molecules

Review
Recent Advances and Prospects in Design of Hydrogen
Permeation Barrier Materials for Energy Applications—A Review
Ewa C. E. Rönnebro * , Robert L. Oelrich and Robert O. Gates

Pacific Northwest National Laboratory, Richland, WA 99352, USA

* Correspondence: [email protected]

Abstract: The hydrogen infrastructure involves hydrogen production, storage and delivery for uti-
lization with clean energy applications. Hydrogen ingress into structural materials can be detrimental
due to corrosion and embrittlement. To enable safe operation in applications that need protection
from hydrogen isotopes, this review article summarizes most recent advances in materials design and
performance characterization of barrier coatings to prevent hydrogen isotopes’ absorption ingress
and permeation. Barriers are crucial to prevent hydride formation and unwanted hydrogen effects
to increase safety, materials’ lifetime and reduce cost for applications within nuclear and renewable
energy. The coating may be applied on a material that requires protection from hydrogen pick-up,
transport and hydride formation in hydrogen storage containers, in pipelines, spent nuclear fuel
storage or in nuclear reactors. While existing, commercial coatings that have been much in use may be
satisfactory for various applications, it is desirable to evaluate whether alternative coating concepts
can provide a greater resistance to hydrogen isotope permeation along with other improved proper-
ties, such as mechanical strength and thermal resistance. The information presented here is focusing
on recent findings within the past 5–7 years of promising hydrogen barriers including oxides, nitrides,
carbon, carbide, MAX-phases and metals and their mechanical strength, hydrogen pick-up, radiation
Citation: Rönnebro, E.C.E.; Oelrich, resistance and coating manufacturing techniques. A brief introduction to hydrogen permeation is
R.L.; Gates, R.O. Recent Advances provided. Knowledge gaps were identified to provide guidance for material’s research prospects.
and Prospects in Design of Hydrogen
Permeation Barrier Materials for Keywords: hydrogen permeation; hydrogen absorption; barrier coatings; hydrogen pick-up; tritium;
Energy Applications—A Review. renewable energy; nuclear reactor; fusion reactor; radiation resistance; coating manufacturing; tritium
Molecules 2022, 27, 6528. https:// permeation barrier; permeation reduction factor
doi.org/10.3390/molecules27196528

Academic Editor:
Boggavarapu Kiran
1. Introduction
Received: 14 September 2022
1.1. Hydrogen Barriers
Accepted: 27 September 2022
Published: 2 October 2022
The hydrogen infrastructure includes hydrogen production, storage and delivery. To
store hydrogen in materials with high gravimetric and volumetric energy density, a variety
Publisher’s Note: MDPI stays neutral of different classes of materials have been explored extensively in the past 20 years. If,
with regard to jurisdictional claims in
however using containers to store hydrogen gas, materials that do not pick-up hydrogen
published maps and institutional affil-
is needed. To further reduce hydrogen pick-up and permeation in container materials, a
iations.
hydrogen barrier can be applied as a coating on the substrate materials.
Hydrogen barriers are crucial to enable safe energy solutions in support of a clean
energy infrastructure and for safety of nuclear reactors such as fusion reactors, development
Copyright: © 2022 by the authors.
of future Gen IV nuclear reactors as well as to contain spent fuel [1–3]. Some of the Gen
Licensee MDPI, Basel, Switzerland. IV reactors will be used for hydrogen production and some use high-temperature salt-
This article is an open access article coolants [4]. With an excellent barrier, accidents could be avoided or reduced in severity by
distributed under the terms and preventing tank, structural or pipe-line material failure and help mitigate the consequences
conditions of the Creative Commons of Zirconium-water reactions in nuclear reactor incidents such as the one in Fukushima in
Attribution (CC BY) license (https:// 2011 which spurred an increase in materials research. By preventing ingress of hydrogen
creativecommons.org/licenses/by/ isotopes, the material will exhibit longer lifetime and avoid costly replacements of parts
4.0/). due to embrittlement. For nuclear applications, many of these hydrogen barriers exhibit

Molecules 2022, 27, 6528. https://doi.org/10.3390/molecules27196528 https://www.mdpi.com/journal/molecules

Molecules 2022, 27, 6528 2 of 21

excellent permeation-resistant behavior in the laboratory but fail when used in a radiation
environment. Irradiation and implantation can affect the transport of hydrogen isotopes in
materials. In addition to resistance to hydrogen absorption and permeation, the coatings
must be reasonably ductile and have good strength to preclude cracking during fabrication
and service.
Various materials which could serve as effective hydrogen barriers have been identi-
fied and some are commercially available. Their function for a desired application depends
on various factors including temperature, pressure, microstructure, coating thickness,
compatibility with the substrate and sometimes compatibility with chemical reactions.
Therefore, the barrier must be carefully selected per application along with appropriate
manufacturing method. Among classes of hydrogen permeation barriers that have been
explored are oxides, nitrides, carbides, carbon, metals and intermetallics. Although metals
such as tungsten and gold possess permeabilities low enough to permit them to be con-
sidered as hydrogen permeation barriers, most of the recent work has been focused on
ceramic-based barriers.
The hydrogen barrier is typically applied as a thin coating/film onto a substrate
material, although the container itself can be the hydrogen barrier [3]. With the emerging
of nanoscience and computational science, several novel approaches and strategies have
been applied in recent years to design better hydrogen permeation barriers that can also
meet other requirements. The following minimum criteria needs to be considered for the
function of a hydrogen barrier:
n Reduced hydrogen pick-up to avoid hydrogen transport and formation of hydrides
and hydrogen effects
n Show mechanical strength
o Coating needs to maintain integrity and to not weaken strength of cladding
n Reduced embrittlement due to hydride formation during service
n Reduced thermal stress or thermal expansion between cladding and coating
n Corrosion resistance (in water and/or oxygen)
n Manufacturing feasibility
In addition, the following criteria are important in nuclear applications:
n Reduce hydrogen isotope permeation into the reactor coolant system (RCS)
n Reduce hydrogen isotope ingress into nuclear reactor’s structural materials
n High-temperature resistance up to loss-of-coolant accident (LOCA) conditions
(≥1200 ◦ C)
n Neutron transparency
n Long term endurance in the radiation environment of a nuclear reactor
With this review article, we have summarized advanced coatings and prospects to
prevent hydride formation and hydrogen effects due to hydrogen (H1 , H2 , H3 ) pick-up
and transportation. When using ‘hydrogen’, we include all isotopes (protium, deuterium
and tritium). Research in this area has intensified in the past decade due to the increased
investment in development of future nuclear reactors and a hydrogen infrastructure. Most
of the cited literature is from within 5–7 years of publication date and represents promising
approaches to further advance hydrogen barriers including materials design, nanoengineer-
ing and computational science. The hydrogen barrier coating may be applied to a container,
such as FeCrAl, zirconium, CrN or SiC, with the purpose to avoid safety concerns due
to hydrogen effects that can reduce materials integrity. Or, the container itself can be the
hydrogen barrier. For nuclear applications, neutron transparency and minimal impact on
the neutron economy also need to be taken in consideration along with radiation endurance.
With the understanding that barriers work by limiting the area available for the gas to
contact the underlying metal surface, and possibly by creating low enough permeation for
recombination to occur and even further reduce the permeation, the questions are how ra-
diation affects this process and whether it enhances permeation which could be detrimental
if causing embrittlement in a nuclear reactor and further studies are much needed.
Molecules 2022, 27, 6528 3 of 21

The key challenge is to identify a material that is an excellent hydrogen barrier but
not brittle and with mechanical strength. Another challenge is fabrication of the coating
without creating cracks or thermal stresses during welding and joining.
We start out discussing the mechanism for hydrogen permeation, how to measure
permeation according to ISO and ASTM standards, and coating/thin film preparation
methods. The following sections summarize recent findings for various coatings, i.e., oxides,
nitrides, carbon materials, MAX phases, metals and intermetallic alloys and knowledge
gaps are identified with a focus on hydrogen barriers for nuclear reactor related applications.
To further advance these materials towards commercial use, these selected barriers should
be subjected to studies to evaluate materials’ performance related to atomic structure
and chemical composition, including mechanical strength, hydrogen pick-up resistance,
radiation resistance, corrosion and coating preparation techniques that are feasible for
manufacturing.

