Seminar Report on

Environmental assisted Cracking

Date: 24/2/2009 SUBMITTED BY:

Shivaprasad.P

080922004.

M.Tech CAMDA.

Manipal Institute of Technology, Manipal

Introduction:
It was argued that fracture-toughness parameter KIC, value represents the lowest possible material
toughness corresponding to the maximum allowable stress-intensity factor that could be applied
short of fracture. Yet, failures are known to occur when the initial stress-intensity-factor level is
considerably below KIC . These failures arise because cracks are able to grow to critical
dimensions with the initial stress-intensity level increasing to the point where K = KIC .
Such crack extension can occur by a number of processes. Subcritical flaw growth mechanisms
involving a cooperative interaction between a static stress and the environment include stress
corrosion cracking (SCC), hydrogen embrittlement (HE), and liquid-metal embrittlement (LME).
Fracture mechanics tests can provide a characterization of the phenomenology of EAC such as
the rate of crack advance and the associated crack velocity dependence on temperature, pressure,
and concentration of aggressive species. Surface chemistry and electrochemistry studies are
needed to identify the rate limiting processes, whereas metallurgical investigations are important
to identify what alloy compositions and microstructures are susceptible to the cracking process
and what fracture micro mechanisms are operative. These processes are mutually dependent on
one another. By contrast, final fracture can result from several mutually independent fracture
mechanisms; in this instance, the fastest process will dominate the fracture mode.

Embrittlement models:
These are the models which describe the SCC, HE,LME process. The need for so many models
is to attests to the complexity of EAC phenomena. Yet, certain clear similarities and differences
in proposed mechanisms are becoming apparent and have led some investigators to conclude that
these embrittling processes are often interrelated consequently,EAC may occur by either SCC or
HAC processes or by both. The latter condition is illustrated by the iron plus water system; in
this instance, the chemical reaction between Fe and H20 involves the liberation of hydrogen,
which then introduces the basis for HAC.

Hydrogen-Embrittlement Models:
The embrittlement of metal or alloy by atomic hydrogen involves the ingress of hydrogen into a
component, an event that can seriously reduce the ductility and load-bearing capacity, cause
cracking and catastrophic brittle failures at stresses below the yield stress of susceptible
materials. Hydrogen embrittlement occurs in a number of forms but the common features are an
applied tensile stress and hydrogen dissolved in the metal.
Hydrogen can also be picked up from the electrode cover material or from residual water during
welding. After diffusing into the base plate while the weld is hot, embrittlement occurs upon-
cooling by a process referred to as cold cracking in the weld heat affected zone.
Hydrogen may also enter the material as a result of electroplating (i.e., cathodic charging), which
contributes to early failure. It is ironic that the electroplating process, designed to protect a
material against aqueous environments and SCC, actually undermines fracture resistance of the
component by simultaneously introducing another cracking process.
Hydrogen pickup and associated embrittlement can also be introduced into the metal whenever a
sample under stress is exposed to a hydrogen gas atmosphere. It should be noted that
embrittlement does not occur as a result of prior exposure to Hydrogen gas in the absence of
stress. Hydrogen can diffuse rapidly through the lattice because of its small size. Calculations
have shown that hydrogen transport rates in association with dislocation motion can be several
orders of magnitude greater than that associated with lattice diffusion. Hence Hydrogen

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embrittlement is considered as a major contributing factor in a cracking process even though the
EAC rate is greater than the rate of hydrogen diffusion through the lattice.
Hydrogen tends to accumulate at grain boundaries, inclusions, voids, dislocation arrays, and
solute atoms. HAC is controlled by those hydrogen accumulation sites that are most sensitive to
fracture. From Fig.2 it is observed that the cracking process can involve cleavage, intergranular,
or ductile (micro void coalescence) fracture micro mechanisms.

The hydrogen-embrittling process, depends on three major factors:

• The original location and form of the hydrogen.
• The transport reactions involved in moving the hydrogen from its source to the' locations
where it reacts with the metal to cause embrittlement.
• The embrittling mechanism.

