HYDROGEN DAMAGE OF METALLIC MATERIALS

T.K. G. NAMBOODHIRI PROFESSOR OF METALLURGICAL ENGINEERING (Retired) BANARAS HINDU UNIVERSITY VARANASI

Introduction
HydrogenHydrogen-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
HYDROGEN ENVIRONMENT EMBRITTLEMENT HYDROGEN STRESS CRACKING DEGRADATION OF OTHER MECHANICAL PROPERTIES LOSS IN TENSILE DUCTILITY

SLOW STRAIN RATE EMBRITTLEMENT HYDRIDE EMBRITTLEMENT

HYDROGEN EMBRITTLEMENT

HYDROGEN DAMAGE
CREATION OF INTERNAL DEFECTS

SOLID SOLUTION HARDENING

HIGH STRAIN RATE EMBRITTLEMENT

SHATTER CRACKS, POROSITY FLAKES, FISH EYES BLISTERING

HYDROGEN ATTACK

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 embrittlement: low H concentrations. Similar to H.E.. Caused by stress-nucleated hydrides stressHigh strain rate embrittlement: At embrittlement: 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 buildleading to formation and growth of blisters

Shatter cracks and flakes: Internal fissures
seen in large forgings due to segregated H

FishFish-eyes: bright patches of embrittled regions
visible on fracture surfaces of weldments.

Creation of internal defects

MicroMicro-perforations: Exposure to high
hydrogen pressures at R.T. may develop small fissures or micro-perforations micro-

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 quasihigh 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: NonNonmetallic 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 stressstressHSLA/Line pipe steels. Straight or stepstep-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 build-

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

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