1

FORMS OF CORROSION
INTRODUCTION
Corrosion can manifest itself in many forms and the identification
of the forms of corrosion through careful observation of the corroded
parts, is always helpful in understanding the problem and suggesting ways of
solution. Each form can be identified by mere visual observation, though
sometimes magnification is required. The most common and easily identified
form of corrosion is uniform corrosion where corrosion proceeds uniformly over
the entire exposed area. It is also easy to evaluate uniform corrosion by simple
weight loss measurements.
PART I: LOCALISED AND SELECTIVE ATTACK
The forms of corrosion arising due to localized and selective attack are
considered in this part.
Pitting [1,2]
It is one of the most destructive and insidious forms, as the attack is
extremely localised resulting in holes in metal and causing equipment and
pipeline failures. It is often difficult to identify pits because of their small size and
they are often covered with corrosion products. In absence of any mechanical
stress, the pits formed are generally saucer shaped. The term pitting is applied
when the surface diameter is about the same or less than the depth. The
number, size and depth of pits vary widely. A dotted appearance of the
corrosion product or a surface with well defined irregularities is likely to be an
indication of pits underneath. Pits usually grow in the direction of gravity and
only rarely do pits grow in the direction of gravity and only rarely do pits grows
upward from the bottom of horizontal surfaces.
Occasionally the pits may start on vertical surfaces. In some cases pits
may undercut or be so irregular as to present a honey combed surface. Pitting
is difficult to evaluate. The term, pitting factor, is used to express the ratio of the
depth of the deepest pit to the average penetration as calculated from weight
loss. The depth is measured by a micrometer having a properly shaped tip or
by a calibrated microscope focusing on the surface and then on the pit
bottom. Pitting usually requires
an initiation period which may vary
considerably depending on the metal and the environment. After initiation, pits
tend to grow at a rapid rate.
Environmental conditions favorable for pitting

2
Pitting is generally associated with halide ions, with chlorides, bromides
and hypochlorites being the most prevalent. Fluorides and iodides have
comparatively little pitting tendencies. From a practical standpoint, most pitting
failures are caused by chloride and chlorine containing ions. This is due not
only to their greater aggressiveness but also to the wider distribution of
chlorides in nature. Oxidising metal ions with chlorides (cupric, ferric and
mercuric halides) are extremely aggressive.
Non-oxidising metal halides (NaCl, CaCl 2) are less aggressive.
Aggressive anions can stimulate the development of pitting corrosion only
when they exceed a certain critical concentration. Potentiostatic studies show
that the aggressive action of ions is displayed only at potentials more positive
than a certain critical value. The value of this potential greatly depends both on
the nature of metal or ally and on the nature and concentration of
aggressive anion. Table 1 shows critical potentials for certain metals and
alloys. Pitting is usually associated with stagnant conditions. Movement of
fluid often decreases pitting attack.
Metallurgical factor
Iron, nickel, aluminium, magnesium, zirconium, copper, tin, zinc and many of
their alloys are subject to pitting. But, as a class the stainless steel alloys are
more susceptible to damage. The effects of alloying on pitting resistance of
stainless steels are given in Table-2. Severe cold working increases the
pitting attack of 18-8 stainless steels in ferric chloride. Holding types 304 and 316
stainless steel in sensitizing temperature range (950 to 1450 oF) decreases
their pitting resistance. Austenitic stainless steels exhibit the greatest pitting
resistance when solution quenched from 1800oF. Pitting is less likely to occur
on polished than on etched or ground surfaces. Generally, the pits that form
on a polished surface are larger and penetrate more rapidly than those on
rough surfaces.
Mechanism
The autocatalytic process occurring in a corrosion pit when a metal `M'
is being pitted by an aerated sodium chloride solution is illustrated in Fig.1. This
process is self-stimulating and self-propagating. Electrochemically the pit
formation is associated with a small anode surrounded by a large cathodic
surface. Small anodes arise from local heterogeneity or local breakdown of
passive film. The rapid dissolution of metal within the pit tends to produce an
excessive positive charge in this area, resulting in the migration of chloride
ions to maintain electroneutrality.

