Tutorial: Liquid Metal Cracking 1 1

Tutorial: Liquid Metal Cracking

 Description
 Causes & Mechanisms
 Recognition
 Examples from the MTI Atlas
 Example from the Corrosion Atlas
 Prevention

Description

"Liquid Metal Cracking" (LMC), "Liquation", "Liquid Metal Assisted Cracking", or "Liquid Metal Embrittlement" (LME) is the
intergranular penetration of one metal by another which is liquid or molten.

Most often, the aggressive environment is molten, such as molten zinc with stainless steel, or mercury with Alloy 400 (UNS
N04400).
LME may also be the result of an electrochemical reduction of specific metal salts in aqueous solution. For example, mercury salts
will produce metallic mercury which will cause LME of cold-worked brass.

Other examples of LME or LMC are cracking of steels by molten copper brazing alloys, of stainless steel Type 304 (UNS S30400) or
Type 316 (UNS S31600) by molten zinc and of high-strength copper alloys by mercury.

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Causes & Mechanisms

Liquid Metal Embrittlement (LME) and Liquid Metal Cracking (LMC) may be caused by the electrochemical reduction of salts in
aqueous solution. For example, mercury salts will produce metallic mercury which will cause LME of cold-worked brass.
Usually, however, LME or LMC does not involve typical -electrochemical- "corrosion" phenomena (the electrochemical reduction of
mercurous salts in aqueous solution is an exception). Nevertheless, liquid metal penetration along the grain boundaries constitutes a
very real problem.

A thorough discussion of the entire subject is available in the book "Embrittlement by Liquid Metals" (W. Rostocker, Reinhold Publ.,
New York, NY, 1960).

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Recognition

EXAMPLES from the MTI Atlas of Corrosion and Related Failures : View

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Example from the Corrosion Atlas:

Case01.01.22.02 (click on photo to zoom)

Material: Carbon steel.

System: Utility boiler (14 MPa).
Part: Water-wall tube, 3rd burner level.
Phenomenon: Liquid metal embrittlement.
Appearance: Longitudinal through-wall cracks initiating on internal surface in
region of metallic copper plating on hot side of tube. There was only minor wall
thinning at the fracture lip, and some necking was apparent.
Time to Failure: Boiler had been in service for 20 years. Cracking occurred in
less than 20 minutes during the overheating event.

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Prevention

 Select suitably resistant materials of construction.

 Keep dangerous species or (liquid) metals away from susceptible metals or alloys (e.g. do not allow 'contamination' of
stainless steel by galvanized steel).

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Intergranular Penetration Processes

Introduction
There are several forms of intergranular attack of metals which are distinguished from stress corrosion by the apparent absence of
stress. Grain boundaries are attacked preferentially because of their disordered structure relative to that of the interior of the grains.
This effect may be accentuated in an alloy by the depletion of beneficial elements or the concentration of detrimental elements at or
near the grain boundaries; see "Sensitization".

 Intergranular Attack (aqueous media)

 Intergranular Attack (hot gases)
 Weld Decay and Sensitization
 Knife Line Attack
 Liquid Metal Penetration
 Tutorials:
 Intergranular Attack (Corrosion)
 Liquid Metal Penetration (Cracking)

Intergranular Attack (aqueous media)

Intergranular penetration occurs during attack by aqueous solutions of specific aggressive agents, such as nitric acid or dilute
sulfuric acid with oxidisers, which penetrate deeply along the grain boundaries of sensitised austenitic steels to produce a network of
branching cracks which rapidly destroy the integrity of the material.

Intergranular penetration closely resembles intergranular stress corrosion. It may be diagnosed unequivocally in an austenitic steel
which has suffered corrosive attack, has been sensitized and is not stressed, either by impressed or residual surface tensile stresses.
It can be prevented by desensitising the material. It may not be possible in practice absolutely to exclude contact with aqueous
halides.

