Spent Fuel Behavior

Spent fuel in nuclear energy is stored in either specially designed pools for wet storage or dry cask storage. To
reduce radiotoxicity and decay heat of spent fuel, the dry storage (heat dissipation with natural air circulation)
process is used following the wet storage with structural integrity assurance (C. Lee & Lee, 2023). Cooling in dry
storage is achieved by natural convection of helium in a canister and air in the environment. But the hydrogen
uptake during normal operation due to waterside corrosion challenge the spent fuel safety since formation of brittle
layer degrades the cladding (Motta et al., 2019). Further, the non-uniform temperature and concentration
distribution on fuel rod cladding cause the hydrogen to migrate. Since the low temperature in wet storage and surface
exposure to inert gas or vacuum in dry storage, no appreciable oxidation takes place in both storage conditions.
Mostly hydrides precipitate at relatively low temperature in spent fuel which is highly important and concerning
phenomena for structural integrity especially for long term dry storage (S. Kim, Kang, et al., 2022). The reason for
the focus on the dry storage is to prevent rupture of spent fuel cladding under normal conditions including
transportation. Beyond this, the dry storage is highly resistant, passive system and safe storage with the capability
to predict the spent fuel performance during period of storage. Since wet spent fuel storage is characterized by low
temperature, low stress and negligible irradiation damage; no regulatory limit are prescribed in relation to ensuring
structural integrity. However the hydride formation at lower temperature make it more brittle which should not be
neglected. Spent fuel management is an important area to ensure safety and economic relevance of nuclear
technology.

Hydride reorientation (re-precipitation of dissolved hydrogen) driven by various factors (such as biaxial stress,
temperature,…) deteriorate spent fuel cladding mechanical ductility during dry storage making it more susceptible
to brittle failure (Y. J. Kim et al., 2015). The ductility of spent fuel cladding in wet storage conditions like the dry
cask is also deteriorated by the formation of hydrides at low temperature conditions experiencing the highest
brittleness. So the design of cask should explore the heat load regionalization, relative position of air inlet-outlet
orientations and local climate temperature to determine the most relevant factor to guarantee the cooling of fuel
assemblies ensuring safety (Cui et al., 2011; Herranz et al., 2015). The steady state operation histories such as
fission product generation, cladding creep rate and cladding material hydride embrittlement due to hydrogen uptake
and waterside corrosion highly affect the spent fuel behavior of LWRs (Dehyeon Woo, 2019; Nam et al., 2020).
No reactor induced defects challenge the dry storage of fuel rods and conditions under inert gases are not expected
to cause cladding failure as long as the dry storage cladding peak temperature is limited within a permissible value.

Radial and circumferential hydrides

The major mechanism for zircaloy fuel rod strength degradation is hydride reorientation by reducing the threshold
stress under dry storage conditions. The radial hydrides favor their formation on locations with larger number of
existing sites and/or low strain energy when the externally applied stress exceeds the threshold value (Donguk Kim,
Kim, et al., 2022; Dongyeon Kim, Kang, et al., 2022). The main concern in spent fuel management comes from
the cladding hydride embrittlement due to the hydrogen uptake during the normal operation and formation of
hydrides above the solubility limit which create strain misfit at the interface with zircaloy deteriorating the
mechanical integrity of cladding (Dongyeon Kim, Woo, et al., 2022). During dry storage cool-down, the
precipitated hydrides reoriented in the radial direction (major axis within ±400) derived by hoop stress (thermo-
mechanical condition) which is higher than the threshold make the zircaloy cladding tubes prone to fracture. Further
the hydrogen content and tube internal pressure variation affect the radial hydride fraction (RHF) which need deep
understanding to predict the extent of cladding embrittlement. Under high burnup conditions the higher hydrogen
content, increased corrosion, higher level of radiation damage, and storage-handling operations influence the
formation of radial hydrides (Daum et al., 2006). These hydrides affect the cladding ductility and cracking behavior
under non-irradiated and high burnup conditions. The fraction of hydride formation on zircaloy cladding mainly
depends on the total uptaken hydrogen concentration and the alloy’s terminal solid solubility (TSS) for hydrogen
atoms (Motta et al., 2019). Since circumferential hydrides at higher hydrogen content and non-irradiated cladding
promote plasticity-induced stable crack growth, the susceptibility to radial hydride embrittlement (due to unstable
crack propagation) becomes lower compared to that of lower hydrogen content. The combination of low hydrogen
content and slower cool-down process (relatively longer residence time at a higher temperature) generate larger
radial hydride fraction (RHF) with longer length and smaller ultimate tensile strength for zirconium based alloy
cladding (Cha et al., 2015). Longer radial hydrides are dangerous for zircaloy cladding tube integrity since they
can form inter-linked configuration which can possibility be transformed into through wall fracture.