3
Table 1
Critical Potential for Certain Metals and Alloys in Chloride and Bromide Solutions
Metal or Alloy
Mg
Al
Zr
Alloys, Fe Cr
13% Cr
17% Cr
28%
Alloys Fe-Cr, Ni
Ti
(Cr22%,
Ti
0.5%)
0% Ni
1% Ni
2% Ni

1.0 N
- 1.419
-0.509
+0.380

Critical potential* V volts

Cl 1
0.1 N
----+0.450

+0.140

+0.320
+0.360
+0.750

0
-----

+0.360
+0.420
+0.470

Br1.0 N
-1.269
-0.369
+0.660

* with respect to normal hydrogen electrode

Source :

Ja. M. Kolotyrkin : Proceedings of 2nd International Congress on

Metallic Corrosion by NACE, 980, M2M Building, Houston 2
Texas, USA (1966) p.24.
TABLE - 2
EFFECTS OF ALLOYING ON PITTING RESISTANCE OF
STAINLESS STEEL ALLOYS

Element
Chromium
Nickel
Molybdenum
Silicon
Titanium & Columbium
Sulfur and selenium
Carbon
Nitrogen

Pitting resistance
Increases
Increases
Increases
Decreases; Increases when present with
molybdenum
Decreases in FeCl3 No effect in other media
Decreases
Decreases, especially insensitized condition
Increases

4
Thus in the pit there is a high concentration of MCl and hydrolysis takes
place as follows :
M+ Cl- + H2O MOH + H+Clresulting in a high concentration of hydrogen ions. Both hydrogen and chloride
ions stimulate the dissolution of most metals and alloys and the entire process
accelerates with time. Since the solubility of oxygen is virtually zero in corrosive
solutions, no oxygen reduction occurs within a pit. The gravity effect
mentioned before is a direct result of the autocatalytic nature of pitting. Since
the dense concentrated solution is necessary within a pit, pits are more stable
when growing in the direction of gravity.
Crevice Corrosion [2]
This type of attack is usually associated with small volumes of stagnant
solution caused by holes, gasket surface, lap joints, surface deposits and
crevice under bolt and rivet heads. To function as a corrosion site, a crevice
must be wide enough to permit liquid entry but sufficiently narrow to
maintain a stagnant zone. Crevice corrosion usually occurs at openings, a few
thousandth of an inch or less in width. Contact between metal and non metallic
surface (gaskets) can cause crevice corrosion. Fibrous gaskets (asbestos fabric)
provide ideal crevices. Metals or alloys which depend on oxide films for
corrosion resistance are particularly susceptible. Stainless steels are most
vulnerable.
Mechanism
Consider a riveted plate section of metal (N) immersed in aerated sea
water (pH 7) as shown in Fig.2. Initially the oxidation reaction (M M+ + e-)
and reduction reaction (O2 + 2H2O + 4e- 4OH-) occur uniformly over the entire
surface including the crevice. After a short interval, the oxygen within the crevice
is depleted because of the restricted convection. After oxygen is depleted, no
further oxygen reduction occurs within the crevice, although dissolution of metal
M continues. This tends to produce an excess of positive charge in the solution
which is necessarily balanced by the migration of chloride ions into the
crevice (hydroxide ions are less mobile) and autocatalytic process as in the case
of pitting occurs.
Prevention
1.
2.
3.

The best method is to avoid crevices by proper design (the various design
procedures are discussed elsewhere)
Solids in suspension and wet packing materials should be removed.
Solid non-absorbent gaskets (Teflon) should be used.

