Hydrogen Induced Corrosion

March 22nd, 2001

Matthew Avery
Benjamin Chui
Y. Gordon Kariya
Kenneth Larson

Outline
Mechanisms

Hydrogen Embrittlement
Hydrogen Induced Blistering
Precipitation of Internal Hydrogen
Hydrogen Attack
Cracking from Hydride Formation

Prevention
Case Studies
Questions

Hydrogen Embrittlement
Hydrogen in steel reduces the tensile ductility
causes premature failure under static loads.
Only a few parts per million of hydrogen is
necessary to embrittle steel.
Three primary theories:
Decohesion Theory
Reduced Surface Theory
Planar Pressure Theory

Hydrogen Embrittlement
Basic Mechanism

Crack Tip
H2(gas)

Hydrogen Embrittlement
Basic Mechanism

H2(gas)
Dissociative Chemical Adsorption
Physical Adsorption

Hydrogen Embrittlement
Basic Mechanism

H2(gas)

Hydrogen Diffusion

Hydrogen Embrittlement
Decohesion Theory

H2(gas)

max

Hydrogen Embrittlement
Reduced Surface Theory
The absorption of hydrogen decreases the surface
free energy of the metal
Propagation of the crack tip is enhanced
Explains crack propagation of high-strength steels
in low-pressure hydrogen environments

Hydrogen Embrittlement
Planar Pressure Theory
Occurs when metals are charged with hydrogen
during solidification
High-pressure hydrogen can form in microvoids
Same mechanism as hydrogen blistering

Hydrogen Embrittlement
Crack Direction

Hydrogen Embrittlement
General Trends
Tendency to embrittle increases with decreased
strain rate
Embrittlement is more prevalent at room
temperature
Tendency to embrittle decreases with increasing
temperature

Hydrogen Embrittlement
Prevention in Design
High-strength metals and alloys are more
susceptible to embrittlement
Common mistake is to overcompensate on
strength requirements for service
At ambient conditions :

Minimize strength of material!

Hydrogen Embrittlement
Prevention in Processing
Embrittlement can originate from poor production
techniques
Problems arise when hydrogen is allowed into
production environment
Remedies
Maintain low hydrogen atmosphere
Heat treatment

Hydrogen Embrittlement
Prevention in Welding
Embrittlement can be localized around a weld
Welding rods containing hydrogen are the source
Remedies
Low hydrogen welding rods stored in a dry
place
Local heat treatment before & after welding

Hydrogen Embrittlement
Prevention
Design: Minimize strength of material
Production: Minimize hydrogen sources in
production area & Heat treatment
Welding: Welding rod storage & Heat treatment
Reversal: Baking 100-650C under vacuum
conditions can rid a metals of hydrogen inclusions

Hydrogen Embrittlement
Case Study

Unalloyed steel
High pressure boiler
Evaporator tube
Time to failure: over 10
years
Environment: flue gas
deposits with sulphuric
acid compounds
Remedy: Use lowalloyed (hydrogenresistant) steel

Hydrogen Embrittlement
Case Study
Steel Fastener
Multiple fracture origins
Subsurface cracking at
inclusions

Hydrogen Induced Blistering

Hydrogen is absorbed into metal, diffuses inward,
and precipitates as molecular hydrogen
Precipitates as laminations, inclusions, matrix
interfaces
When cracks are just below surface, the exterior
layer of metal will bulge
Enough pressure builds to produce internal cracks

Hydrogen Induced Blistering

Basic Mechanism

H2(gas)

Physical Adsorption

Hydrogen Induced Blistering

Basic Mechanism

H2(gas)

Dissociative Chemical Adsorption

Hydrogen Induced Blistering

Basic Mechanism

H2(gas)

Hydrogen Diffusion

Hydrogen Induced Blistering

Basic Mechanism

H2(gas)

Blister Formation

Hydrogen Induced Blistering

General Notes
Hydrogen induced blistering can be seen as a
special case of hydrogen embrittlement
Blistering most prevalent in low-strength alloys or
metals that have been exposed to hydrogencharging conditions

Hydrogen Induced Blistering

Prevention
Surface phenomenon
Source: Hydrogen absorbed from the environment
Minimized hydrogen at surface
Corrosion inhibitors
Avoid cathodic protection and galvanic couples

Hydrogen Induced Blistering

Case Study
Unalloyed steel wall
Carbon dioxide
scrubbing tower
Time to failure: many
years
Environment: water and
CO2
Use a non-corrosive
scrubbing liquid,
Accept corrosion;
monitor its progress

Precipitation of Internal Hydrogen

Processing
Introduces 5-8 ppm
RT equilibrium at 0.1 ppm
Diatomic precipitation
Occurs at existing inclusions
Pressure causes enlargement of cracks
Cracks = Embrittlement