1.2. Mechanism for Hydrogen Permeation

The permeation of hydrogen isotope through solid materials is accepted to proceed
via adsorption, dissociation, diffusion, and recombination coupled with desorption. An
effective barrier would prevent (or at least significantly reduce) ingress followed by dif-
fusion into film and further into the substrate. Figure 1 shows a schematic illustration of
hydrogen permeation in a coated sample if the permeation proceeded all the way through
the substrate to desorption and recombination. A hydrogen molecule (H2 ) is adsorbed on
the surface of the film and disassociates to hydrogen atoms (H). The adsorbed hydrogen
atoms diffuse into the film from the film surface (absorption) and move toward the interface
with the substrate. The hydrogen pick-up barrier should effectively prevent hydrogen
atoms to diffuse into the film and further into the substrate. Hydrogen atoms can diffuse
into the substrate from the interface of the film to the non-coated side of the substrate
where the hydrogen atoms form hydrogen molecules and then desorption occurs. When
performing a permeation measurement per an ISO procedure, the hydrogen isotope
Molecules 2022, 27, x FOR PEER REVIEW 4 of is
22
entering on the coated side and permeates through the substrate to be measured on the
other side as discussed below in Section 1.3.

Figure1.1.Illustration
Figure Illustrationofofhydrogen
hydrogenpermeation
permeationin in
a thin film
a thin coated
film substrate;
coated dissociation,
substrate; adsorption
dissociation, adsorp-
on surface,
tion diffusion
on surface, in thin
diffusion infilm
thincoating, diffusion
film coating, in substrate,
diffusion recombination
in substrate, and desorption.
recombination and desorption.

We will briefly discuss the basic equations related to permeation. Permeability of hy-
drogen and its isotopes is the steady state diffusional transport of atoms through a mate-
rial as illustrated in Figure 1 that supports a differential pressure of the hydrogen isotope.
Wipf showed in 2001 that most metals follow an Arrhenius relationship (or va not Hoff
 Molecules 2022, 27, 6528 4 of 21

We will briefly discuss the basic equations related to permeation. Permeability of

hydrogen and its isotopes is the steady state diffusional transport of atoms through a
material as illustrated in Figure 1 that supports a differential pressure of the hydrogen
isotope. Wipf showed in 2001 that most metals follow an Arrhenius relationship (or
va not Hoff plot) for hydrogen isotope diffusion [5]. Wipf focused on crystalline host
metals without defects like vacancies, dislocations and grain boundaries or impurity atoms
which have an impact on permeability. Other factors that also impact permeation are
microstructure and material composition. Lattice defects are potential hydrogen traps
and can therefore modify the behavior of hydrogen substantially. Trapping occurs if
potential energies for hydrogen atoms are lowered in interstitial sites. This is equivalent
with a larger time of residence in the corresponding sites and, therefore, H-diffusivity is
reduced. Kirchheim developed in 2001 a general model based on Statistical Mechanics
and Random Walk which allows to describe the behavior of hydrogen in disordered
systems, i.e., metallic glasses, amorphous silicon, nanocrystalline metals, deformed metals,
disordered metallic solutions, and metallic multi layers [6]. The reader is referred to this
paper for the mathematical models.
Assuming a clean surface, permeation (Pm) is the product of diffusion (D0 ) and
solubility (S0 ) which are temperature dependent, and both follow Arrhenius equation
which can be expressed in following equation where E is activation energy (J/mol), H is
enthalpy (J/mol), R is the ideal gas constant and T is temperature (K).
E ∆H
Pm = Do e− RT ∗So e− RT (1)

Diffusion (D) refers to transport of atoms within a single phase. “Permeation” refers
Molecules 2022, 27, x FOR PEER REVIEW to transport of atoms in molecules in a gas phase across a solid phase to another 5 of gas
22 phase.
Permeation is diffusion combined with chemical reactions that convert molecules to their
constituent atoms that then diffuse across a solid and then, by the same chemical reactions
in reverse, form molecular species in a gas phase. Diffusion is driven by differences in
rate in the metal driven by concentration differences across it established through Sievert’s
concentration within a phase. The permeation through a layer of metal is the diffusion rate
Law.
in the metal driven by concentration differences across it established through Sievert’s Law.
Fick’s first law of diffusion relates the steady state diffusional flux (J) in mol/m2s to 2
Fick’s first law of diffusion relates the steady state diffusional flux (J) in mol/m s to
diffusivity (D) in m2/s and2the concentration gradient dc/dx across the solid where c is in
diffusivity (D) in m /s and the concentration gradient dc/dx across the solid where c is in
mol/m3 and x is3 the thickness in meter. It postulates that the flux goes from regions of high
mol/m and x is the thickness in meter. It postulates that the flux goes from regions of high
concentration to regions of low concentration, with a magnitude that is proportional to
concentration to regions of low concentration, with a magnitude that is proportional to the
the concentration gradient (spatial derivative). The diffusional flux (J) can be expressed
concentration gradient (spatial derivative). The diffusional flux (J) can be expressed as:
as:
J = −D(dc/dx)
J = − D(dc/dx) (2) (2)

The solubility (S) represents

The solubility equilibrium
(S) represents between
equilibrium the diatomic
between the diatomichydrogen
hydrogenmolecule
molecule and
and hydrogen
hydrogen atoms
atoms inina ametal
metalaccording
accordingto toHH22 (gas)
(gas) ↔ 2H2H(metal).
(metal).TheThepressure
pressuredependence
de-
pendence follows
follows Sievert’s
Sievert’s lawlawforfor
thethe solubilityofofdiatomic
solubility diatomicgases
gases(hydrogen
(hydrogenisotopes)
isotopes) in
in metals,
metals,where
where ccHH is concentration of the atomic hydrogen isotope, S is the Sievert’s
concentration of the atomic hydrogen isotope, S is the Sievert’s solubility solu-
bility constant
constantininmol/m
mol/m 3Pa3 Pa
1/2 1/2
andand
PH isPHhydrogen
is hydrogenpressure (Pa):(Pa):
pressure
cH = S·PH1/2 (3)
cH = S·PH 1/2 (3)
Hydrogen permeation is defined as the transport of hydrogen as dissociated hydro-
gen atoms and Hydrogen permeation
has units of moles isofdefined
hydrogen as the
gastransport
per square of hydrogen
meter peras dissociated
second (mol·m hydrogen
–
–2 −1 ),
2·sec−1), which is the permeation rate. By combining equations 2 and 3, we get a relation ·sec
atoms and has units of moles of hydrogen gas per square meter per second (mol · m
that canwhich is the permeation
be expressed as rate. By combining equations 2 and 3, we get a relation that can be
expressed as
J =JD·
= S/t (Phigh
D·S/t (P1/2 −P1/2
high −) Plow 1/2 )
low1/2 (4) (4)
where Jwhere
is the permeation rate (mol·
J is the permeation m−2
rate ·sec·−1m),−D2 ·is
(mol secthe diffusion
−1 ), D is the coefficient of hydrogen
diffusion coefficient in
of hydrogen
the material, S is solubility coefficient or Sievert’s constant for the material, which
in the material, S is solubility coefficient or Sievert’s constant for the material, which deter-
mines the hydrogen solubility, and t is the thickness of the solid material. The product of
D and S is referred to as Φ, the permeation coefficient or permeability of the material.

1.3. Permeation Measurements—Gas Transmission Rate

The International Organization for Standardization describes ISO 15105 which spec-
ifies two methods for determining the gas transmission rate of single-layer plastic film or
Molecules 2022, 27, 6528 5 of 21

determines the hydrogen solubility, and t is the thickness of the solid material. The product
of D and S is referred to as Φ, the permeation coefficient or permeability of the material.

1.3. Permeation Measurements—Gas Transmission Rate

The International Organization for Standardization describes ISO 15105 which specifies
two methods for determining the gas transmission rate of single-layer plastic film or sheet
and multi-layer structures under a differential pressure or equal pressure [7,8]. One method
uses a pressure sensor, the other a gas chromatograph, to measure the amount of gas which
permeates through a test specimen. The two methods are summarized below.
Differential pressure method; ISO 15105-1. A test specimen is placed in a gas transmis-
sion cell and forms a sealed barrier between two chambers; a low-pressure (LP) chamber
and a high-pressure (HP) chamber that both are evacuated. A gas is introduced into the
evacuated HP-chamber and permeates into the LP-chamber. The amount of gas which
permeates through the specimen is determined by the increase in pressure on the lower-
pressure side or by gas chromatography. The gas transmission rate (GTR) is the volume of
gas passing through a plastic material (film/sheet), per unit area and unit time, under unit
partial-pressure difference between the two sides of the material. Gas permeability (P) is
the volume of gas passing through a plastic material of unit thickness, per unit area and
unit time, under unit partial-pressure difference between the two sides of the material.
The gas transmission rate (GTR) and the gas permeability, or coefficient of gas perme-
ability is calculated from Equations below.
If using a gas chromatograph:

GTR = 273 × (Vs − Vb ) × k/(22,4·T·A·t·ph ) (5)

Or if using a pressure sensor:

GTR = Vc /(R·T · Ph ·A)·dp/dt (6)

where GTR is the gas transmission rate [mol/(m2 ·s·Pa)]; T is the test temperature (K); t
is the time (seconds) during which test gas was collected in the sampling loop; Vs is the
amount of test gas collected in the sampling loop (liters); Vb is the blank reading (liters); Vc
is the volume of the low-pressure chamber (liters); ph is the pressure in the high-pressure
chamber (Pa); A is the transmission area of the specimen (m2 ); k is a conversion factor for
converting the sampling loop volume to the total volume of the low pressure chamber;
dp/dt is the change in pressure per unit time in the low-pressure chamber (Pa/s); R is the
gas constant = 8.31 × 103 (l·Pa)/(K·mol).
Gas permeability is calculated from GTR and specimen thickness:

P = GTR × d (7)

where P is the gas permeability, or coefficient of gas permeability [mol·m/(m2 ·s·Pa)]; GTR
is the gas transmission rate [mol/(m2 ·s·Pa)]; d is the average thickness of the specimen
(meters).
Equal Pressure Method; ISO 15105-2. A test specimen is placed in a gas-transmission
cell with two chambers forming a sealed barrier in between. One chamber is slowly
swept with a carrier gas and the test gas is inserted into the second chamber. Since the
partial pressure of the test gas is higher in the second chamber, the test gas permeates
through the barrier into the carrier gas in the first chamber. The test gas which permeates
through the specimen is carried by the carrier gas to a sensor. Permeability is calculated
per above equations.

1.4. Permeation Measurements—Electrochemical Technique

ASTM G148 describes a procedure for the evaluation of hydrogen uptake, perme-
ation and transport in metals using an electrochemical technique which was developed
Molecules 2022, 27, 6528 6 of 21

by Devanathan and Stachurski [9,10]. This practice describes calculation of an effective

diffusivity of hydrogen atoms in a metal and for distinguishing reversible and irreversible
trapping. It is based on the steady-state hydrogen flux. In above described solid-gas
ISO-15105 permeation measurement, hydrogen atoms are generated by gas adsorption and
dissociation on the solid surface. In the electrochemical technique, hydrogen atoms are
produced by electrochemical reactions in an electrolyte. The experimental set-up consists
of a separate charging and oxidation cell as described in ASTM G148. Specimens may be in
the form of plate or pipe. In many cases, the measurements of permeation current versus
time are useful in characterizing the severity of hydrogen charging.
The steady state permeation current (Jss ) in mol/s/cm2 gives information on the
subsurface concentration of hydrogen atoms at the charging surface as follows:

Jss = Jss /(A·F) = D1· C0 /L (8)

where D1 is the lattice diffusion coefficient; C0 is the sub-surface concentration of atomic

hydrogen at the charging side of the specimen (mol/cm3 ); F is Faraday’s constant (9.6485
× 104 coulombs/mol); A is area (cm2 ); L is the specimen thickness (cm). The ASTM
G148 procedure provides information related to how to determine D1 and analysis of the
permeation transient. For all equations related to this method, the reader is referred to
ASTM G148.

1.5. Coating Application Methods

Selecting the most appropriate coating deposition method can be crucial for the
performance of the barrier material. There are several methods to apply coatings including:
vapor deposition, sol-gel, spray coating, electrodeposition, pack cementation and hot
dipping. A recent extensive review article by Fotovvati et al. from 2019 summarizes
Molecules 2022, 27, x FOR PEER REVIEW 7 of 22
coating techniques for surface protection [11] and we will here provide a brief overview to
highlight the most common methods, i.e., vapor deposition and a new promising method
that industry is adopting, i.e., cold spray. Figure 2 provides a summary of five common
industry is adopting, i.e., cold spray. Figure 2 provides a summary of five common tech-
techniques and their pros and cons along with important analysis methods.
niques and their pros and cons along with important analysis methods.

Figure 2.
Figure 2. Comparison
Comparison of of five
five selected
selected Coating
Coating Application
Application techniques,
techniques, pros
pros (green)
(green) and
and cons
cons (red).
(red).
The right column has basic characterization techniques to analyze hydrogen permeation fabrication
The right column has basic characterization techniques to analyze hydrogen permeation fabrication
applicability, materials integrity, etc.
applicability, materials integrity, etc.

There are two main types of vapor deposition processes: chemical vapor deposition
(CVD) and physical vapor deposition (PVD). These are atomistic deposition methods that
involve vaporization and subsequent deposition of the coating species as a thin film on a
substrate. Vapor-deposited coatings are essentially pore-free and dense provided a thick
Molecules 2022, 27, 6528 7 of 21

There are two main types of vapor deposition processes: chemical vapor deposition
(CVD) and physical vapor deposition (PVD). These are atomistic deposition methods that
involve vaporization and subsequent deposition of the coating species as a thin film on a
substrate. Vapor-deposited coatings are essentially pore-free and dense provided a thick
enough layer is applied. This type of coating results in a reduction in the amount of
moisture or gas that can penetrate through the film and is therefore considered ideal to
reduce corrosion and hydrogen isotope ingress into materials. It has been proposed that
coatings applied by PVD could be suited to reduce corrosion in a nuclear environment in
present day reactors and in Generation IV type of reactors.
An alternative to PVD and CVD is a relatively new coating process that has been
under development since the 80s with recent big strides is Cold Spray (CS) by VRC Metal
Systems [12], also referred to as supersonic particle deposition. It is a high-energy solid-
state coating and powder consolidation process with the lowest temperatures and highest
velocities relative to other thermal spray processes resulting in high strength coatings. The
cold spray technique is beneficial when it is necessary to avoid introduction of thermal
stress that can occur at high temperatures. It can be used to apply coatings of metals, metal
alloys and metal blends for various applications including corrosion-resistant coatings
(zinc and aluminum), dimensional restoration and repair (nickel, stainless steel, titanium,
and aluminum), wear-resistant coatings (chromium carbide–nickel chromium, tungsten
carbide–cobalt, and tungsten copper), electromagnetic interference (EMI) shielding of com-
ponents and structures, high strength dissimilar material coatings for unique manufacturing
solutions, and field repair of components and systems.
Cold spray coatings cause almost no microstructural changes in the powder materials
deposited except for extreme plastic deformation, and it does not increase the oxide because
the process is so rapid [12]. In fact, the process may reduce or even eliminate the existing
oxide layer during cold spray deposition. Other benefits include no “heat-affected zone”
(HAZ) due to very low heat input, no real limit on deposition thickness, low porosity below
1%, coating strength above 275 MPa and bond strength above 68 MPa.
To guarantee fabrication applicability for desired coating on a specific substrate/
cladding, several characterization methods are needed including analyzing coating plus
cladding/substrate compatibility, materials integrity in applied environment, permeation
resistance, mechanical strength. For studying microstructure and surface chemistry, various
advanced tools are available, such as SEM, TEM, AFM, XPS, but will not be reviewed here.
If the material is aimed for use in nuclear reactors, tests in irradiation are needed to learn
irradiation impact on materials integrity and performance.

2. Recent Advances in Hydrogen Permeation Barriers

2.1. Oxides
Several oxide coatings have been explored throughout the years, including Al2 O3 ,
Cr2 O3 , Er2 O3 , ZrO2 . Recently, focus has been on nano-engineering of oxides to improve
properties. Other strategies for materials engineering include structural modifications and
using dopants and mixtures. We summarize the most recent findings.

2.1.1. Aluminum Oxide

Aluminum oxide, Al2 O3 (alumina), has been selected for hydrogen permeation barrier
on stainless steel and is used in various applications. Alumina exists in many meta-
stable polymorphs besides the thermodynamically stable α-Al2 O3 (corundum form) [13].
The commercially available corundum is considered an excellent hydrogen permeation
barrier [14,15] with a permeation reduction factor PRF > 1000–10,000, however mechanical
and thermal strength needs improvement and during irradiation in a nuclear reactor, the
coating does not maintain integrity. Other crystal structures of alumina are not as great
hydrogen barriers as the alpha phase.
Youngman et al. [16] neutron irradiated bulk samples of single crystalline and poly-
crystalline alpha alumina to doses of 1026 n/m2 at temperatures of 925 K and 1100 K.
Molecules 2022, 27, 6528 8 of 21