Galvanic Corrosion [2]

It often becomes necessary to couple dissimilar metals in the process
flow system and a potential difference usually exists between two dissimilar
metals when in contact with a corrosive or conductive solution. Corrosion of the
less corrosion resistant material in the couple is usually accelerated and that
of the more resistant material is decreased, as compared with the behaviour
of these metals when they are not in contact. This form of corrosion is known
as galvanic or two metal corrosion, the driving force for current and corrosion
being the potential difference. In the absence of actual tests in a given
environment, the galvanic series given in Table-3 gives us a good indication of
possible galvanic effects. Two metal corrosion is readily recognized by the
localized attack near the junction with attack decreasing with increasing
distance from the junction depending on the conductivity of the solution. A
couple which has a large cathode and small anode increases the corrosion rate
of the anode (by 100 or 1000 times) considerably. Cathodic area controls the
amount of corrosion current while anodic area controls anode current density
and thus severity of galvanic corrosion. The main factor preventing severity of
corrosion is polarisation. Some couples polarise strongly (e.g. Al-S.S) so that
only a small corrosion current flows while others polarise very little (e.g. Al-Cu)
and the initial high corrosion current is maintained. Some couples (e.g. Fe-Zn)
reverse their polarity with temperature.
Galvanic corrosion is normally observed when metals are kept
immersed in electrolytes e.g. ship hulls, boilers and cooling water systems,
chemicals plants etc., Bimetallic effect can occur even in humid atmospheric
exposure but it is restricted to an area close to the contact. Intense bimetallic
effect can take place when metals with low over potentials such as copper,
silver, carbon etc are coupled to metals with high over potentials such as zinc,
iron, aluminium.etc.,
Intergranular Corrosion [2,4]
The most stable configuration of the metal is the particular crystal
lattice and grain boundaries are high energy areas, but are usually only slightly
more reactive than the lattice. However, under certain conditions, grain
boundaries are very reactive and localised attack at and adjacent to grain
boundaries with relatively little corrosion of the grains takes place which is
known as intergranular corrosion. The alloy disintegrates and / or loses its
strength. Intergranular corrosion can be caused by impurities at the grain
boundaries, enrichment of one of the alloying elements or depletion of one of
these elements in the gain boundary areas.

Table - 3

6
GALVANIC SERIES OF SOME COMMERCIAL METALS AND
ALLOYS IN SEAWATER
Noble or cathodic

Active or anodic

Source

Platinum, Gold graphite

Titanium, Silver
Chlorimet 3 (62 Ni, 18 Cr, 18 Mo)
Hastelloy C (62 Ni, 17 Cr, 15 Mo)
18-8 Mo Stainless steel (passive)
18-8 Stainless steel (Passive)
11-30% Cr Stainless steel (Passive)
Inconel (Passive) (80 Ni,13 Cr, 7 Fe)
Nickel (Passive)
Silver solder
Monel (70 Ni, 30 Cu)
Cupronickels (60-90 Cu, 40-10 Ni)
Bronzes (Cu-Sn)
Brasses (Cu-Zn)
Copper
Chlorimet 2 (66 Ni, 32 Mo, 1Fe)
Hastelloy B (60 Ni, 30 Mo, 6 Fe, 1 Mn)
Inconel (Active)
Nickel (Active)
Tin, lead, lead-tin solders
18-8 Mo Stainless Steel (Active)
18-8 Stainless Steel (Active)
High nickel cast iron
13% Cr Stainless steel (Active)
Cast iron
Steel or iron
2024 Aluminium
Cadmium
commercially pure aluminium (1100)
Zinc
Magnesium and magnesium alloys

Fontana,
M.G.,
Greene
N.D.,
Corrosion
McGraw - Hill Book Company, New York, 1967.

