HYDROGEN DAMAGE OF

METALLIC MATERIALS
T.K. G. NAMBOODHIRI
PROFESSOR OF METALLURGICAL ENGINEERING
(Retired)
BANARAS HINDU UNIVERSITY
VARANASI
Introduction
• Hydrogen-most ubiquitous element
• Minute amounts can damage metals
• Can be easily picked up by metals during
melting, casting, working, fabrication and
use
• Many forms of hydrogen damage
Classification of hydrogen damage
DEGRADATION OF
LOSS IN TENSILE
HYDROGEN HYDROGEN STRESS OTHER MECHANICAL
ENVIRONMENT
EMBRITTLEMENT CRACKING PROPERTIES DUCTILITY

HYDROGEN
SLOW STRAIN RATE EMBRITTLEMENT
EMBRITTLEMENT
HYDRIDE SOLID SOLUTION
HYDROGEN
HARDENING
EMBRITTLEMENT DAMAGE

HIGH STRAIN RATE CREATION OF

INTERNAL DEFECTS
EMBRITTLEMENT

SHATTER CRACKS, HYDROGEN

POROSITY BLISTERING ATTACK
FLAKES, FISH EYES
Solid solution hardening.

• Hydrogen hardens metals like Nb,Ta

and Ti at concentrations within solid
solubility limits. These metals may be
Embrittled at high strain rates.
HYDROGEN EMBRITTLEMENT

HYDROGEN EMBRITTLEMENT

HYDROGEN ENVIRONMENT EMBRITTLEMENT

HYDROGEN STRESS CRACKING

LOSS IN TENSILE DUCTILITY & OTHER MECHANICAL PROPERTIES

Hydride embrittlement
• Seen in hydride forming metals like Ti, V, Zr
• Low strain rate embrittlement: At low H
concentrations. Similar to H.E.. Caused by
stress-nucleated hydrides
• High strain rate embrittlement: At high
H concentrations. Due to hydride
precipitates. Enhanced by high strain rates.
Creation of internal defects
• Blistering: Formation and collection of molecular
hydrogen at internal defects like grain boundaries,
inclusions and laminations, build-up of high pressures
leading to formation and growth of blisters
• Shatter cracks and flakes: Internal fissures
seen in large forgings due to segregated H
• Fish-eyes: bright patches of embrittled regions
visible on fracture surfaces of weldments.
Creation of internal
defects
• Micro-perforations: Exposure to high hydrogen
pressures at R.T. may develop small fissures or micro-
perforations
• Porosity: Liquid metals containing large amounts of H
liberate it during solidification causing porosity in Fe, Al
and Mg. H content, cooling rate, external pressure and
H partial pressure control porosity
• Hydrogen attack: Exposure of steels to high pressure
H at high temperatures causes H to react with carbon
of steel to produce methane. Leads to decarburization,
dissolution of carbides and weakening of the steel.
CHARACTERISTICS OF
IMPORTANT H. D. PROCESSES

• HYDROGEN EMBRITTLEMENT
• HYDROGEN INDUCED BLISTER
CRACKING
• HYDROGEN ATTACK
Characteristics of Hydrogen
Embrittlement
• Strain rate and temperature sensitivity
• Delayed failure
• Sub critical cracking and threshold
stress intensity
• Effects on tensile properties
• Fracture mechanisms
Strain rate and temperature
sensitivity of H.E.
• Most pronounced at
slow strain rates and
ambient temperatures
• Decreases
monotonically with
increasing strain rate
• Minimum at around
room temperature
Delayed failure in H.E.
• Incubation period
independent of stress
• Time to failure increases
with decreasing stress
• Discontinuous crack
propagation
• Lower critical stress below
which no failure
• H causes delayed failure in
many materials
• Parameters strongly
dependent on H content
Effects of H on tensile
properties
• Increased/decreased/unaffected Y.S.
• Strain localization/Luders band/serrated
yielding
• Increased/decreased flow stress and work
hardening rate
• Increased screw dislocation velocity and
dislocation multiplication
• Loss in tensile ductility
Fracture mechanisms in H.E.
• H promotes all fracture mechanisms
• MVC in low strength steels
• Ductile, quasi-cleavage or I.G. fractures in high
strength steels
• I.G.failure in Ni
• I.G. or Transgranular cleavage(fluted
morphology) in Ti alloys.
• I.G., cleavage or M.V.C. in Al alloys.
H induced fracture morphology
Hydrogen Induced Blister Cracking
(HIBC)
• Metallurgical parameters: Non-metallic
inclusions, Sulfur content, alloy segregation
and microstructure. Very low S levels and
inclusion shape control to eliminate HIBC
nucleation. Reduction in hardness of
segregated zones to prevent HIBC
propagation.
• Environmental parameters: Hydrogen fugacity.
A threshold fugacity below which HIBC does
not occur.
HYDROGEN INDUCED BLISTERS

• Top picture shows

hydrogen induced
blisters in a pipe line
carrying hydrogen
sulfide containing
fluids
• Bottom picture shows
the cross section of a
blister
Hydrogen Induced Blister Cracking
(HIBC)
• Hydrogen blisters
nucleate on inclusion
stringers and cause
cracking when their
internal gas pressure
exceeds the fracture
stress- HSLA/Line
pipe steels. Straight
or step-wise cracking
HYDROGEN ATTACK

• Equipment in contact with hydrogen at

temperatures above 260 C and hydrogen partial
pressures above 690 KPa may suffer from high
temperature hydrogen attack.
• Atomic hydrogen diffuses readily in steels and
reacts with carbon present to form methane
which collects at grain boundaries and in minute
voids.
• Methane pressure build-up leads to cracking
Hydrogen attack : Nelson curves
for steels
• Nelson curves show
safe operating limits
of temperature and
hydrogen partial
pressure for steels.
Empirical curves
drawn from actual
experience
Prevention of Hydrogen damage
• Metallurgical control: Alloy chemistry,
crystal structure, microstructure and
substructure.
• Environmental control: Inhibition by
organic compounds like nitriles, sulfoxides,
azoles and amines.
CONCLUSIONS

• SMALL QUANTITIES OF HYDROGEN CAN

SERIOUSLY AFFECT THE PROPERTIES OF
MANY STRUCTURAL MATERIALS
• HYDROGEN DAMAGE HAS MANY FORMS
• CAREFUL SELECTION OF MATERIALS,
PROCESSING STEPS AND ENVIRONMENTS
CAN PREVENT HYDROGEN DAMAGE