Now what is embrittling mechanism?

There are number of theories that have been proposed. According to one model, called
the "planar pressure mechanism," the high pressures developed within internal hydrogen
gas pores of charged material cause cracking. Although this mechanism appears valid for
hydrogen-charged steels, it cannot be operative for the embrittlement of steel by low-pressure
hydrogen atmospheres. In the latter situation, there would be no thermodynamic reason for a low
gas pressure external atmosphere to produce a high gas pressure within the solid.
Different type HE model was proposed by Beachem and discussed by
Hirth, among others. Beachem suggested that the presence of hydrogen in the metal lattice
greatly enhances dislocation mobility at very low applied stress levels. Brittle behavior is then
envisioned to occur as a result of extensive but highly localized plastic flow, which can occur at
very low shear stress levels.
Fig1. Various
processes involved
in the hydrogen
embrittlement of
ferrous alloys.

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 Fig 2. Flow diagram
depicting hydrogen
sources, transport
paths, destinations,
and induced fracture
micromechanisms.

Fig 3. Schematic representation

of different hydrogen-induced
fracture paths as a function of
stress level. (a) High K level
generates microvoid
coalescence;
(b) intermediate K level
generates transgranular fracture
by a quasi cleavage
mechanism;
(c) low K level leads to
intergranular fracture path.

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Stress Corrosion Cracking Models :
Stress corrosion cracking is a failure mechanism that is caused by environment, susceptible
material, and tensile stress. Stress corrosion cracking is an insidious type of failure as it can
occur without an externally applied load or at loads significantly below yield stress. Thus,
catastrophic failure can occur without significant deformation or obvious deterioration of the
component. Pitting is commonly associated with stress corrosion cracking phenomena.
The film rupture model, involving anodic dissolution at the crack tip, is capable of explaining
most examples of intergranular SCC. The principal feature of this model is that the protective
surface film in the vicinity of the crack tip is ruptured by localized plastic flow. Consequently, an
electrolytic cell is created with the bare metal at the crack tip serving as the anode and the
unbroken protective surface film serving as the cathode. The exposed bare metal is then
subjected to rapid anodic dissolution, thereby allowing the crack to advance, Since the protective
film is generally regarded to be passive in character, the rate of anodic dissolution and associated
crack extension will depend, in part, on the repassivation rate.
When the passivation rate is low, the crack tip becomes blunt because of
excessive dissolution on the crack sides; when the passivation rate is high, the amount of crack-
tip penetration per film-rupture event is minimized.

Fig 4.
Diagram showing film-rupture model.
Localized plastic flow at crack (a)
results in numerous film-rupture events
associated with transient anodic dissolution
(b).

Liquid-Metal Embrittlement:
Liquid metal embrittlement is the decrease in ductility of a metal caused by contact with liquid
metal. The decrease in ductility can result in catastrophic brittle failure of a normally ductile
material. Very small amounts of liquid metal are sufficient to result in embrittlement. When
many ductile metals are coated with a micron-thin layer of certain liquid metals.
Intergranular or transgranular cleavage fracture are the common fracture modes associated with
liquid metal embrittlement. However reduction in mechanical properties due to decohesion can
occur. This results in a ductile fracture mode occurring at reduced tensile strength.
Fracture times are extremely short, with crack velocities as high as 500 cm/s being reported for
aluminum alloys and brass in the presence of liquid mercury (Hg).

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Liquid-metal embrittlement is a result from liquid-metal chemisorptions induced reduction in the
cohesive strength of atomic bonds in the region of a stress concentration.
The liquid-metal atom (L) is believed to reduce the interatomic bond strength between solid
atoms, S1 and S2 at the crack tip, thereby causing bond rupture to occur at reduced stress levels.
Once the S1-S2 bond is broken, liquid-metal atoms then reduce the strength of the atomic bond
between solid atoms S1 and S3 with local fracture continuing at a rapid pace.