Causes & Recognition

Essential Conditions
Austenitic steel. Resistance of grain boundaries to corrosion reduced (e.g. sensitized). Too high carbon. Lack of strong
carbide formers. Incorrect heat treatment.
Analysis
In the case of steels analyze for excessive carbon content or too low contents of stabilizing elements (Nb, Ti, Mo).
Alternatives
Resembles stress corrosion.
Distinguished by
Apparent absence of stress.

Morphology

Surface Appearance Metallographic Section

Multiple crack system oriented at random. X 1 Sensitization (of ferritic steel) revealed by etching. X 100
Other Characteristic Features

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Intergranular fracture (in this case of columnar cast structure). X0.5

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Intergranular Attack (hot gases)

Intergranular corrosion attack by reducing sulphur gases on nickel alloys or aqueous solutions on aluminium-iron alloys does not
penetrate deeply but surrounds and removes grains in layers so that the surface exfoliates but the material does not crack.

Intergranular corrosion can be recognised by the characteristic morphology of attack and the study of corrosion products formed in
the scale.

The cures are specific to the aggressive agent and the substrate. Typical palliatives for gaseous corrosion are, reducing temperature,
increasing the chromium content of a nickel alloy, removing aggressive agents such as sulphur from the corroding gas or changing
conditions from reducing to oxidising or vice versa.

Causes & Recognition

Essential Conditions
Presence of constituent along grain boundaries; e.g. reducing sulfur on nickel alloy which forms eutectic.
Analysis
Analyze surface or seek aggressive constituent, e.g. sulfur.
Analyze environment for aggressive agent, e.g. reducing sulfur.
Analyze fuel for sulfur.
Alternatives
Intergranular penetration in aqueous environment.
Distinguished by
No liquid water. Corrosion does not penetrate deeply but removes grains in layers, sometimes causing exfoliation (or pits).

Morphology

Surface Appearance Metallographic Section

Rough surface originally covered with

Sub-surface attack on tube. X 45
heavy scale and/or deposits. Most
severe on up stream surface. X 0.5
Other Characteristic Features

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Underside of scale. X 2 Nickel sulfide on underside of scale.

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Weld Decay and Sensitization

WELD DECAY

Weld decay is a form of intergranular penetration which occurs in austenitic steel weld-heat-affected zones which have been
sensitized by the heating developed during welding.

It may be distinguished from general intergranular penetration by its occurrence in a band of limited width which maintains a
constant distance from the fusion zone of a weld. In extreme cases, metal is completely removed to form two parallel trenches
which may penetrate right through the metal. Micro examination always reveals intergranular attack at the surface of the residual
material.

Weld decay can be prevented by eliminating sensitisation by choice of composition or by post weld heat treatment.

SENSITIZATION

Sensitization, the depletion of chromium in the vicinity of grain boundaries is one mechanism that decreases the resistance of 17%
chromium ferritic stainless steels to intergranular stress corrosion, and that of austenitic stainless steels to intergranular stress
corrosion, intergranular penetration and weld decay.

Ferritic stainless steels are sensitised when heated to above 900°C, so that austenite forms and some of the carbides and nitrides
dissolve. On cooling to between 700 and 400°C chromium-rich carbides and nitrides precipitate chiefly at the grain boundaries and
deplete chromium in the vicinity. Severely sensitised 430 will stress corrode in tap water. The problem still exists with carbon
contents near the 0.03% level. It can be reduced by adding stabilizing elements Ti and Nb, and material can be desensitised by
annealing at 800°C to allow the chromium to diffuse back to the sensitised regions.

An austenitic steel which contains more than 0.03% carbon and no strong carbide forming elements other than chromium is
sensitised when heated in the temperature range 430 to 800°C. Complex chromium carbides precipitate preferentially because of
the extra mobilityin the grain boundaries and the adjacent areas are depleted of chromium and therefore become susceptible to
attack by corrosive media including some considered only mildly corrosive. This form of sensitization has been extensively studied
and can be eliminated by:

 Heating the entire component after welding to a "solution treatment" temperature within the range 1040 to 1150°C to
dissolve the carbides and cooling rapidly enough to prevent precipitation.
 "Stabilizing" adding sufficient niobium or titanium to combine preferentially with the carbon and thereby prevent the
precipitation of the chromium carbides.
 Reducing the carbon content of the steel and, if welded, also the filler metal.