The samples were found to swell macroscopically between 3% and 6%, depending on the
temperature of irradiation and the form of the material. The damaged microstructures were
investigated with transmission electron microscopy (TEM) to understand the origin of the
macroscopic swelling and they found that the polycrystalline samples were extensively
microcracked, which could be due to anisotropic swelling of the grains which in turn
leads to stresses and fracturing at the grain boundaries. Pells reviewed in 1994 known
radiation damage mechanisms, including microstructure damage and swelling [17]. It
can be noted that experimental in-reactor studies indicate that oxides do not maintain full
integrity during prolonged irradiation which leads to radiation damage due to damaged
microstructure [15,16]. Therefore, structural modification may be necessary to improve the
irradiation tolerance and examples are provided below.
Morono et al. investigated in 2013 the ionizing radiation induced absorption of
hydrogen isotopes in Al2 O3 using thermos-stimulated desorption measurements (TDS)
up to 750 ◦ C on both electron irradiated and unirradiated deuterated samples [18]. The
TDS results indicate that deuterium desorption temperature increases due to the ionizing
radiation that modifies how hydrogen isotopes are trapped within the material, increasing
the energy required to desorb. However, the nature of the chemical process is not known.
In 2014, Greer’s group published a fascinating finding in Science [19]: By creation of
ultralight hollow ceramic nanolattices that absorb energy, it can recover after compression.
This is a possible path towards enhancing mechanical strength. When compressing lattices
by 50% with a lower ratio of 10 nanometers wall thickness to tube diameter leads to defor-
mation that springs back. Although this is a promising result, the synthesis route involves
5 steps which are not likely feasible for low-cost manufacturing. If this phenomenon is to be
further explored for a practical application, a new synthesis route needs to be established.
Another result that points towards improved radiation endurance when using nanolat-
tices was published by García Ferré in 2016 in Scientific Reports [20]. Amorphous/
nanocrystalline Al2 O3 thin films were deposited on austenitic steel substrates and irradi-
ated with heavy ions at 600 ◦ C as a surrogate for neutron irradiation. Irradiation induces
anamorphous-to-crystalline transformation resulting in a nanograined structure, while
continued irradiations induce grain growth. Their findings show promise for use of nanoce-
ramic coatings beyond alumina for in-core, high radiation field components with enhanced
corrosion and wear resistance in applications for accident tolerant fuels for advanced light
water reactors, fuel cladding for Generation IV systems, and tritium breeding components
for fusion tokamaks.

2.1.2. Zirconium Oxide

Zirconium oxide can be used as a hydrogen permeation barrier by naturally forming
zirconium oxide on the surface of zirconium or zirconium alloy by corrosion in water or
intentional heat-induced oxidation and has mainly been considered for nuclear applica-
tions [21]. It has also been used as a debris-resistant feature at the bottom of some fuel rods.
Zirconium oxide and yttria stabilized zirconia (YSZ) have been evaluated for hydrogen
permeation barriers [22].
A coating of zirconium oxide naturally forms on the surface of the zirconium in high-
temperature water (such as in a nuclear reactor), and it acts as a protective barrier. If
engineered, this layer of oxide can inhibit hydrogen from entering the crystal structure
of the metal. A fundamental understanding of the interaction of hydrogen with ZrO2 is
necessary to allow for designing reliable alloys that can reduce hydrogen entry into the
substrate metal. Youssef et al. [23] performed density functional theory (DFT) calculations
in 2016 to assess how doping ZrO2 with 3d transition metals can reduce hydrogen pick-
up. They suggested two design strategies that mitigate the ingress of hydrogen into the
alloy through this barrier oxide; Either a dopant such as Cr that reduces the solubility of
hydrogen in the oxide, or a dopant such as Nb, Ta, W, P, and Mo that speeds up hydrogen
evolution at the oxide surface. A future research prospect is experimental validation of the
theoretical results.
Molecules 2022, 27, 6528 9 of 21

Hatano et al. prepared layers of tetragonal ZrO2 (180 nm) on the surfaces of ferritic
steel substrates by dip coating and electrolytic deposition techniques [24]. These prepa-
ration methods were chosen because they can be applied to larger structures. Hydrogen
permeation tests were carried out at 300–550 ◦ C and compared with a test of a thinner
ZrO2 coating (100 nm). The permeation reduction factor (PRF) for the thicker layer was
larger by an order of magnitude (ca 1000). The thicker layer results in less defects in the
coating which resulted in reduced permeation rate.

2.1.3. Aluminide + Alumina; FeAl-Al2 O3

Iron aluminides have been among the most studied intermetallics since the 1930s.
They have excellent oxidation resistance and their low cost of production, low density, high
strength-to-weight ratios, good wear resistance, ease of fabrication make them attractive as
a substitute for stainless steel in industrial applications.
Among various developed tritium permeation barrier (TPB) coatings, an aluminide
coating typically composed of an inner Fe–Al transition layer with an outer Al2 O3 film
has been selected as the first choice of test blanket module (TBM) TPBs by China, Europe,
India, and the United States for its high permeation reduction factor (PRF), metallurgical
bonding, excellent compatibility, and self-healing. However, in a molten salt reactor (MSR),
the aluminide coating is incompatible with the molten salts, and another tritium barrier
must be used [25].
Oxides, especially Al2 O3 attract much interest as typical candidate TPB materials
for their high melting point, chemical stability, low hydrogen solubility and permeability.
However, the thermal expansion coefficient shows a large difference between the metal
substrate and oxide ceramics, and thus significant thermal mismatch exists, leading to the
failure of the coatings when used in applications with wide variations in temperature. The
common adopted solution method is to form a functional gradient transition layer between
the substrate and the coating, such as the Fe-Al layer.
The preparation process of the aluminide coating generally involves two steps of
aluminization and oxidation. Interdiffusion occurs between Al atoms and Fe atoms on the
substrate surface to form (Fe, Al) solid solution or Fe-Al intermetallic transition layer in
the aluminization step. In the oxidation process, the aluminide layer surface is selectively
oxidized to form an Al2 O3 film. The aluminide coating can be prepared by the technique
of physical vapor deposition (PVD), chemical vapor deposition (CVD), hot-dipping alu-
minization (HDA), electro-chemical deposition (ECD), packing cementation (PC), plasma
sputtering (PS) and sol-gel, etc. A recent review of aluminide preparation methods was
published in 2015 [26].
Yang et al. found in 2016 that the tritium permeability of an γ-Al2 O3 /FeAl coated
container of 321 stainless steel was reduced by 3 orders of magnitude at 500–700 ◦ C relative
to a non-coated container [27], thus the permeation reduction factor (PRF) was in the order
of 1000–6000. It is noteworthy that the commercially available α-Al2 O3 is typically used for
coatings and has lower permeability, however in Yang’s study, they prepared γ-Al2 O3 using
a relatively low temperature route. The Al2 O3 /FeAl barrier resists the tritium permeation
by the diffusion in the bulk substrate at a limited number of defect sites with an effective
area and thickness. The permeation process of the Al2 O3 /FeAl barrier can be described by
the area defect model and all hydrogen isotopic transport occurs through a limited number
of defects with an effective area and thickness.
Xiang et al. investigated how different steel substrates impacts deuterium permeation
resistance of aluminide coatings for tritium permeation barrier (TPB) applications [28].
Their conclusion is that the deuterium permeation resistance of the aluminide TPBs depends
on the steel substrate composition and microstructure.
The method of doping alloying elements adjust and control the structures and perfor-
mance of TPB coatings. Prakash showed that increasing carbon and aluminum contents
leads to decreased hydrogen diffusivity (increased PRF) [29]. At present, studies on benefi-
cial alloying elements of aluminide coatings are mainly focused on rare earth elements such
Molecules 2022, 27, 6528 10 of 21

as Y, Ce and Hf, which can improve the wear, high temperature oxidation and corrosion
resistance of aluminide coatings [26].

2.1.4. Bipolar Oxide: Chromium Oxide-Aluminum Oxide

Recently Xin et al. showed that a Cr2 O3 /Al2 O3 bipolar oxide has better thermal
stability than that of Al2 O3 /stainless steel and promotes the formation of thermodynami-
cally stable phase of α-Al2 O3 [30]. The bipolar oxide was prepared by first electroplating
chromium coating on 316L stainless steel followed by oxidation to form the Cr2 O3 film.
Thereafter, high purity metallic Al was sputtered on Cr2 O3 film and then oxidized before
finally annealing the bipolar samples. The bipolar oxides are composed of P-type Cr2 O3
semiconducting properties and N-type Al2 O3 and show better hydrogen permeation resis-
tance compared with Cr2 O3 or Al2 O3 coatings. Since aluminum oxide has been shown to
have manufacturing feasibility, this bipolar oxide should be similar and therefore this is a
new coating recommended to be evaluated with regard to mechanical strength, corrosion
resistance, neutron resistance, etc.