Engineering,

Lattice deformations in the grain boundary zone localises excess potential

energy and if the zone contains atoms of dissolved additional elements which
decrease its excess energy then the concentration of the additional element
in this zone will increase which is called intercrystalline internal adsorption.
This adsorption may have either a positive or negative effect
on the
development of intergranular corrosion. Adsorption of carbon in some types of

7
steel may facilitate carbide formation leading to the depletion of chromium at
grain boundary (Fig.3). On the other hand, some additional elements can be
adsorbed at the same time and they can act as stabilisers and increase the
resistance.
Austenitic stainless steels
Referring to Table-4, the maximum susceptibility is when these steels
are heated in approximately temperature range 950 - 1450 oF. If carbon
content is about 0.02% or higher (Type 304 - 18-8 S.S. Usually contains from
0.06 to 0.08% carbon) in the temperature range indicated, carbon diffuses
towards the grain boundary quite readily (but chromium is much less mobile)
and Cr23 C6 precipitates out of solid solution, thereby removing chromium
from the zone near grain boundary. The chromium carbide in the grain
boundary is not attacked but the chromium depleted zone the grain boundary is
corroded. 18-8 stainless steel welded structures are sometimes attacked
intergranularly (called weld decay) since the metal in the weld-decay zone
(base metal along both sides of weld seams) are heated to the sensitizing
temperature. Preventive measures adopted are,
1.
2.
3.

quench
annealing or solution quenching
above
the
sensitizing temperature.
adding stabilising elements that are strong carbide formers
(columbium or columbium + tantalum and titanium are used
to produce type 347 and 321 SS respectively)
Lowering the carbon content to below 0.03%
Table - 4

SHEMATIC CHART SHOWING SOLUTION AND PRECIPITATION REACTIONS

IN TYPES 304 AND 347
2250oF

Columbium carbide
carbide dissolves.

11450oF

Columbium
carbide
Chromium carbide dissolves

950oF

Chromium carbide precipitates

70oF

No reaction

Source :

Fontana, M.G and Greene, N.D.,

McGraw Hill Company, New York, 1967.

dissolves

Corrosion

Chromium
precipitates

Engineering,

8
Aluminium alloys
Heat treatment to precipitate intermetallic compounds like
CuAl2 in
Duraluminium type alloys (Al-Cu) along the grain boundary results in the
strengthening of alloy. But at the same time the Cu depleted zone is subjected
to intergranular corrosion (CuAl2 is the cathodic grain boundary precipitate).
In Al alloy containing 5-11% Mg the intermatallic compound Al3Mg2 is the
strengthening phase, but is corrosion resistance is lower than that of
aluminium. In aluminium alloys containing 3% Mg, no reactive grain boundary
precipitate takes place. Mn Al6 and Mg2Si are not susceptible. In aluminium
alloys containing 3 Mg, anodic grain boundary precipitates Mg5Al8 and MgZn2
are susceptible.
Exfoliation or layer corrosion
Rolled aluminium alloys such arrearage Al-Mg or Al-Zn-Mg alloys can suffer
exfoliation. It is a special form of intergranular corrosion but with flattering of
grain and flaking effect strength is significantly reduced. Corrosion product due
to its wedging effect can often lead to SCC.
Dezincification [2]
Dezincification is the selective removal of zinc in brass alloys and is readily
observed with the naked eye, because the alloy assumes a red or copper
colour contrasting with the original yellow. Overall dimension do not change
appreciably when dezincification occurs but the dezincified portion is weak,
permeable and porous. Uniform or layer - type of dezincification seems to
favour the high brasses (high zinc content) and definitely acidic
environments. The plug type (localised sem to occur in low brasses and
neutral, alkaline or slightly acidic environments. Stagnant conditions usually
favour dezincification.
The commonly accepted mechanism of dezincification consists of three steps
1. the brass dissolves
2. the zinc ions stay in solution and
3. the copper plates back on
Conditions favouring dezincification
1.

High zinc content, e.g Muntzmetal (60% Cu, 40% Zn). Al brass (76%Cu,
22% Zn, 2%Al) and yellow brass (66%Cu, 33%Zn).

2.

Contact with slightly acid or alkaline waters not highly aerated.

3.

Low rates of flow

4.

High tube wall temperatures in condensers

5.

Permeable deposits and coatings over the tube surfaces.

