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Hydrogen Permeation Barrier Coatings

Chapter · December 2007

DOI: 10.1201/9781420006070.ch8

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 Hydrogen Permeation Barrier Coatings
C. H. Henager, Jr.
Materials Science Division, PNNL, Richland, WA 99352

Hydrogen Permeation Barrier Coatings

Introduction
Gaseous hydrogen, H2, has many physical properties that allow it to move rapidly into

and through materials, which causes problems in keeping hydrogen from materials that are

sensitive to hydrogen-induced degradation. Hydrogen molecules are the smallest diatomic

molecules, with a molecular radius of about 37 x 10-12 m and the hydrogen atom is smaller

still. Since it is small and light it is easily transported within materials by diffusion processes.

The process of hydrogen entering and transporting through a materials is generally known as

permeation and this section reviews the development of hydrogen permeation barriers and

barrier coatings for the upcoming hydrogen economy.

Background
Hydrogen permeation is defined as the transport of hydrogen as dissociated hydrogen

atoms [1] and has units of moles of hydrogen gas per square meter per second (mol m-2 s-1),

which is the permeation rate. Known as Richardson’s Law this relation can be expressed as

DK 1/ 2
J= 1/ 2
(Phigh " Plow ) (1)
d

where J is the permeation rate, D is the diffusion coefficient of hydrogen in the material, K is

Sievert’s constant for the!material, which determines the hydrogen solubility. The product of

D and K is referred to as Φ, the permeation coefficient or permeability of the material.

Sievert’s Law gives the solubility in terms of the pressure as

c H = KPH1/ 2 (2)

and equation (1) can be expressed as

!
 " #PH1/ 2
J= (3)
d

where Φ is the material permeability for hydrogen and ΔPH is the hydrogen pressure
! d of the given material. Both D and K, therefore, Φ, are
difference across the thickness

temperature dependent and have associated activation energies such that permeation is much

higher at elevated temperatures for all materials than at low temperatures. For many

materials, these permeation constants are too high for a given application and a permeation

barrier must be considered.

Historical Overview
The concept of a hydrogen barrier seems to have arisen due to two separate issues in

technology. One is the concern regarding hydrogen embrittlement of steels [2,3] and the

other is the required low permeation rate of tritium in the conceptual designs for Fusion

Power that involve deuterium-tritium plasmas and tritium breeding blankets. These two

technological areas have made advances in hydrogen barrier development that greatly impact

current knowledge and state-of-the-art. By far the most important advances and studies

relevant to steels and metallic alloys has originated from the Fusion Energy materials

community and this will become apparent as this section looks more closely at specific barrier

coatings and coating technologies.

Hydrogen Barrier Coatings

The principal concern for hydrogen barrier coatings is to be able to prevent hydrogen

ingress into a material that could be damaged or degraded due to hydrogen uptake. Data for

hydrogen solubility and diffusivity is readily available for many materials and, for most

metals, is significant in terms of amount of hydrogen and in terms of mobility of hydrogen.

For example, a common stainless steel, 316SS, will dissolve about 20 parts per million
hydrogen atoms at room temperature and a 1-cm thick piece of this steel will have a hydrogen

permeation rate of about 6 x 10-13 moles of H2 per square meter of steel per second (moles-H2

m-2 s-1) for a hydrogen pressure of 5000 psi, which amounts to about 3.5 x 1011 atoms of

hydrogen per square meter of this 1-cm thick steel plate. The solubility of the steel and its

permeation rate increase exponentially with temperature and a solubility of several thousands

parts per million can exist at 800˚C in 316SS and the permeation rate has increased by

8-orders of magnitude over room temperature [1]. This is quite remarkable but of serious

consequences since many steels and other alloys can be embrittled by this much hydrogen [2].