2.1.5. Rare-Earth Oxides

Rare earth oxides have also been explored for hydrogen barrier applications. They
have high thermal and mechanical stability in reducing atmosphere. Li et al. [31] studied
Er2 O3 coatings on stainless steel in 2017 and showed that nanocrystalline Er2 O3 coating
made by sol-gel method can prevent hydrogen isotopes permeation with PRF of 300. In
2016, Mao et al. fabricated high-quality Er2 O3 thin films by ion beam sputter deposition on
Si(100) as an epitaxial substrate [32], obtaining very low permeability at 873 K or 4 × 10−22
mol Pa−1/2 m−1 s−1 which is several order of magnitude lower than Er2 O3 coatings made
by other methods. However, several Er isotopes have relatively strong neutron absorption
cross-sections which limits their application in nuclear reactors.

2.2. Nitrides
Nitride based thin films have been shown to reduce hydrogen uptake. The binary
nitrides of CrN and ZrN are commercially used as coatings on stainless steels. TiN and
CrN have recently been much explored for use in the nuclear industry to prevent corrosion
and reduce hydrogen ingress and diffusion into cladding and structural materials. Several
groups are working on improving properties for tailored applications by using dopants,
multilayers and various fabrication methods to change microstructure features.

2.2.1. Titanium Nitride

Titanium nitride has been proposed as an excellent hydrogen barrier. It has high
melting temperature, high hardness, excellent exhibited ion-irradiation tolerance and
high thermal conductivity. Recent findings have shown promise in development towards
application to prevent corrosion and hydrogen uptake, however further studies of hydrogen
permeation behavior is needed.
Tamura studied hydrogen permeation characteristics of TiN coated stainless steel and
measured permeation reduction to be 100 to 5000 times compared to uncoated substrate
depending on film’s grain size with the larger grain sizes showing higher hydrogen perme-
ability [33,34]. As is well known, grain boundaries are trap sites for hydrogen, therefore,
microcrystalline structures with many grain boundaries are expected to provide effective
hydrogen-barrier performance. Their recommendation is to focus future studies to un-
derstand the correlation between the hydrogen permeation behavior and microstructure
between various film formations.
Zirconium-based alloys such as Zr–1Nb, Zr–2.5Nb are widely used in nuclear industry
as cladding materials for nuclear fuel. Kashkarov et al. published a review in 2021 of
protective coatings of accident tolerant Zr-based fuel claddings [35]. Hydriding of zirco-
nium alloys leads to degradation of their mechanical properties, hydride cracking and
stress corrosion cracking which can be detrimental for structural materials in contact with
Molecules 2022, 27, 6528 11 of 21

hydrogen isotopes. Kashkarov et al. researched hydrogenation behavior of titanium nitride

(TiN) deposited on Ti-implanted Zr-1Nb alloy [36]. They conducted a comparative analysis
on hydrogenation behavior of the Ti-implanted alloy with sputtered and evaporated TiN
films. Hydrogenation was performed at 350 ◦ C and 2 atm hydrogen pressure. The lowest
hydrogen absorption rate was obtained for Ti-implanted layer with evaporated TiN film
and was reduced about 75 times relative to uncoated Zr-1Nb alloy. Morphology of the films
impacted hydrogen permeation through TiN films: denser film resulted in lower hydrogen
permeation. A dense structure of TiN without voids is necessary along with sufficient grain
boundaries that traps hydrogen. Thus, the fabrication of Ti-implanted layer with dense
TiN films can be an effective way to protect Zr-1Nb alloy from hydrogen embrittlement.
Alat et al. studied ceramic multilayered coatings with waterside corrosion resistance
in an attempt to develop accident tolerant fuel (ATF) [37]. Hydrogen is evolved during
the corrosion reaction which with time will precipitate hydrides in Zr-cladding, causing
embrittlement, therefore, it’s important to reduce corrosion. They found that monolithic
and multilayer Ti1−x Alx N (where x ~ 0.54–0.67) and TiN coatings on ZIRLO® substrate
by cathodic arc physical vapor deposition (CA-PVD) to improve corrosion resistance.
Multilayers with TiN prevents formation of Boehmite and layer architecture optimized to 8
multi layers coating. No crack or delamination/spallation was observed, indicating good
corrosion resistance. Only a thin TiN layer is required as a barrier to minimize Al migration
and prevent boehmite formation. However, hydrogen permeation was not evaluated and
such a study could be of interest for future prospects.

2.2.2. Chromium Nitride

Chromium nitride is commercially used as a corrosion barrier on stainless steel.
Chromium nitride has received a lot of attention in the nuclear industry and nuclear
energy world. In 2015, Daub et al. [38] published a study on commercially available coat-
ings of CrN, TiAlN and AlCrN applied by physical vapor deposition to obtain 2–4 µm
thick coatings on Zircaloy-4. The corrosion resistance, as well as the impact on hydrogen
permeability of these coatings, was investigated. The corrosion resistance was investigated
under pure water at 350 ◦ C for 24 h and under CANDU conditions (300 ◦ C and pH 10.5)
for 30 d. Limited experiments were also performed in superheated steam at temperatures
up to 1100 ◦ C. The CrN-coated samples have shown the best corrosion resistance to date,
under pressurized water reactor, CANDU, and superheated steam conditions. Additionally,
oxidation of the CrN and TiAlN coatings caused a significant reduction in the hydrogen
uptake.
In 2018, Kashkarov et al. [39] studied CrNx coatings on Inconel 718 superalloy with
respect to microstructure, hydrogen permeability and tribology. They found that a mixed
cubic CrN and hexagonal Cr2 N structure has the lowest hydrogen permeability at 873 K
(500 ◦ C) and 2 atm hydrogen pressure due to higher packing density of the cubic phase.

2.2.3. Less Common Nitrides

Matějíček et al. studied “less-common nitrides” for physical vapor deposited coatings
of AlCrN, CrN, Cr2 N, CrWN, WN and ZrN for their suitability as hydrogen permeation
barriers [40]. The permeation reduction factor (PRF) ranged from ~102 to ~5×103 ; the best
result being achieved by the ZrN coating and is a promising candidate for future studies.
Tamura et al. studied a new multi-layered coating of TiAlN/TiMoN [41]. Hydrogen
permeabilities of TiAlN-coated, TiN-coated, and TiAlN/TiMoN multi-layered coating
samples were measured at 573 K to be 1/100, <1/100 and <1/1000, respectively, relative to
the uncoated 316L stainless steel substrate, thus, the new multi-layered coating performs
10 times better as a hydrogen permeation barrier than TiN and TiAlN.
Houben et al. [42] investigated in 2020 tungsten (W), tungsten nitride (WN) and
WN+W layers on Eurofer97 steel substrates. Deuterium permeation measurements at
400 ◦ C showed PRF = 8 for W, PRF = 31 for WN and PRF = 1000 for WNW. The thermal
expansion coefficient between W and martensitic steels are different and therefore W
Molecules 2022, 27, 6528 12 of 21

coatings cracks during thermal annealing and therefore is not useful as TPB on steels.
However, WN and WNW coatings do not crack up and can be used as TPB on steels.
In 2022, Diaz-Rodriguez et al. [43] studied hydrogen permeation along grain bound-
aries in nanostructured tungsten deposited on nickel substrate. Their permeation measure-
ments at 520–705 K (247–432 ◦ C) resulted in PRF ~ 4 at all temperatures. The obtained
permeability is much higher than reported in the literature for specimens with larger grain
size. Their explanation is to be due to grain boundaries perpendicularly oriented relative
to surface which facilitates hydrogen migration resulting in higher permeability.

2.2.4. Irradiation Experiments on Nitrides

In-pile testing of CrN, TiAlN and AlCrN coatings on Zircaloy cladding was performed
in the Halden Reactor by Van Nieuwenhove et al. [44]. Their conclusions were that TiAlN
and AlCrN coatings disappeared but that CrN coating was chemically stable (BWR and
PWR). The fact that the TiAlN and AlCrN coatings disappeared is probably related to the
fact that the oxide formed on aluminum, namely Al2 O3 , dissolved rapidly in BWR or PWR
water. Moreover, there was no reduction in coating thickness and CrN coatings reduce
hydrogen uptake in zircaloy. Despite accident like conditions, most of the CrN coating was
still intact after 150 d. When a crack occurs, oxide forms underneath and the expansion
leads to further cracking. Irradiation experiments on ternary and layered nitrides in a
hydrogen gas environment to study hydrogen pick-up have not been performed. CrN
appears to be a viable hydrogen barrier for use in nuclear reactors.
Structural modification has been considered as one of the most promising ways to
improve irradiation tolerance of transition metal nitride coatings. Numerous structural
modification methods have been proposed to enhance the irradiation tolerance of coatings
during recent years. Among them, two traditional structure design strategies; multilayer
and compositional gradient, have been attracting research interest. A multilayered struc-
ture is formed by assembling two different sublayer materials resulting in introducing
abundant interlayer interfaces into the coating, which act as sinks to absorb and/or dis-
perse irradiation induced defects. A multilayered coating often shows superior irradiation
resistance and mechanical properties. A compositional gradient is produced along the
coating thickness direction resulting in continuous change of microstructure and chemical
composition, and also absence of interlayer interfaces. A compositionally graded coating
has good mechanical reliability; high adhesion strength and thermal shock resistance. It is
proposed that a coating system of hybrid architecture of multilayered and compositionally
graded structures is a new direction to enhance irradiation resistance.