Fig 5. Model for liquid-metal embrittlement. Liquid-metal atom

L reduces interatomic bond strength between atoms S1 and S2. S1
and S3. and so on.

Variables Affecting Environment-Assisted Cracking:

EAC depends on a number of factors, including alloy chemistry and thermo mechanical
treatment, the environment itself, temperature, and pressure.

1. Alloy Chemistry and Thermo mechanical Treatment:

Many studies have been conducted to examine the relative EAC propensity of different families
of alloys and specific alloys thermo mechanically treated to different specifications. Studies
indicate that overaging is the most effective way to accomplish improvement of EAC
resistance . Toughness is improved while strength decreases as a result of the overaging process.
The effect of overaging on 7079 and 7178 aluminum alloys is shown in Fig.6. Although Stage I
in the 7079 alloy is shifted markedly to higher K levels, reflecting a sharp increase in KIEAC,the
growth rates associated with Stage II cracking remain relatively unchanged. Consequently, the
major problem of very high Stage II cracking rates in this material remains even after overaging.
By contrast, preliminary data for the 7178 alloy show a marked decrease in Stage II crack growth
rate with increasing aging time, while Stage I cracking is shifted to a much lesser extent. It
would be most desirable to have the overaging treatment effect a simultaneous lowering of the
Stage II cracking rate and a displacement of the Stage I regime to higher K levels. This may
prove to be the case in other alloy systems.
In general, KIEAC values tend to be greater in materials possessing higher K1C levels and lower
yield strength.
If the relative degree of susceptibility to environment-assisted cracking is defined by the ratio
KIEAC/KIC., the generally observed trend is for KIEAC/KIC to decrease with increasing alloy
strength. That is, KIEAC values drop faster than K1Cvalues with increasing strength.

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Most often, hydrogen and stress corrosion cracks follow an intergranular path in the important
high-strength steel, titanium, and aluminum alloys . Consequently, environment-assisted
cracking in wrought alloys is usually of greater concern in the short transverse direction
than in other orientations. As such, EAC orientation sensitivity parallels KIC orientation
dependence.

Fig.6. Effect of overaging on EAC (salt water) in 7xxx series aluminum alloys: (a) 7079 alloy
shows pronounced shift of Stage I behavior to higher K levels while (daldt)II remains relatively
constant; (b) 7178 alloy shows sharp drop in (daldt)lI.

2.Environment
The kinetics of crack growth and the threshold KIEAC level depend on the material-environment
system. The complex aspects of the material-environment interaction can be greatly simplified
by treating the problem from the phenomenological viewpoint in terms of a single mechanism,
environmental-assisted cracking.
This concept is supported by Speidel's results shown in Fig.7, which reveal parallel Stage I and II
responses for the 7075 aluminum alloy in liquid mercury and aqueous potassium iodide
environments. The liquid metal represents a more severe environment for this aluminum alloy,
but the phenomenology is the same. Furthermore, we see that the alloy in the overaged condition
is more resistant to the liquid-metal EAC. However, with increasing moisture content, cracking
develops with increasing speed. Consequently, EAC in aluminum alloys may take the form of
stress corrosion cracking and liquid-metal embrittlement but not gaseous hydrogen
embrittlement.

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 Fig 7. Environment-assisted cracking
with liquid mercury and aqueous iodide
solution in 7075 aluminum alloy

3. Temperature and Pressure.

EAC processes involve chemical reactions, it is to be expected that temperature and pressure
would be important variables. Test results, such as those shown in Fig., for hydrogen cracking in
a titanium alloy show the strong effect of temperature on the Stage II cracking rate. These data
can be expressed mathematically :

Where is activation energy for the rate-controlling process.