The temperature, thermal history, hydrogen content, thermal cycling and multi-axial stresses affect the reorientation
triggering threshold stress of zircaloy cladding (J. M. Lee et al., 2018). The content and morphology of hydrides
determine the degree of cladding hydride embrittlement. Although the crystallographic texture of cladding can be
controlled to precipitate the hydrides in circumferential direction, the hydrides can reorient to radial direction under
dry storage condition and deteriorate the cladding mechanical integrity since radial hydrides act as crack linkage
path reducing fracture toughness and ductility of zircaloy cladding material (J. S. Kim et al., 2015). The dissolved
hydrogen in the zircaloy matrix re-precipitates to radial hydrides when there is sufficient hoop stress exceeding the
threshold during cool-down process. More dissolved hydrogen diffuse to the radial direction of cladding to relieve
hoop stress with faster growth and longer length while reducing the threshold stress limit. However the
circumferential hydrides remained in the cladding matrix at peak temperature prevents the migration of dissolved
hydrides in the radial direction in addition to the memory effect which reduce the source of radial hydride
precipitation. Heating spent fuel rods during vacuum drying period dissolves the circumferential hydrides and some
of them re-precipitate to radial direction upon cooling process for tensile hoop stress exceeding the hoop stress.
This condition can be affected by the hydrogen content, cooling rate, cladding memory effect, extent of cladding
hoop stress, the temperature dependent hydrogen solubility or stress driven hydrogen transport, cladding texture
(manufacturing technique to control precipitation direction) and neutron irradiation induced micro-structural
changes (Jang & Kim, 2017). From the study it was indicated that the mechanical property degradation for
irradiated conditions comes from the tensile hoop stress induced crack propagation on the radial and/or
circumferential hydrides and the irradiation damaged cladding matrix micro-crack nucleation. Irradiated specimens
with higher hydrogen content under cool-down process result smaller radial hydride fraction although the ultimate
tensile strength become lower due to the additional irradiation damage on microstructure of the cladding.

To investigate the effect of radial hydrides in zircaloy cladding, (Chu et al., 2007) prepared specimens subjected
to radial hydrides utilizing hydride reorientation process and explored the cladding ductility under plain strain
tensile loading to assess the cladding integrity. The zircaloy cladding is always manufactured to ensure the
circumferential hydrides to retain ductility and structural integrity. But slow cool-down under higher hoop stress
due to temperature facilitate the formation of radial hydrides since fraction of circumferential hydrides dissolve and
re-precipitate while cracking of hydrides initiate at the low plastic region (Bang et al., 2022). The existence of
mixed hydrides in test specimen result scattered outputs although they may indicate the trend of mechanical property
degradation for increased radial hydride fractions. Further small amount of radial hydrides extremely challenge the
cladding material integrity of the higher hydrogen concentration. To prevent the hydride induced cladding
embrittlement, increasing grain size with a careful advancement can be used since it deteriorate the mechanical
strength of the cladding material investigated on zircaloy-4 (larger grain size hence higher hydride embrittlement
resistance) and Zr-Nb alloy in comparative context (S. Kim, Kang, et al., 2022). Inter-granular hydride
precipitation can be reduced by using larger size grains which limit the hydride inter-link configuration (hence
limiting occurrence of abrupt ductile to brittle transition) and reduce the available sites for hydride precipitation.
But the transition also depend on the cladding material microstructure and the hydride morphology mainly the radial
ones. Although circumferentially hydride zircaloy is brittle at room temperature, it recovered ductility of the matrix
when temperature get increased while radially hydride remain relatively brittle with micro-cracking propagation
along the hydride continuous path (J. S. Kim et al., 2015). Due to the aforementioned reasons, the hydride
morphology effect (whether circumferential or radial) on cladding ductility become negligible at high temperatures.
As the number of thermal cycles increase, hydride particles precipitate closer (inter-linked configuration by
increased connectivity) which facilitate the radial cracking (Motta et al., 2019).