2.3. Carbon Materials

Carbon materials have been explored for use as hydrogen storage materials at room
temperature to liquid nitrogen temperatures and for high-temperature applications within
nuclear energy. Graphite is used as a structural and moderator material in nuclear power
reactions and in next-generation nuclear reactors. Carbon materials have also been inves-
tigated for hydrogen storage at very cold temperatures. Carbides have been studied for
hydrogen barriers and recently other forms of carbon have been proposed, i.e., diamond-
like carbon (DLC), graphene, metal-graphene and graphene oxide which will be discussed
below.

2.3.1. Diamond-Like Carbon (DLC)

In 2017, Tamura reported the use of Diamond-Like Carbon (DLC) as an amorphous
coating on 316L stainless steel with much lower hydrogen permeation resistance at 573–773
K (200–500 ◦ C) relative to stainless steel and nitride coatings of ZrN, TiAlN, AlCrN, CrN [45].
The coatings that were pre-absorbed with hydrogen showed even lower permeability due
to hydrogen being trapped and hence reducing diffusion through the coating.
DLC is an amorphous coating with a mixture of diamond structure (sp3 ) and graphite
structure (sp2 ). DLC coatings have superior properties such as high hardness, high resis-
Molecules 2022, 27, 6528 13 of 21

tance to abrasion, low friction and high insulation. DLC coatings have a wide range of
applications, but tests on hydrogen barrier functions are quite limited.
Tamura showed that DLC + buffer layers has even better permeation resistance [45]. The
buffer layer consists of two layers on the 316L stainless steel substrate; a metallic Cr coating
coated with CrN with DLC coated on top of the buffer layers. The combination of the
buffer layer and the DLC coating [DLC (20% H2 )] had the lowest hydrogen permeation rate.
Compared to stainless steel, the hydrogen permeation rate was reduced at least 1000 times.

2.3.2. Graphene and Graphite

Graphene has been explored for hydrogen barrier application to prevent embrittle-
ment and oxidation of metals in industry and nuclear reactor applications [46–48]. It has
also been investigated for hydrogen storage, typically at high pressures and very low tem-
peratures [49]. Graphene is a monolayer of carbon atoms bound in a hexagonal honeycomb
lattice forming planes of sp2 -bonded atoms. Layers of graphene stacked on top of each
other form graphite. Graphene is the thinnest material known at one atom thick, and about
200 times stronger than steel. Furthermore, graphene is a conductor of heat and electricity.
It is a diverse material and can be combined with other elements (including gases and
metals) to produce different materials with various superior properties. Producing high
quality materials is however a challenge. Dozens of companies around the world are
producing different types and grades of graphene materials, ranging from high quality
single-layer graphene synthesized using a CVD-based process to graphene flakes produced
from graphite in large volumes.
A paper in Nature Communications by Su et al. in 2014 [50] showed that chemically
reduced graphite oxide (GO) films exhibit exceptional barrier properties with respect to all
tested gases, liquids, salts and acids, with no detectable permeation. The GO films can be
considered as thin graphitic linings and graphite is one of the most stable and chemically
inert materials. Su et al. believes that many applications are possible when a barrier against
moisture, oxygen and other gases and liquids is required. However, they do not mention
hydrogen or mechanical strength and further exploration is needed.
Kim et al. [51] developed in 2016 ultra-high strength V-graphene nanolayers and the
He+ irradiation study revealed excellent radiation tolerance. Interestingly, they found that
inclusion of graphene in the form of V-graphene nanolayers can result in a high strength
material, but the graphene can also self-heal the crystalline defects that are introduced
during irradiation. Nanocrystalline V-graphene nanolayers composites were synthesized
by first depositing V-monolayers with RF sputtering and then graphene was fabricated
using CVD. Hydrogen permeation of metal-graphene nanolayers have not been explored.
Yang et al. [52] investigated in 2020 GO-Al2 O3 for tritium permeation barrier. The
composite coating was prepared by sol-gel, creating nanosheet layers that according to
their deuterium permeability tests blocked diffusion nine times higher (PRF = 9) compared
to Al2 O3 coating at 500 ◦ C. Furthermore, the toughness of the GO-Al2 O3 coating was
enhanced 40%.
The performance and lifetime of nuclear graphite are closely related to the irradiation
environment and are affected by the specifics of the graphite: manufacturing process,
graphitization temperature, composition, etc. Most graphite programs are researching
unirradiated and irradiation material property performance, with a focus on irradiation
creep behavior as the life-limiting mechanism for graphitic components. Irradiation damage
from fast neutrons creates lattice defects leading to changes in physical and mechanical
properties and the accumulation of stresses. Atsumi et al. [53] studied impact of neutron
irradiation on hydrogen retention in graphite and showed that the amount of retained
hydrogen increased by 100 times and the absorption rate decreased to one seventieth
compared to unirradiated samples. Hydrogen trapping sites can be created by neutron
irradiation which reduces hydrogen diffusivity.
Carbon in the form of isotropic graphite is used in fluoride salt-cooled high-temperature
reactors (FHRs) and thermal-spectrum Molten Salt Reactors (MSRs) as a neutron moderator.
Molecules 2022, 27, 6528 14 of 21

The current status of tritium control and capture is that limited data indicate it is feasible
to maintain very low levels of tritium in a salt-cooled reactor using carbon. Forsberg et al.
published a review in 2017 of tritium control and capture in salt-cooled fission and fusion
reactors: status, challenges, and path forward [25].

2.3.3. Carbides
Carbides have been studied for hydrogen permeation barriers, mainly TiC and SiC.
TiC is difficult to deposit with CVD and therefore TiC-TiN has been applied obtaining
10 times higher permeation rate factor (PRF) than TiC alone [54]. Nemanič summarized
PRFs for selected carbides, nitrides and oxides in a recent article from 2019 [54].
Tamura et al. [34] recently studied TiC along with Al2 O3 and TiN, using the radio-
frequency (RF) ion plating method to form films on type 316L austenitic stainless steel
substrates. The hydrogen permeability decreased by at least two orders of magnitude in all
test specimens after the Type SUS316L substrates were coated. Tamura et al. observed that
the microstructure had an impact on hydrogen permeability.
Silicon carbide (SiC), Carborundum, is one of the proposed candidates to protect
or replace zirconium fuel claddings due to higher melting temperature, better corrosion
resistance at high temperatures and similar thermal neutron capture cross-section compared
to zirconium. SiC coatings demonstrate high hardness, high thermal conductivity and
good oxidation resistance at high temperatures. Silicon carbide is an excellent hydrogen
permeation barrier. A trade-off study by INL [55] in 2012 highlights that irradiation studies
have been performed and SiC was shown stable; SiC retain strength during LOCA up to at
least 1300 ◦ C.
Although SiC is very promising, the industry must still develop a robust and com-
mercially viable end plug joining process for final fuel rod fabrication, as current industry
methods for welding end plugs on Zirconium rods will not apply to SiC composite ceramics.
Recently, nuclear fuel vendors and others have focused on cladding options and
SiC/SiC composite ceramics, which provide most of the enhanced accident-tolerant char-
acteristics. SiC is one of the hardest substances known and is widely used in wheels for
cutting stone. SiC composites are structures made up of SiC fibers and SiC monolith pieces
that resist the shattering experienced by most ceramics.
Kashkarov et al. [56] coated SiC as a hydrogen barrier on Zr-1Nb. Amorphous SiC
coating of 1.5-µm thickness was deposited on Zr-1Nb alloy substrate by direct current
(DC) magnetron sputtering of composite cathode. Hydrogen absorption decreased 8 times
due to low hydrogen permeability of the coating. Hydrogenation tests show that SiC
coating provides protective properties against hydrogen permeation in the investigated
temperature range of 350–450 ◦ C.
In 2020, Wang et al. [57] published a new important finding in Nature Materials on
radiation-induced temperature dependent segregation in a ceramic which is different from
that shown in metallic systems. Irradiation of silicon carbide at 300 ◦ C leads to carbon
enrichment near grain boundaries (GB), whereas the enrichment diminishes for irradiation
at 600 ◦ C. Wang et al. point out that radiation-induced segregation (RIS) is one of the most
dramatic changes that can take place in GBs under irradiation or ion implantation and has
been observed in many metallic alloys. The segregation in SiC occurred at a much lower
irradiation temperature than typical RIS in metals. An ab initio informed rate theory model
was used to demonstrate that this difference is introduced by the unique defect energy
landscapes present in the covalent system. It is unknown how the carbon enrichment
impact hydrogen behavior in SiC, but it is well known that hydride phases grow at grain
boundaries. Depending on use of SiC in a nuclear reactor, it could be important to explore
this effect to avoid hydrogen trapping or permeation enhancement effects.
In 2019, Hu et al. at ORNL [58] reported hydrogen isotope permeability of SiC-based
cladding. Deuterium permeation flux was measured after exposing SiC fiber-reinforced
SiC matrix ceramic composites to high heat flux neutron irradiation. They studied SiC/SiC
tubes as is and as coated with CrN, Cr and TiN using cathodic arc physical vapor deposition.
Molecules 2022, 27, 6528 15 of 21