For Fusion Energy concerns this is manifested in a tritium inventory in materials that is

unacceptably high or permeation through metallic components into flowing coolants that is

too high [4].1

Therefore, hydrogen barriers have been developed and evolved from these twin concerns:

1) reducing hydrogen uptake into materials to prevent degradation, and 2) preventing tritium

permeation through materials to reduce radioactive transport to increase public health and

safety for Fusion power plants. Most hydrogen barriers have been conceived as external

coatings on existing metallic alloys in order to prevent hydrogen uptake into the metal. In

some cases exposure treatments can be designed to produce an external scale on the metal or

alloy that also serve this purpose. In general, the most effective approach seems to be the

application of a suitable external coating having low hydrogen solubility and slow hydrogen

transport. Some materials possess intrinsically low hydrogen permeation, such as gold or

tungsten as pure metal examples, while many oxides, carbides, and nitrides possess low

hydrogen permeation and have other desirable properties such as high-temperature utility and

1
Interested readers are referred to References 1-4 for more information regarding
embrittlement and hydrogen permeation.
corrosion protection. Typical coating related issues, such as thermal expansion mismatch,

coating defects, and inferior mechanical properties must be dealt with for ceramic-based

barrier coatings.

External Coatings
This class of coatings comprises those barrier coatings that are applied externally to a

material in order to prevent hydrogen permeation and are designed specifically for that

purpose. In the next section we will consider barriers that may evolve or be developed on the

surface of a material using a natural process, such as oxidation. For this section, however, we

have two main cases, one for which a barrier coating is conceived and applied as an external

coating using some physical or chemical deposition process, including electrochemical

processes using liquids. We then consider the second case where a coating is applied and then

post-processed to produce a hydrogen barrier layer.

The most widely used permeation barrier coating is aluminum oxide, or alumina, since it

possesses one of the lowest hydrogen permeation rates of any material and one that is many

orders of magnitude lower than most metals [5]. Table 1 lists, in decreasing order of

hydrogen permeability, the permeability of a variety of materials at 500˚C (773K) in units of

moles-H2 m-1 s-1 Pa-0.5, which are moles of hydrogen gas per meter thickness of material per

second per square root of hydrogen pressure in Pa. Several ceramic coatings are listed and

make good barrier coatings, but alumina seems to be superior. The work of Roberts et al.

showed that permeation was controlled by dissolution and transport through the grains of

dense sintered alumina. Hydrogen transport and solubility is greatly reduced in alumina

compared to metals [6,7]. More recent data mainly confirms the earlier work but all the data

for alumina is at high temperatures and must be extrapolated for our purposes [7].
 Table 1. Hydrogen permeability of various materials

Material Permeability Reference Comments

Vanadium 2.9 x 10-8 [8] Extremely sensitive
to surface oxides
Niobium 7.5 x 10-9 [8]
Titanium 7.5 x 10-9 [8] Stable hydrides
Iron 1.8 x 10-10 [8] Iron
Ni 1.2 x 10-10 [8]
Ferritic Steels 3 x 10-11 [8,9] Tritium
Inconel 600 2.8 x 10-11 [8]
Austenitic Steels 0.7-1.2 x 10-11 [8] Large data
compilation
Molybdenum 1.2 x 10-11 [8] Variable
Titanium carbide ~ 1 to 8 x 10-15 [10,11] External PVD
coating
Tungsten 4.3 x 10-15 [8] Extrapolated from
high T tests
Titanium ~ 7 x 10-16 [10] External PVD
carbide/Titanium coating
nitride layered
Aluminum oxide ~9 x 10-17 [7,10,11] Extrapolated form
high T tests
Beta-SiC ~ 1 x 10-20 [10] Extrapolated

As noted, the majority of research into hydrogen permeation barriers has been performed

in the Fusion Materials research community concerned with tritium fate and transport in

structures and breeding blankets. Since the work of Roberts et al. showing the excellent

permeation resistance of alumina [5], one thread of research has concentrated on ceramic

coatings on fusion alloys, either 316 stainless steels or ferritic-martensitic alloys, such as

MANET2, MANET-II, etc. Mühlratzer et al. [12] discuss a 1000-fold reduction3 in hydrogen

permeation through Hastelloy-X that is coated with CVD alumina., although this work also

points out the difficulties with forming a dense external ceramic coating on a metal substrate.

2
Designation for European ferritic-martensitic Nb-rich steel DIN 1.4914
3
A permeation reduction factor (PRF) is often quoted for comparison between treated and
untreated metals. For this case a PRF of 1000 would be given.
Film defects, cracks, and spallation are issues that must be addressed for external permeation

barrier coatings. This becomes apparent when either improved coating methods are used or

there is a better mechanical and thermal property match between the coating and the substrate.