Hydride accumulation in the cladding periphery form hydride rim or radially localized hydride layer due to the
cladding radial temperature gradient which drive the cladding to behave brittle fracture at low temperature
conditions with propagation of axial cracks or burst opening (Nagase & Fuketa, 2005). The micro-structural and
crystallographic features of the circumferential and radial hydrides in terms of hydride distribution and stress
reorientation behavior require detailed characterization (Li et al., 2020). Here the hoop stress exceeding certain
threshold stress change the growth direction of hydrides from tangential direction to the radial direction of the
cladding tube. Since the spent fuel decay heat reduction through time, and hydrogen precipitation occur at lower
(around 50 years) of the dry storage (Dehyeon Woo, 2019). The increased hydride content decrease ductility related
parameters such as total elongation, strain energy density, and offset strain (Bang et al., 2022). But the effect of
hydride orientations on the mechanical properties of hydride zircaloy-4 cladding material become limited. End-cape
weld zone suppress hydride precipitation while increasing embrittlement resistance due to the combined effect of
higher critical nucleation due to matrix stiffness, higher misfit strain and greater grain boundary disorientation angle
(Sangbum Kim, Joo-He Kang, 2023). Large amounts of hydride precipitation make nuclear fuel cladding to be
subjected to increased embrittlement conditions due to mechanical strength (mainly ductility and fracture
toughness) degradation. The extent of hydride interlink facilitates the ductility to brittle transition imparting
discharge burnup limit. Zircaloy also shows embrittlement for circumferential hydrides which cannot be avoided in
characterizing the fuel rod cladding integrity by formation of hydrides.

Reference:

Bang, S., Kim, H., Noh, J., Kim, D., Keum, K., & Lee, Y. (2022). Temperature-dependent axial mechanical properties of
Zircaloy-4 with various hydrogen amounts and hydride orientations. Nuclear Engineering and Technology, 54(5),
1579–1587. https://doi.org/10.1016/j.net.2021.11.007

Cha, H. J., Jang, K. N., An, J. H., & Kim, K. T. (2015). The effect of hydrogen and oxygen contents on hydride reorientations
of zirconium alloy cladding tubes. Nuclear Engineering and Technology, 47(6), 746–755.
https://doi.org/10.1016/j.net.2015.06.004

Chu, H. C., Wu, S. K., Chien, K. F., & Kuo, R. C. (2007). Effect of radial hydrides on the axial and hoop mechanical
properties of Zircaloy-4 cladding. Journal of Nuclear Materials, 362(1), 93–103.
https://doi.org/10.1016/j.jnucmat.2006.11.008

Cui, D., Low, J., & Spahiu, K. (2011). Environmental behaviors of spent nuclear fuel and canister materials. Energy and
Environmental Science, 4(7), 2537–2545. https://doi.org/10.1039/c0ee00582g

Daum, R. S., Majumdar, S., Liu, Y., & Billone, M. C. (2006). Radial-hydride embrittlement of high-burnup zircaloy-4 fuel
cladding. Journal of Nuclear Science and Technology, 43(9), 1054–1067.
https://doi.org/10.1080/18811248.2006.9711195

Dehyeon Woo, Y. L. (2019). Spent fuel simulation during dry storage via FRAPCON-4.0 Modification: comparison between
 PWR and SMR and discharge burnup effect. Nuclear Engineering and Technology, 54 (12) 4499-4513.
https://doi.org/10.7551/mitpress/6965.003.0030

Herranz, L. E., Penalva, J., & Feria, F. (2015). CFD analysis of a cask for spent fuel dry storage: Model fundamentals and
sensitivity studies. Annals of Nuclear Energy, 76, 54–62. https://doi.org/10.1016/j.anucene.2014.09.032