Dezincification can be minimized by using low zinc brasses, e.g Red brass
(85% Cu, 15%Zn) or by using better brasses containing small amounts or
arsenic, antimony or phosphorous as "inhibitors". e.g Admiralty brass
(70%Cu, 29%Zn, 1%Sn and 0.05%As) and Al brass (76%Cu
sometimes
being as high as 2V. The iron is dissolved leaving a porous mass of graphite
plus voids and corrosion. Overall dimensions do not change, but the materials
loses its mechanical strength and dangerous situations may develop without
detection. (A buried pipeline may function adequately for a long time but
suddenly rupture due to graphitizonal). The surface usually shows rusting
that appears superficial, but the metal has lost its strength. Graphitization is
usually a slow process. Graphitization does not occur in nodular or malleable
cast ions because the graphite network is not present to hold together the
residue. White cast iron has essentially no free carbon and is not subject to
graphitization.
Filiform Corrosion [2,6,7]
Filiform corrosion is thread-like (filamental) type of corrosion which develops
under protective coatings on certain metals, usually in humid atmospheres.
This type of corrosion may be found on such things as jelly can covers, tools
coated with a film or oil, refrigerator doors, coated metal tile and on chromium
plated automobile
hardware and even under paper wraps.
Filiform
corrosion has been observed on steel magnesium and aluminium surfaces
covered by tin, silver, gold phosphate, enamel and lacquer coatings. It does
not weaken or destroy metallic components but only affects the surface
appearance and so it is a major problem in the canning industry.
Characteristics of filiform corrosion on steel
It occur at room temperature in the relative humidity range of 65 to 95% growing
with wider filaments at the higher humidities. Thread is normally 001-005mm
thick and grow @ a typical rate of 3 mm a week. Growth is more vigorous under
thicker organic films than under thin films though it is inhibited by films that are
impermeable to moisture. It will grow under organic films only when they are
formulated below their critical pigment volume concentrations where the film
serves as a
semi-permeable membrane. Secondly, the film must have
sufficient elasticity to yield without breaking to provide for the expansion of
corrosion product. Corrosion filaments are initiated at edges (or at weak points
or discontinuities in the film) and tend to move in straight lines. Their growth is

10
independent of light and of the metallurgical structure of the substrate. It can
be grown in complete darkness, in direct and diffuse sunlight and under
critical illumination. There is no relation between filiform growth and biological
activity. Filaments do not cross inactive tails and other filaments, rather
deflect or join in a predictable manner the angle of incidence being usually
equal to the angle of reflection (Fig.4). The growing filament has a blue-green
coloured active head -V shaped (which contains ferrous ions in a liquid solution)
and a red-brown coloured inactive tail (which contains the dry stable corrosion
product, viz. ferric oxide and hydrated ferric oxide). The filaments are 1/10" or
less in width and corrosion occurs only in the filament head.

Mechanism
The basic mechanism appears to be a special case of crevice corrosion.
During growth, the head is supplied with water from the surrounding
atmosphere by osmotic action due to the high concentration of dissolved
ferrous ions. Osmosis tends to remove water from the inactive tail, because of
the low concentration of soluble salts. The oxygen concentration at the interface
between the tail and the head is high because of lateral diffusion. Corrosion
is restricted to the head where hydrolysis of the corrosion products produces
an acidic environment. The active head is exclusively anodic towards all
other parts of the corroding system and the cathode areas are randomly
scattered over the remainder of the metal surface.
Some of the hydroxy ions formed at the cathode diffuse sideways and reinforce
the oxide film render the area passive and slightly alkaline which prevents attack
if another active head approaches.In magnesium metals, active head is black in
colour and inactive tail is white in colour.
Prevention
In the field of product finishing, it is advisable to avoid high humidities during the
finishing operations and during the storage of finished product. An impermeable
film can be expected to inhibit filiform growth. The use of highly permeable
pigmented films has also been suggested. The elimination of water soluble
components or extractives in the coating is another method.
FORMS OF CORROSION
PART - II
EFFECT OF STRESS AND WEAR STRESS CORROSION CRACKING [2,8,11]