A condition resembling sensitisation may affect titanium and niobium stainless steels when they are heated during welding for a long
period at the top of the sensitisation range. The titanium or niobium carbides are decomposed and the carbon is free to combine
with chromium and thus sensitise the steel which then becomes prone to knife line attack.

Causes & Recognition

Essential Conditions
Austenitic steel. Weld HAZ sensitized by heating during welding. Too high carbon. No strong carbide formers. Incorrect (or
no) heat treatment.
Analysis

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Analyze for excessive carbon or too low content of stabilizing elements (Nb, Ti).
Alternatives
Unmistakeable.

Morphology

Surface Appearance Metallographic Section

Metal removed by corrosion to form Intergranular nature of attack at

parallel trenches either side of fusion zone. sides and base of trenches. X 66
Other Characteristic Features

Section showing configuration of trenches. X2

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Knife Line Attack (KLA)

Knife-line attack is a form of intergranular penetration which occurs in a very narrow band very close to the fusion zone of an
austenitic steel stabilised with titanium or niobium which has been subjected to intense and prolonged heating during welding.

It may be distinguished from weld decay by the thinness of the bands, and by the presence of titanium or niobium in the metal.

Knife line attack is of very rare occurrence and is best avoided by adopting welding procedures which do not impose prolonged and
intense heating. Failing that, the condition can be remedied by solution heat treating after welding.

Causes & Recognition

Essential Conditions
Prolonged and intense heating during welding of steel stabilized with Nb or Ti. Corrosive aqueous environment.
Analysis
Analyze for Nb, Ti.
Alternatives
In early stages resembles HAZ cracking (e.g due to weld decay).
Distinguished by
Conditions different.

Morphology

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Surface Appearance Metallographic Section

Metal deeply grooved by corrosion

Knife line attack on metal at fusion zone. X 50
at edges of fusion zone. X 1.3
Other Characteristic Features

(Section) Early stage of knife line attack. X 8 (Section) Advanced stage of knife line attack. X 2.5

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Liquid Metal Penetration

Liquation, Liquid Metal Cracking (LMC), Liquid Metal Embrittlement (LME) or Liquid Metal Penetration is a form of (stress) corrosion
in which the aggressive agent is a liquid metal. Metals such as lead, bismuth, cadmium, tin and zinc in contact with steel at elevated
temperature and stressed in tension penetrate rapidly along grain boundaries and cause failure by cracking.

Many metal systems, including copper, aluminum and titanium as well as the stainless steels and nickel alloys, are subject to LMC,
usually by molten metals which react specifically with the alloy system.

The threshold temperature required for liquid metal penetration to occur may be below the melting point of the metal.

Common Examples
Zinc melted from galvanized components has often caused liquid metal penetration of the wall of an austenitic steel vessel or
component, e.g. heated in a fire. Another practical example is copper derived from brazing metal which has precipitated failure in an
overheated shaft. The latter incident is illustrated in the photographs shown under the Morphology heading below.

Causes & Recognition

Essential Conditions
Contact with liquid metal at high temperature. Surface tensile stress which may be applied or residual.
Analysis
Examine surface for aggressive metal.
Alternatives
Stress corrosion (intergranular).
Distinguished by
Different aggressive agent.

Morphology

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Surface Appearance Metallographic Section

Intergranular cracking and copper colored deposition.

Shaft cracked and partially covered
with molten brass. (a) Lower left corner : fracture;
(b) Upper right corner : laboratory test specimen.
Fracture Low Mag Fracture High Mag

Multiple fracture types. Intergranular cracking and copper colored deposits.

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