Jang, K. N., & Kim, K. T. (2017). The effect of neutron irradiation on hydride reorientation and mechanical property
degradation of zirconium alloy cladding. Nuclear Engineering and Technology, 49(7), 1472–1482.
https://doi.org/10.1016/j.net.2017.05.006

Kim, Donguk, Kim, D., Woo, D., & Lee, Y. (2022). Development of an image analysis code for hydrided Zircaloy using
Dijkstra’s algorithm and sensitivity analysis of radial hydride continuous path. In Journal of Nuclear Materials (Vol.
564). https://doi.org/10.1016/j.jnucmat.2022.153647

Kim, Dongyeon, Kang, J. H., & Lee, Y. (2022). Accurate prediction of threshold stress for hydride reorientation in Zircaloy-
4 with directly measured interface orientation relationship. In Materialia (Vol. 21).
https://doi.org/10.1016/j.mtla.2021.101291

Kim, Dongyeon, Woo, D., & Lee, Y. (2022). Radial hydride fraction with various rod internal pressures and hydrogen
contents for Zr-Nb alloy cladding tube. In Journal of Nuclear Materials (Vol. 572).
https://doi.org/10.1016/j.jnucmat.2022.154036

Kim, J. S., Kim, T. H., Kook, D. H., & Kim, Y. S. (2015). Effects of hydride morphology on the embrittlement of Zircaloy-4
cladding. Journal of Nuclear Materials, 456, 235–245. https://doi.org/10.1016/j.jnucmat.2014.09.025

Kim, S., Kang, J. H., & Lee, Y. (2022). Hydride embrittlement resistance of Zircaloy-4 and Zr-Nb alloy cladding tubes and
its implications on spent fuel management. Journal of Nuclear Materials, 559.
https://doi.org/10.1016/j.jnucmat.2021.153393

Kim, Y. J., Kook, D. H., Kim, T. H., & Kim, J. S. (2015). Stress and temperature-dependent hydride reorientation of
Zircaloy-4 cladding and its effect on the ductility degradation. Journal of Nuclear Science and Technology, 52(5), 717–
727. https://doi.org/10.1080/00223131.2014.978829

Lee, C., & Lee, Y. (2023). Simulation of hydrogen diffusion along the axial direction in zirconium cladding tube during dry
storage. In Journal of Nuclear Materials (Vol. 579, p. 154352). https://doi.org/10.1016/j.jnucmat.2023.154352

Lee, J. M., Kim, H. A., Kook, D. H., & Kim, Y. S. (2018). A study on the effects of hydrogen content and peak temperature
on threshold stress for hydride reorientation in Zircaloy-4 cladding. Journal of Nuclear Materials, 509, 285–294.
https://doi.org/10.1016/j.jnucmat.2018.07.005

Li, J., Wang, Z., Wu, H., & Chen, G. (2020). Microstructural and crystallographic analysis of hydride reorientation in a
zirconium alloy cladding tube. Journal of Nuclear Materials, 537, 152232.
https://doi.org/10.1016/j.jnucmat.2020.152232

Motta, A. T., Capolungo, L., Chen, L. Q., Cinbiz, M. N., Daymond, M. R., Koss, D. A., Lacroix, E., Pastore, G., Simon, P. C.
A., Tonks, M. R., Wirth, B. D., & Zikry, M. A. (2019). Hydrogen in zirconium alloys: A review. In Journal of Nuclear
Materials (Vol. 518). Elsevier B.V. https://doi.org/10.1016/j.jnucmat.2019.02.042

Nagase, F., & Fuketa, T. (2005). Investigation of hydride rim effect on failure of zircaloy-4 cladding with tube burst test.
Journal of Nuclear Science and Technology, 42(1), 58–65. https://doi.org/10.1080/18811248.2005.9726364

Nam, G., Hong, J., & Lee, Y. (2020). Comparison for spent fuel behavior of PWR and SMRs. Transactions of the Korean
Nuclear Society Virtual Spring Meeting, 1, 1–4.

Sangbum Kim, Joo-He Kang, Y. L. (2023). Suppressed hydride precipitation in the welding zone of Zircaloy cladding tube.
Journal of Nuclear Materials.