For example, thin alumina deposited on amorphous tungsten oxide, WO3, by a filtered

vacuum arc method can reduce hydrogen permeation by a factor greater that 3000 even for

only thicknesses of 500 nm [13]. However, plasma sprayed coatings of alumina on steels are

not very effective permeation barriers since the films are highly defected [14]. Table 1

suggests that much higher permeation reductions are possible relative to steels provided the

coatings are dense and relatively defect free, which remains the principal reason that PRF

values of only 1000 to 10,000 are reported.

Another class of external coatings that has been investigated is TiC and TiN, alone and in

combination as a composite film [4,11,15-17]. Although TiC and TiN have low intrinsic

permeabilities relative to steels, vapor deposited films on steels do not reach this potential and

often exhibit activation energies for permeation equal to that of the steel, which indicates

permeation is being controlled by defects in the coating rather than permeation through the

coating material [16]. Thus, permeation reduction factors of about 10 or so have been

realized but not the full potential of these materials as barriers. The large tritium permeation

reduction reported by Shan et al. [17] for TiN and TiC/TiN coatings on stainless steel, which

was on the order to 105 to 106, does not appear to be reasonable and their measurement

technique is questionable [4].

The choice of permeation barrier materials selected here for coatings are reasonable

based on permeation resistance but external coatings of ceramics on metals are difficult to

perfect since many metals have high thermal expansion coefficients and most ceramics have
low ones. This causes large thermal stresses in the coatings to develop, which leads to defect

formation in the coatings and lowers permeation resistance. A better technique, which will be

discussed in the next section, relies on the formation of intrinsic oxide films on the surface of

the metals, either by direct oxidation or by alloying followed by oxidation [4].

Grown-on oxide films

Since oxides appear to have intrinsic low hydrogen permeabilities one avenue of barrier

development has pursued the direct oxidation of suitable alloys and, which has proven more

successful, the aluminization of steels with subsequent alumina surface film formation.

Direct oxidation relies on the intrinsic oxide layers that can be grown on alloys to provide

hydrogen barrier capabilities. Such films typically consist of Fe-Cr-Al mixed oxides,

depending on the steel, and several researchers have oxidized Fecralloy for this very reason

[18-21]. In general, some concerns with oxidized steels are that spallation of the typical Fe-

and Cr-containing oxides prevents excellent hydrogen barrier formation. Fecralloy, however,

forms an alumina film that is more adherent and a better hydrogen barrier. Permeation

reduction of 1000 have been determined in Fecralloy steels [21]. Grown-on coatings perform

better than plasma-sprayed Fe-Cr-Al coatings [20].

Aluminizing steels, as noted above, has produced the best hydrogen barriers on steels and

other compatible alloys [22-33]. Interestingly, the process of aluminization or aluminizing is

flexible and robust such that a wide variety of techniques can be used and this adds to the

success of this method. Steels are aluminized by the in-diffusion of aluminum from the

surface via the melt or vapor phase. In a relatively short time, one the order of hours, a 50

micron-thick aluminide alloy layer can be produced on the surface of a given steel and

subsequently oxidized to form an alumina layer on top of hard aluminide intermetallic layers.
In Figure 1 the phase diagram for Fe-Al is shown to illustrate the varied layers that form

during this diffusion-reaction process.

Figure 1. AlFe phase diagram showing intermetallic phases, such as FeAl3, Fe2Al5, FeAl2,

and FeAl that can form as separate layers in aluminized steel.

Although the diffusion-reaction method may vary the results of aluminization remain

similar and depend on the steel composition and on the temperature of the reaction

processing. Methods that have been used for steels include hot-dipping [24,27-29,34-37],

plasma spraying [14,20,37,38], pack-aluminizing, which is a form of chemical vapor

deposition or CVD [22,25,27,33], vacuum evaporation [39], and polymer slurry methods [40].