11

Stress corrosion cracking (SCC) is the sponaneous cracking that may result
from the conjoint action of tensile stress and corrosive media. In the
abosence of either stress or corrosion, the failure would not occur. The failure
is a type of brittle fracture of normally ductile metals by the presence of
specific environments. During SCC, the metal or alloy is virutally unattached
over most of its surface, while fine cracks progress through it. It is important to
differentiate clearly between SCC and stress accelerated corrosion where
structural corrosion is intense even in the absence of stress and the effect of
stress is to rupture the grain boundaries and to promote penetration of the
environment.

Practically all metallic structural systems contain alloys susceptible to SCC

in some environmental conditions (Table-5).Caustic embrittlement of steel
boilers and seasonal cracking of brass cartridge cases are well known
examples of SCC. Even pure metals may be subjected to SCC (e.g pure Cu
in Cupric-Ammonium complexed [4]). Alloys subject to cracking are normally
considered to be passive and no-corroding alloys. Environments in which
cracking occurs are those in which corrosion is highly localised. If the initial
localised corrosion is intergranular, the subsequent cracking is predominantly
intergranular (e.g Al-Cu alloys, Al-7% Mg alloys, Cu-base alloys, mild steel, Mg
alloys with impurities at grain boundaries, etc. ) If the initial attack is in the body
of grain, transgranular cracking develops (e.g Mg alloys, 18-8 stainless steel,
etc.,) Variations in composition, heat treatment, fabrication and mechanical
processing affect the microstructure and consequently SCC susceptibility. SCC
is well known in various aqueous media but it also occurs in certain liquid
metals, fused salts and non-aqueous inorganic liquids. The presence of
oxidisers often has a pronounced effect on cracking tendencies. SCC is
accelerated by increasing temperature.
SCC is service results from tensile stresses at the surface or subsurface
usually of considerable mangitude acting for prolonged periods of time. Stresses
of this nature are usually residual, produced by methods of manufacture
(quenching, cold forming, tube drawing without internal mandrel etc.,) or
assembly (welding, press or shrink fits, wrapping of sheet to fit a structure,
joining of poorly fitted parts etc.). Stresses due to applied loads are seldom
met in practice because of design considerations. Once a crack starts, it is
possible for it to continue with no applied or residual stress but simply to bee
driven by pressures from corrosion products [5] (of the order of 4000 - 7000
psi) SCC has never been observed to result from surface compressive stress
(indeed, the introduction of surface compressive stress may be used as a
preventive measure). As the magnitude of stress increases the time for total
failure decease. Although high stresses approaching the yield point are generally

12
needed for SCC, frequently stresses that are small relative to the yield
produce failure. For many alloy systems a "threshold" stress ( a stress below
which SCC does not occur in some finite period of time) has been observed.
SCC grow in a plane perpendicular to the operative tensile stress and may
take either an intergranular or a transgranular path. The crack propagation is a
discontinuous process.

Table 5
ENVIRONMENTS THAT MAY CAUSE STRESS CORROSION OF METALS AND
ALLOYS
Materials

Environment

Aluminium alloys

NaCl-H2O2 solutions
NaCl Solutions, Sea water
Air, water vapour

Copper alloys

Ammonia vapours and solutions

Amines water, water vapour

Gold alloys

FeCl3 solutions
Acetic acid - salt solutions

Inconel

Lead acetate solutions

Magnesium alloys

NaCl - K2CrO4 solutions

Rural and coastal atmospheres
Distilled water

Monel

Fused caustic soda

Hydrofluoric acid

Nickel

Hydrofluosilicic acid

Ordinary steels

NaOH solutions
NaOH - Na2 SiO2 solutions
Calcium, ammonium and sodium Nitrate
solutions

13
Acidic H2S solutions
Sea water Molten Na-Pb alloys
Stainless steels

Titanium alloys
Source :

Acid chloride solutions such as MgCl2

& BaCl2 Acl - H2O2 solutions.
sea water H2S NaOH - H2S solutions
condensing steam from chloride waters
Red fuming nitric acid, sea water, N2O4
methanol HCl.