At <250 ◦ C, hydrogen permeability in SiC has been measured to be <1 × 10−21 mol
H2 m−1 s−1 MPa−1/2 [59]. Hu et al. measured deuterium leak rates at 300–500 ◦ C as a
function of deuterium pressure. A low heat flux resulted in deuterium leak rates down to
10−11 atm-cc/s. Higher heat flux resulted in deuterium lek rates in the range of 10−6 to
10−9 atm-cc/s. Cr-coated SiC/SiC showed lower deuterium leak rates of 10−12 atm-cc/s at
low heat flux and lower for CrN-coated SiC/SiC. This is their first-generation coatings and
they expect that future generation coatings will show better performance.
In 2019, Terrani et al. at ORNL [60], demonstrated a new promising method to produce
crystalline, high-purity SiC coatings using 3D binder jet printing. They claim that their
advanced manufacturing method give complete freedom in geometric complexity which
opens use of SiC on surfaces that previously were difficult to coat with other methods.
They did not report hydrogen permeability which would be of interest to measure in the
future to compare with previous permeability measurements of SiC.

2.4. MAX-Phases and MXenes

MAX phases can also provide excellent hydrogen barrier properties depending on
environment. They are a group of ternary ceramic compounds composed of: M: early
transition metals (Sc, Ti, V, Cr, Zr, Cr, Nb, Mo); A: elements in the A group (mainly Al, Si, P,
S, Ga, Ge, Pb); X: carbon or nitrogen [61]. Recently, several MAX phases have been studied
for hydrogen isotope barrier or nuclear cladding materials including: Ti3 AlC, Ti3 SiC2 ,
Ti2 AlC and TiAlN.
This group of materials needs to be much more explored to learn hydrogen barrier
behavior, mechanical strength, irradiation resistance, etc. Recently, testing in radiation
has been performed. Ward et al. [62] suggest that MAX phases are not suitable for in-core
nuclear applications below 350 ◦ C. The use of Ti3 SiC2 and Ti3 AlC2 are good examples of
the inherent problem with MAX phases in irradiating environments at low temperatures.
The results have shown that similar observations to neutron and heavy ion irradiation are
seen with proton irradiation of Ti-based MAX phases, namely: anisotropic changes in unit
cell dimensions and decomposition of the MAX phase to TiC.
In 2018, Tang et al [63] studied Cr2 AlC and Ti2 AlC coated on Zircaloy-4 as accident
tolerant fuel cladding. Neutron radiography was used to measure hydrogen permeability
but the detection limit is in the order of magnitude of 10−4 gm−2 s−2 and the permeation
rate of the coatings is lower than that. Although these two coatings appear to be reducing
permeation rate, more sensitive detection system is required to quantify permeability.
In 2020, Gröner et al. [64] measured deuterium permeation of Ti2 AlN coated on ferritic
stainless-steel substrates. They also studied pre-oxidized coatings finding that that the
Ti2 AlN coating obtained a PRF = 45 relative to stainless-steel and the pre-oxidized coating
obtained a PRF = 3700.
In 2021, Tunes et al. [65] studied radiation resistance of Cr2 AlC thin film by submitting
them to heavy ion irradiations relevant to nuclear reactors. Their test was done in situ in
a TEM at 623 K (350 ◦ C). Importantly, the Cr2 AlC material did not undergo catastrophic
failure or localized fracture in contrast to other materials such as TiFeN and CrN.
Naguib et al. [66] reviewed in 2021 ten years of progress in development of MXenes.
MXenes are a new class of two-dimensional layered materials of carbides, nitrides and
carbonitrides. They are called ‘MXenes’ because they are made by etching ‘A’ layer from
MAX phases and the suffix ‘ene’ is added due to the similarity to grapheneThere are
currently about 150 MAX-phases and 40 MXenes. MXenes can be made by selective etching
of a MAX phase.
Shi et al. [67] reported in 2021 MXene coatings as new hydrogen permeation barriers
for pipe steels. The MXene (Ti3 C2 Tx ) nanosheets were synthesized and coated on X70
pipe steel using spin-coating in a colloidal suspension. Shi et al. measured hydrogen
permeability using an electrochemical method and also assessed hydrogen embrittlement
and corrosion resistance. The calculated permeability is two times lower for coated pipe
compared to uncoated pipe. The barrier mechanism is due to the multilayered structures,
Molecules 2022, 27, 6528 16 of 21

and they discuss how difficult it is to break Ti-C bonds and form C-H bonds when hydrogen
atoms diffuse.

2.5. Metals
2.5.1. Chromium
Chromium coatings have been much investigated recently and is a leading candidate
in the nuclear industry. Framatome (formerly AREVA NP) and Westinghouse are actively
developing several enhanced accident tolerant fuel claddings including Cr-coated zircaloy
and SiC/SiC composite sandwich cladding. A paper by Bischoff et al. [68] focused on
developing Cr-coated M5 cladding using a physical vapor deposition (PVD) prototype
machine to coat full-length cladding tubes. Their characterization confirmed that Cr-coated
M5 can provide significant benefits in normal operating conditions in terms of susceptibility
to corrosion in harsh environments such as high lithiated water chemistry and in terms of
wear resistance.
Cr is a better high-temperature oxidation resistant than Zr-4 alloy. A recent paper by
Sevecek et al. [69] developed a cold spray Cr coated Zirconium-4 cladding. The coating
is more nonuniform compared to PVD, but cold spray has a high deposition rate and is
suitable for industry production. The samples were oxidized in high-temperature steam at
1200 ◦ C and efficiently prevented oxidation.

2.5.2. Tungsten, Gold, Silver, Platinum, etc.

A review of hydrogen permeability data of solid metals in Table 1 shows that there are
a few pure metals with very low permeability [70]. Some of the above discussed carbides,
nitrides and oxides have lower permeability than the metals [54].

Table 1. Hydrogen permeability of selected metals at 500 ◦ C [70].

Permeability
Metal
mol H2 /m/s/Pa0.5
Vanadium 2.9 × 10−8
Niobium 7.5 × 10−9
Titanium 7.5 × 10−9
Nickel 1.2 × 10−10
Ferritic Steels 3 × 10−11
Austenitic Steels 0.7–1.2 × 10−11
Molybdenum 1.2 × 10−11
Tungsten 4.3 × 10−15

REB Research and Consulting published a graph [71] in 1996 that displays hydrogen
permeability vs. inversed temperature for numerous metals, including Ag, Au, Pt, Cu.
Gold has the lowest permeability followed by silver, aluminum, platinum, cupper, iron
and palladium.