Each of these methods has advantages and disadvantages compared to each other and have

been used to create permeation barrier coatings on steels. One consideration is the

temperature required for the process relative to heat-treatment temperatures of steels. The
treatment temperature of the MANET-II ferritic-martensitic steel limits the process

temperature to about 750˚C, which in turn limits the amount of aluminum and depth of

diffusion of aluminum in the surface. For this case, hot-dipping was chosen as a preferred

method [41].

Permeation reduction factors of up to 10,000 or 104 have been realized with the best

coatings based on aluminized steels. Ferritic-martensitic steels that were aluminized had the

Fe2Al5 phase predominate in the layer sequence, while a 316L steel had FeAl3 and FeAl2 as

the main aluminide phases [25]. The best permeation barrier resulted from an external

alumina film of about 1 micron in thickness grown on the aluminide layers [25].

The vacuum evaporation process and polymer slurry process are quite new processes

relative to the others and have the potential to provide more control in the processing, in the

case of the vacuum evaporation technique, or greatly reduce the cost and environmental

concerns of pack-aluminizing with the polymer slurry methods. The vacuum evaporation

process allows one to diffuse other elements than Al into the steels or to deposit FeAl coatings

directly onto the surface of the steels with Al diffusion occurring to help bond the deposited

coating [39].

This process is referred to as Enclosed Vacuum Evaporation (EVE) coating technology

and is applicable to a variety of coating and substrate materials with a unique capability of

producing smooth and uniform coatings on the inner surface of small-diameter, high-aspect-

ratio cylindrical components or other confined geometries. The technique has been used to

deposit reproducible coatings on the inner surface of tubes as small as 10 mm in diameter in

lengths up to 3.8 m. For larger-diameter tubes or pipes in which radiant heating of the

substrate from the source filament is impractical, separate resistive or inductive heating of the
substrate to the desired temperature is used. Figure 2 shows the inner surface of a steel tube

coated with a Fe-Al alloy for hydrogen barrier testing. The deposition is rapid and substrate

temperature rise can be controlled to avoid de-tempering alloys.

FeAl alloy coating

Steel substrate

Figure 2. FeAl coating on the inner diameter of a 316SS tube that was deposited using the

EVE technique.

The polymer slurry method for aluminizing steel surfaces is straightforward and simple,

and should be low-cost since the raw materials and processing steps are also low-cost.

Aluminum flake of 1 to 2 micron diameter is blended with a preceramic polysiloxane polymer

and heated in air or nitrogen to 700˚C to 800˚C for several hours to allow the aluminum to

diffuse into the steel and to allow an external Si-Al-O film to form from reactions between the

siloxane backbone and the Al. As with all aluminizing reaction-diffusion coatings a series of

aluminide layers forms on the surface of the steel as shown in Figure 3. The outermost layer
of alumina is the hydrogen permeation barrier while the aluminum-rich layers provide

additional aluminum for alumina formation in oxidizing environments as required to maintain

the external oxide layer.

Fe(Al) solid
solution

316SS

Alumina
layer

FeAl

Fe2Al5

Figure 3. A typical aluminized steel surface following the polymer slurry method at 800˚C in

air. Any of the methods mentioned in this section about aluminized films will produce similar

reaction layers. Ease of processing and cost may dictate which method is preferred for a

given application.

The advantages of aluminizing steels goes beyond hydrogen barrier formation, however,

as such surface treatments also provide additional corrosion protection. The fusion materials

community continue to study these processing methods and may continue to be the main

driving force for research in this area until hydrogen infrastructure issues become more

important [27].
Summary
The best hydrogen barrier coatings have been fabricated using aluminized steels

produced by a variety of methods, including pack-aluminizing, hot-dipping, vacuum

evaporation, or polymer slurry techniques. Permeation reduction factors of up to 104 have

been realized in this manner. Titanium-based coatings offer an alternative choice to Al but

are not as permeation resistant as the alumina-based methods and are not as reproducible in

being able to be fabricated. Much work remains to be done in the general area of hydrogen

permeation barriers, particularly in the development of new methods that can provide barriers

over large areas for anticipated hydrogen economy infrastructure needs. Low-cost methods

and better reproducibility are required. Hydrogen remains an elusive species in this regard

and a perfect solution is apparently very challenging.

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