Fontane, M.G and Greene, N.D., Corrosion Engineering, McGraw

Hill Company, New Yourk, 1967.

Mechanism
Corrosion plays an important part in the initiation of cracks. A pit trench or other
discontinuity or the metal surface acts as a stress riser. Once a crack have
started, the tip of advancing crack has a small radius and the stress
concentration is great. Plastic deformation of an alloy can occur in the
region immediately preceding the crack tip because of high stresses. The role of
tensile stress has been shown to be important in rupturing protective films
during both initiation and propagation of cracks. Current theories usually resolve
themselves into one of two mechanisms.
i.

Electrochemical including oxide film rupture or tubular corrosion pit

modifications.

ii.

Stress sorption cracking involving surface energy reduction by adsorbed

components of the environments.

Electrochemical theory
Galvanic cells are set up between continuous intermetallic precipitates and
adjacent metal at grain boundaries or through paths within the grains, the
ensuring corrosion acting under stress to open up a crack. The applied
stress is considered helpful in rupturing surface films thereby exposing fresh
et.al at the tip of the crack allowing the reaction to continue. The main support
of electrochemical mechanism is contributed by potential measurements and
the inhibiting effect of cathodic polarisation. The weakness of this theory is
the required specificity of electrolyte - that some metals crack only in specific
electrolytes whereas electrochemical action would in fact be expected in a
variety of related chemical media - is unexplained. There appears to be no
reasonable electrochemical explanation why addition of extraneous anions
to damaging environments should act as inhibitors for SCC (Chlorides and
acetates for carbon steels in boiling nitrate solutions).

14
Stress sorption cracking
The mechanism precedes by weakening of already strained metal atom
bonds through adosrption of the environmental or its constituents. The
surface energy of the metal is said to be reduced encouraging the metal to
part under tensile stress. This theory explains the specificity of environments
(chemisorption is also specific) and also explains the inhibiting effect of
extraneous anions and of cathodic protection (they may be the corrosion
potential into regions where the damaging species do not adosrb). An
explanation is still required for the immunity of pure metals and importance lattice
structure.

There seems to be general concurrence in the view that cracking by either

mechanism is related to pile-up of dislocations at barriers of one kind or
another. All the theories proposed contain elements of speculation and no
one of them has been demonstrated beyond a doubt.
SCC may be reduced or prevented by application of one or more of the following
methods.
(i)

Lowering the stress below the threshold value if one exists (by annealing
in the case of residual stress, thickening the section of reducing the
load).

(ii)

Eliminating
the critical
environmental
demineralisation or distillation).

(iii)

Chaninging the susceptible alloy

(iv)

Applying cathodic protection

(v)

Adding inhibitors.

species (degasification,

Hydrogen Damage [2,9]

It is convenient to distinguish SCC from hydrogen cracking in which the cause
of fracture is directly related to hydrogen. Some features of hydrogen cracking
are similar to SCC but cause differ. Cathodic polarisation for example
accelerates hydrogen cracking but inhibits SCC, Corrosion, application of
cathodic protection, electroplating and other processes are major sources of
hydrogen in metals. The molecular form of hydrogen (Hv2) does not diffuse
through metals. Atomic hydrogen (H) is the only species capable of diffusing
through steel
and
other
metals. Hydrogen
blistering and hydrogen

15
embrittlement may occur
welding operations.

