Hydrogen Blistering

The schematic diagram below shows hydrogen diffusion, say, in a tank containing
an acid electrolyte. Hydrogen evolution occurs because of a corrosion reaction or
cathodic protection. Most of the hydrogen atoms combine to form hydrogen
molecule at the external surface.
H
a
+ H
c
2H
o
H
2

What is hydrogen blisteering?
Hydrogen Blistering (HB) refers to the formation of subsurface planar cavities, called hydrogen blisters, in a metal
resulting from excessive internal hydrogen pressure. Growth of near-surface blisters in low-strength metals usually
results in surface bulges.

Mechanisms

What causes hydrogen blistering? Hydrogen ions are reduced tohydrogen atoms that adsorb on the steel surface.
Some of the hydrogen atoms will diffuse through the steel and accumulate at hydrogen traps, typically voids around
inclusions.


When hydrogen atoms meet in a trap and
combine, they form hydrogen gas (H
2
)
molecules in the trap. The accumulation
hydrogen gas inside the extremely small cavity
will lead to the buildup of excessive
internal hydrogen pressure. At certain times,
this internal hydrogen pressure will become
sufficient to cause the steel to blister.

Blisters occur usually in low strength steels
(<80ksi yield strength) and are formed
preferentially along elongated nonmetallic
inclusions or laminations in linepipe steels.

Prevention

How to prevent hydrogen blistering? Hydrogen Blistering can be prevented through:
Control of impurity of steel.
Avoid the hydrogen source.
Baking to remove hydrogen.

The combination of some hydrogen atoms to form molecules is prevented by some
poisons like As, Bi and Sb, and the atomic hydrogen diffuses into the metal. They
diffuse in to the small voids, and surface heterogenities present in the metal. In the
void they combine to form molecular hydrogen.
Unfortunately, the molecular hydrogen does not diffuse, the concentration and
pressure of hydrogen gas with a very small void increases enormously, the
equilibrium pressure of molecular hydrogen in contact with atomic hydrogen is in
the order of several hundred thousands atmospheres, sufficient to rupture and form
blisters and cause rupture of the walls. Generally low strength steels are susceptible
to hydrogen blistering.
Hydrogen Damage
Metals and alloys may be damaged by hydrogen blistering, hydrogen
embrittlement and high temperature hydrogen attack. A classification of the three
damages is shown in Table 4.2 below. Often there is a great deal of confusion in
the three phenomena. Each of the above phenomena is presented below.
Table 4.2: Classification of Hydrogen Damages
No. Type of Attack Environments
Source of
Atomic
Hydrogen
Type of Metal
Deterioration
Method of Prevention
1. Hydrogen attack
Temperature > 230C.
H
2
Pressure >7 kg/cm
2
.
Equilibrium
dissociation of
H
2
molecules:
H
2
2H
Decarburization and
fissuring: possibly
methane blisters. Serious
loss of strength.
Use of adequately
resistant alloys.
2.
Hydrogen
blistering(Hydrogen-
Temperature 100C in
presence of moisture
Generated by
Blisters when defects are
shallow from the
Protective linings.
induced crack, HIC) and usually H
2
S.
Promoted by cyanides
corrosion:
H
+
+ e H

surface. Cracks parallel
to the surface, when
defects are deep.
Use of adequate
materials (anti-HIC
steel).
Chemical treatment of
corrosive medium with
water, polysulfides or
inhibitors
3.
Hydrogen
embrittlement

High strength steel in
environments same as
above
Same as above
Severe loss of ductility
at low strain rates and
delayed fracture
Same as hydrogen
blistering
Nearly atmospheric
temperature by rapid
cooling of high
strength equipment
operating at conditions
same as in hydrogen
attack.
Same as
hydrogen attack
Severe loss of ductility
at low strain rates and
hydrogen assisted crack
growth
Use of adequate
materials.
Hydrogen degassing.





In summary, hydrogen attack occurs in these steps
Formation of hydrogen ions (H
+
)
Reduction of hydrogen ions to H atoms
Combination of hydrogen atoms to form hydrogen molecule
Escape of hydrogen molecules from the surface (H
2
)
Diffusion of some H atoms to inside of the surface
Accumulation of hydrogen atoms in voids to form molecular hydrogen
Exertion of significant pressure on the walls of the tank
Blistering followed by rupture depending on the steel in use
Prevention
Use steels metallurgically modified to minimize voids and inclusions to prevent
hydrogen gas formation
Remove poisons like arsenic and cyanide compounds and phosphorous containing
ions. The poisons retard the formation of hydrogen molecules.
Use coatings impervious to hydrogen diffusion.
Use nickel based alloys because of their low hydrogen diffusion rates.
Use inhibitors in closed systems because they prevent hydrogen attacks.