoride salt cooled high temperature reactor (PB-­FHR), Ph.D. thesis, University of California, Berkeley, 2013.
87. Tritium production, releases and population doses at nuclear power reactors10.13182/FST8-2544 ↗
88. An electrochemical study of hydrogen in molten 2LiF-BeF2 (FLiBe) with addition of LiH10.1016/j.electacta.2020.137114 ↗
89. Thermodynamics of hydrogen in graphite at high temperature and the effects of oxidation, irradiation and isotopics10.1016/j.jnucmat.2021.152797 ↗
90. Kinetics and transport of hydrogen in graphite at high temperature and the effects of oxidation, irradiation and isotopics10.1016/j.jnucmat.2021.153142 ↗
91. The impact of neutron irradiation, graphite oxidation and fluorination on tritium uptake into and desorption from graphite in molten salt environments10.1016/j.fusengdes.2021.112627 ↗
92. Tritium content and chemical form in nuclear graphite from molten fluoride salt irradiations10.1080/15361055.2020.1712993 ↗
93. Effect of temperature on graphite oxidation behavior10.1016/j.nucengdes.2003.11.004 ↗
94. Windes · 2014
95. Graphite in gas-cooled reactors
96. Calculation of the graphite weight-loss in civil magnox and advanced gas-cooled reactors10.1016/0368-3230(66)90169-8 ↗
97. Graphite oxidation in sodium carbonate/sodium sulfate melts10.1021/ic00131a021 ↗
98. Graphite oxidation in molten sodium carbonate10.1016/0008-6223(80)90008-1 ↗
99. Air oxidation of graphite in molten salts
100. The catalytic behavior of alkali metal carbonates and oxides in graphite oxidation reactions10.1016/0008-6223(75)90006-8 ↗