The apparent activation energy may then be compared with other data to suggest the nature of the rate-
controlling process.
It has been found that the apparent activation energies for the cracking of high-strength steel in water and
humidified gas are both about 38 kJ/mol, which corresponds to the activation energy for hydrogen
diffusion in the steel lattice. The apparent activation energy for Stage II cracking in the presence of
gaseous hydrogen is only 16 to 17kJ/mo1. Since the embrittling mechanism appears to be the same for the
both environments. The change in probably reflects differences in the rate-controlling
hydrogen-transport process. In this regard, note that the cracking rate in gaseous hydrogen
is higher than that in water.
The increase in Stage II crack growth rate with increasing pressure can be described
mathematically

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Increased pressure enhances hydrogen transport, which in turn increases the cracking rate.

Life and crack-length calculations :

Kinetic crack growth data can be integrated to provide estimates of component life and crack
length as a function of time. The effective steady-state cracking rate is controlled by the slowest
process acting in Regions I, II, and III. If one ignores the contribution of
then the controlling crack growth rate is given by

or

rearrangement of terms, the time devoted to steady-state cracking is given by:

To solve above equation, expressions for are needed in terms of K and the crack length a. In
Stage I

Where
K = stress intensity factor
T = temperature
P = pressure

Since log da/dt-K plots are often linear,

where C1and m are independent of K but may depend on T, P, and environment. For Region II

The lack of K dependence in and the fact that C2 depends on T, P, and environment . C2 can be
evaluated by

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From above equations it is possible to calculate the length of a crack at any given time, once the
various constants are determined from experimental data.
One additional subtle point should be made regarding the life computation. It should be
recognized that the life of a component or test specimen will depend on the rate of change of the
stress-intensity factor with crack length dK/da. Consequently, for the same initial K level, the
sample with the lowest dK/da characteristic will have the longest life. That is, changing
specimen geometry would alter the time to failure.

Fracture mechanics test methods:

For determination of KIC : Precracked samples were placed in the environmental chamber and
stressed in bending at different initial K levels by a loaded scrub bucket hung from the end of the
cantilever beam.
For each test condition associated with a different initial K value (always less than KIC the time
to failure was recorded.

FIG..8.
Environment-assisted cracking test
stand. Specimen is placed in
environment chamber at A and loaded
by weights placed in scrub bucket.

For determining KIEAC :

EAC data have been obtained with a modified compact specimen configuration (Fig. 9)In this
instance, a screw, engaged in the top half of the sample, bears against the bottom crack surface.
This produces a crack-opening displacement corresponding to some initial load. In this manner,
the specimen is self-stressed and does not require a test machine for application of loads. As the
crack extends by environment-assisted cracking, the load and, hence, the K level drop under the

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prevailing constant displacement condition. The crack finally stops when the K level drops below
KIEAC .Consequently, only one specimen is needed to determine KIEAC .Such a test is very easy to
conduct and very portable, since the self-stressed sample can be carried to any environment
rather than vice versa.

FIG.9. Modified compact tension

sample with threaded bolt bearing on load
pin. Initial crack opening displacement
determined by extent to which bolt is engaged.

Engage the screw thread to produce a given crack-opening displacement and place the specimen
in the environment. Samples are .examined periodically to determine when the crack stops
growing. The KIEAC value is then defined by the residual applied load remaining after the crack
has ceased growing and the final crack length as seen on the fracture surface.

Conclusion:
Stress corrosion is caused by the combination of quasi static or cyclic stress and a corrosive
environment. If the material undergoes anodic dissolution at the crack tip, a stress corrosion
cracking (SCC) mechanism dominates with the aid of the static or cyclic stress.

• If K < KIEAC then failure is not expected in an aggressive or corrosive fluid

• If KIEAC <K<KIC then crack growth and fracture occur after a prolong period of time
• If K >KIC then sudden fracture is expected upon loading.

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Reference:

Deformation and Fracture mechanics of Engineering materials by Richard. W. Hetrzberg
, John Wiley and Sons Inc Publication, 4th edition 1995

FRACTURE MECHANICS by Nestor Perez 2nd Edition Reprint ©2004 Kluwer
Academic Publishers

http://www.corrosion-doctors.org/

http://www.uni-saarland.de/fak8/wwm/research/phdbarnoush/

http://www.materialsengineer.com/A-failue.htm

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