2.6. FeCrAl Alloys

FeCrAl alloys have been investigated during the past 50 years for cladding and hydro-
gen permeation barrier applications in nuclear industry; for nuclear power applications
including accident tolerant fuel (ATF) cladding, structural components for fast fission
reactors, and as first wall and blanket structures for fusion reactors. FeCrAl alloys are
under consideration for these applications due to their inherent corrosion resistance, stress
corrosion cracking resistance, radiation-induced swelling resistance, and high temperature
oxidation resistance and hydrogen pick-up resistance. Handbook on the Material Properties
of FeCrAl Alloys for Nuclear Power Production Applications [72] was published in 2018
by Field et al. (ORNL report) and Garud et al. [73] reviewed in 2022 hydrogen isotope
permeation in clean and unoxidized FeCrAl alloys. Hydrogen permeation rates in ferritic
steels are higher and hydrogen solubility is lower than in austenitic steels. The tritium
Molecules 2022, 27, 6528 17 of 21

permeation rates in FeCrAl alloys are between those in austenitic stainless steels and in
ferritic FeCr steels.
Field et al. [72] report that Hydrogen/Tritium permeation has been measured at
200–700 ◦ C for different FeCrAl alloys to determine permeability and possible mitigation
strategies. In general, the higher Cr content FeCrAl alloys show lower permeability than the
Molecules 2022, 27, x FOR PEER REVIEW 18 of 22
lower Cr content alloys. Additionally, a significant difference in the permeability between
non-oxidized and oxidized specimens is apparent. Oxidized specimens with Al2 O3 layer
have been shown to have nearly one order of magnitude lower permeability than typical
bare FeCrAl
optimized alloys. fuel cladding tubes. An optimized FeCrAl-Mo coating was shown to
ZIRLO™
effectively protect the Zr-alloy substrate from oxidation. Hydrogen barrier properties are
Molybdenum Diffusion Barrier Layer with FeCrAl
however unknown and would be of interest to explore.
Yeom et al. [74] showed that Mo diffusion barrier layer between FeCrAl coating and
Zr-alloy
3. Summarysubstrate is essential
of Advanced for accident
Coatings tolerant fuel
for Hydrogen applications.
Barrier To enhance
Applications oxidation
and Future Pro-
resistance ◦
at high temperatures (>1000 C) in the event of loss of coolant accident (LOCA),
spects
the cold spray process was investigated for the deposition of FeCrAl coatings on optimized
We have in this review of recent literature (most papers were published within the
ZIRLO™ fuel cladding tubes. An optimized FeCrAl-Mo coating was shown to effectively
past 5–7 years) identified promising hydrogen isotope barrier coatings and knowledge
protect the Zr-alloy substrate from oxidation. Hydrogen barrier properties are however
gaps to further advance the state of the art. Below is a list of hydrogen barriers that re-
unknown and would be of interest to explore.
cently have been in focus for development for various applications. Figure 3 shows a sum-
mary
3. of recently
Summary developedCoatings
of Advanced hydrogen forbarriers.
Hydrogen Barrier Applications and Future
• Carbon: diamond like carbon (DLC); graphene, metal-graphene, graphene oxide.
Prospects
•We Carbides: SiC,
have in this SiC/SiC,
review TiC, TiAlC
of recent layered
literature phase.
(most papers were published within the
past•5–7MAX-phases and MXenes.
years) identified promising hydrogen isotope barrier coatings and knowledge
gaps•to further
Metals:advance
Cr, FeCrAl alloys,
the state of FeCrAl + Mo diffusion
the art. Below is a list ofbarrier.
hydrogen barriers that recently
• Nitrides: CrN, ZrN, TiN.
have been in focus for development for various applications. Figure 3 shows a summary of
• Oxides:
recently developeddopant+ZrO
hydrogen2;barriers.
bipolar oxide Al2O3/Cr2O3,nano-Al2O3.

Figure 3. Summary of Advanced

Figure Hydrogen
3. Summary Barriers,
of Advanced Application
Hydrogen Techniques
Barriers, and Techniques
Application Characterization.
and Characterization.

•Identified
Carbon: diamond
Knowledge like carbonResearch
Gaps—Future (DLC); graphene,
Prospects metal-graphene, graphene oxide.
• Carbides:
Depending SiC,
onSiC/SiC, TiC, TiAlCapplicable
the environment layered phase.
to the application, further studies are
•neededMAX-phases and MXenes.
to fill knowledge gaps. The following list—in no particular order—represents
•knowledge
Metals: gaps
Cr, FeCrAl
in the alloys, FeCrAl
application of +advanced
Mo diffusion barrier.barriers to reduce hydrogen
hydrogen
•absorption
Nitrides: CrN, ZrN, TiN.
and permeation and identifies plenty future research prospects. Figure 4 illus-
•tratesOxides: dopantand
key materials + ZrO 2 ; bipolar
materials oxide Al2 Ostrategies
modification 3 /Cr2 O3 , nano-Al 2 O3.properties.
to improve
• Perform hydrogen absorption and permeation measurements in environments
relevant to the application.
• Correlate permeation rate with hydrogen trapping, solubility, diffusivity, micro-
structure, phase formation, grain boundaries and fabrication procedure to learn
how to tailor materials to reduce hydrogen permeability.
• Utilize nanoscience, structural modifications and recoverable Nano Lattices to re-
duce hydrogen permeability.
 • Explore diamond like carbon with buffer layer of CrN etc.
o Micro or nanostructure engineering.
o Key is structural control.
• Study of microstructure related to fabrication method to identify improved per-
formance.
Molecules 2022, 27, 6528 18 of 21
• Exploration of multilayer structures with hybrid architecture for evaluation with
respect to mechanical strength and manufacturing feasibility.
• Identification of cost-effective, low-temperature preparation method to avoid
Identified Knowledge
HAZ. Gaps—Future Research Prospects
Depending
o For onexample;
the environment
using cold applicable to theroutes,
spray, sol-gel application,
chemicalfurther
spraystudies areor
pyrolysis
needed to fill knowledge
nitrates andgaps. The
triblock following for
copolymers list—in no particular
wet chemistry order—represents
routes.
• Develop
knowledge gaps in new
the application of advanced
feasible scale-up hydrogen
fabrication barriers
techniques of to
lowreduce
cost. hydrogen ab-
• Study of radiation resistance in nuclear reactor applications. Figure 4 illustrates
sorption and permeation and identifies plenty future research prospects.
key materialso and materials
Structural modificationtostrategies
modifications to improve
improve radiation properties.
resistance in a nuclear reactor.

Figure
Figure 4. 4. Advanced
Advanced Hydrogen
Hydrogen Barriers;
Barriers; key
key materials
materials and
and material
material engineering
engineering strategies.
strategies.

• Author
Perform hydrogen absorption
Contributions: and permeation
Conceptualization, measurements indraft
E.C.E.R.; writing—original environments relevant
preparation, E.C.E.R.;
writing—review and editing, E.C.E.R., R.L.O. and R.O.G.; visualization, E.C.E.R.; funding acquisi-
to the application.
• tion, R.L.O. and
Correlate R.O.G. All authors
permeation have
rate with read and agreed
hydrogen to the
trapping, publisheddiffusivity,
solubility, version of the manuscript.
microstruc-
ture, phase
Funding: formation,
This research grain boundaries
was funded andNuclear
by the National fabrication procedure
Security to learn
Administration how to
(NNSA) Trit-
iumtailor materials Program.
Modernization to reduce hydrogen permeability.
• Utilize nanoscience, structural modifications and recoverable Nano Lattices to reduce
Institutional Review Board Statement: Not applicable.
hydrogen permeability.
• Informed
Advance Consent Statement:
structurally Not applicable.
modified oxide materials; dopants; nano-engineering; nanoce-
ramics.
Data Availability Statement: Not applicable.
• Explore combinations of metals and metal alloys with diffusion barrier.
• Acknowledgments:
Exploration of the This work of
impact was supported
dopants andby the National
alloying Nuclear Security Administration
elements.
• (NNSA) of the U.S. Department
Explore bipolar oxides. of Energy (DOE) and performed at Pacific Northwest National La-
boratory (PNNL). PNNL is operated by Battelle Memorial Institute for US Department of Energy
• Explore diamond like carbon with buffer layer of CrN, etc.
under Contract No. DE-AC05-76RLO1830. We would like to express gratitude to Dr. William Kuhn
o Micro or nanostructure engineering.
o Key is structural control.
• Study of microstructure related to fabrication method to identify improved perfor-
mance.
• Exploration of multilayer structures with hybrid architecture for evaluation with
respect to mechanical strength and manufacturing feasibility.
• Identification of cost-effective, low-temperature preparation method to avoid HAZ.
o For example; using cold spray, sol-gel routes, chemical spray pyrolysis or nitrates
and triblock copolymers for wet chemistry routes.
Molecules 2022, 27, 6528 19 of 21

• Develop new feasible scale-up fabrication techniques of low cost.

• Study of radiation resistance in nuclear reactor applications.
o Structural modifications to improve radiation resistance in a nuclear reactor.

Author Contributions: Conceptualization, E.C.E.R.; writing—original draft preparation, E.C.E.R.;

writing—review and editing, E.C.E.R., R.L.O. and R.O.G.; visualization, E.C.E.R.; funding acquisition,
R.L.O. and R.O.G. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by the National Nuclear Security Administration (NNSA) Tritium
Modernization Program.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: This work was supported by the National Nuclear Security Administration
(NNSA) of the U.S. Department of Energy (DOE) and performed at Pacific Northwest National
Laboratory (PNNL). PNNL is operated by Battelle Memorial Institute for US Department of Energy
under Contract No. DE-AC05-76RLO1830. We would like to express gratitude to William Kuhn
(Emeritus PNNL) for kindly sharing his knowledge and for inspirational discussions related to
hydrogen isotope permeation.
Conflicts of Interest: The authors declare no conflict of interest.

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