Precipitation of Internal Hydrogen

Transgranular Cleavage

Precipitation of Internal Hydrogen

How hydrogen gets there
Atmospheric moisture
Impurities
Welding
Atmosphere
Surface contaminants
Welding rod

Precipitation of Internal Hydrogen

Fracture
Reduced ductility
Fracture initiation
inclusions
pores
Fracture surface
Fisheyes
Flakes

Typical of heavy steel forgings

Caused by internal residual hydrogen
Hairline cracks in center of part
Below 200 degrees C

Precipitation of Internal Hydrogen

Prevention
Internal phenomenon
Source: Hydrogen absorbed during processing
Improved processing techniques with added heat
treatment under vacuum

Precipitation of Internal Hydrogen

Prevention in Processing
Hydrogen solubility in iron
Low in -iron (low T)
High in -iron (high T)
Diffusivity increases with temperature
Result: Quenching metals aids hydrogen corrosion
Low diffusivity traps hydrogen in metal
Hydrogen precipitates internally

Precipitation of Internal Hydrogen

Hot metal during processing
Hydrogen diffuses in at high temperatures
Cool the metal ..
Hydrogen is trapped!

Precipitation of Internal Hydrogen

Hot metal during processing
Longer annealing time under vacuum conditions
Hydrogen is able to diffuse out as the solubility
decreases

Precipitation of Internal Hydrogen

Case study
Viton B (rubber)
Environment: oil well
workover fluids
Time to failure: months
Failure due to pressure
buildup at voids in the
material
The interiors of the
blisters are similar to that
of hydrogen flakes in
steel

Hydrogen Attack
Mechanism
Environment
High P, high T hydrogen environment
Petrochemical plants
Hydrocarbon processing at 21 MPa, 540C

Stress level, exposure time, steel composition

Mechanism
Hydrogen reacts with carbides to form methane
Methane bubbles form at grain boundaries
Bubbles merge to create fissures

Hydrogen Attack

Hydrogen Attack

Hydrogen Attack

Hydrogen Attack

Hydrogen Attack
Characteristics
Symptoms
Unexpected failure
Microstructure
Decarburization along grain boundaries
Fissuring along grain boundaries
Embedded methane bubbles

Hydrogen Attack
Rapid cooling can cause:
Hydrogen embrittlement
Blistering

Hydrogen Attack
Prevention
High temperature phenomenon
Petroleum processing reaches up to 540 C
Reaction with carbon
Methane and decarburized structures formed
Minimize carbon content for high temperature
operation!

Hydrogen Attack
Case Study
Hydrogen attack at the
ID weld in a high
pressure carbon steel
boiler tube

Hydrogen Attack
Case Study
Cracking due to
hydrogen attack at the ID
weld in a high pressure
carbon steel boiler tube

Hydrogen Attack
Case Study
Carbon steel cooler pipe
from heat exchanger
Time to Failure: Several
years.
Environment: high
internal pressure, gas
mixture of hydrogen,
nitrogen and ammonia at
approx. 240C.
Remedy: Use 0.5 Mo
steel or one of the Cr Mo
steels

Hydride Formation Cracking

Affects: Ti, Ta, Zr, U, Th
Hydrogen picked up during processing
Melting
Welding

Hydride formation upon cooling

Hydride Formation Cracking

Characteristics
Lower density than metal matrix
Increases strength
Decreases ductility, toughness
Platelets
Preferred orientation in lattice
Applied stress can cause hydride alignment

Hydride Formation Cracking

Hydrides in Titanium
Passivating at 100 C
Slow diffusion
0.4 mm layer of TiH2
Spalling
Rapid formation above 250 C
Low hydrogen solubility
No spalling
Formation of hydride particles throughout
High susceptibility to failure
Typically occurs upon cooling from higher T

Hydride Formation Cracking

Passivation

Ti

Hydride Formation Cracking

Passivation

Ti

Hydride Formation Cracking

Passivation

Ti

Hydride Formation Cracking

Passivation

Ti

Hydride Formation Cracking

Prevention
Internal phenomenon
Results from high-temperature reactions between
hydrogen and the metal
Remedies
Minimize operating temperatures
Heat treatment

Prevention Review
Design Specifications
Minimize material strength
Minimize carbon content for high-temperature
operation
Avoid titanium for high-temperature operation

Minimize Hydrogen Content

Heat treatment (processing & welding)
Use corrosion inhibitors
Maintain dry environment (storage)

Hydride Formation Cracking

Case Study
Titanium pipe
Used in Ammonium
carbonate condenser.
Time to failure: 5 years
Temp. 130C
Remedies: reduce
operating temperature,
use stainless steel

applause please

applause please
applause please

applause please

Questions?!
applause please
applause please
applause please
applause please
applause please

Have a Great SPRING

BREAK!!!!!!