during exposure to petroleum, during pickling and

Hydrogen embrittlement
Normally metals which absorb large quantities of hydrogen give rise to hydride
formation where as metals which physically absorb small amounts of hydrogen
suffer embrittlement. Sources of hydrogen are must commonly for reactor of
the metal with water during melting, casting, hot working, welding acid treatment
and electrodeposition. Metals most frequently affected are steel, titanium,
copper and silver but vanadium, zirconizim, tantalum, cerium, cobalt and nickel
may also get affected.
Hydrogen blistering
If hydrogen atoms diffuse into a void, (a common defect in rimmed steels) they
combine into molecular hydrogen. Since molecular hydrogen cannot diffuse,
the concentration and pressure of hydrogen gas within the void increases.
The result is local deformation and, in extreme cases, complete destruction of
the vessel well. Blistering may bee prevented by
1.
2.
3.
4.
5.

using clean steel

using impervious coatings
using inhibitors
removing hydrogen - evolution poisons such as sulfides, arsenic
compounds, cyanides, and phosphorous containing ions and
substituting alloys (nickel steels and nickel base alloys have very low
hydrogen diffusion rates)

Hydrogen embrittlement
This is also caused by penetration of hydrogen into a metal, which results in
a loss of ductility and tensile strength. For titanium
and other strong
hydrideforming metals
dissolved hydrogen reacts to form brittle hydride
compounds. The mechanism is based on slip interference by dissolved
hydrogen.
Embrittlement may be prevented by
1.
2.
3.
4.
5.

reducing corrosion rate

altering plating conditions
baking
substituting alloys
practicing proper welding.

16
Use of clean steels has relatively no influence.
Corrosion Fatigue [2,12-14]
The tendency for a metal to break under conditions of repeated cyclic stressing
considerably below the ultimate tensile strength has been termed fatigue. If in
addition to cyclic stressing, the environment is such as to cause corrosive attack
on the metal, the deterioration will be even marked and this damaging effect
due to the simultaneous action of corrosion and cyclic stress is known as
corrosion fatigue. The damage from corrosion fatigue is greater than that from
corrosion. The pits produced in steel unstressed or under static stress are
saucer shaped. But under cyclic stressing, sharp, deep pits are formed and as
corrosion fatigue continues, many of the pits become the origin of cracks which
are filled with corrosion products. Failure occurs subsequently from the
progress of one of the cracks across the metal. Fatigue failures show a large
smooth area and a smaller area which has roughened and somewhat
crystalline appearance, whereas corrosion fatigue failures show a large area
covered with corrosion products and a smaller roughened area result from the
brittle fracture (Fig.5). But the corrosion fatigue is not defined in terms of the
appearance, only interms of mechanical properties. A corrosion fatigue failure is
usually transgranular and does not show the branching which is characteristics
of SCC.
Equipments and accessories which are frequently subjected to corrosion
fatigue are wires in sea water, aircraft parts, road and rail vehicle springs,
steering arms and stub axles of road vehicles, marine propeller shafts,
turbine parts and pies carrying corrosive liquor under pressure, steel railway
sleepers, etc.,
In the absence of corrosion, steels tested in atmospheric temperature under
cyclic stresses possess what is known as fatigue limit(maximum safe range
of stress which can be repeatedly applied to a material for an indefinite period
without causing failure). For practical purposes, materials other than steel do
not posses a fatigue limit. For such materials it is necessary to quote the
fatigue properties on the basis of the endurance limit (highest stress which the
material will withstand for a given number of cycles). In presence of
corrosive environment, the endurance limit of a material is considerable
reduced. Although metals have a definite fatigue limit, there is no corrosion
fatigue limit. Oxygen content, temperature, pH and solution composition
influence corrosion fatigue.
The process of failure by corrosion fatigue is composed of two stages :
1. Initiation - The combined action of corrosion and cyclic stress damages the
metal by pitting and crack formation to such a degree that fracture by cyclic

17
stresses would occur even in the absence of corrosive environment. (They
cyclic stress cause rupture of protective films at a greaer rate than repair can
occur and this allows localised corrosion to proceed. From the moment a pit is
formed, there is significant stress concentration at the base.
2.
Propagation - Failure proceeds by crack propagation controlled
primarily by stress concentration effects and physical properties.
Corrosion fatigue may be eliminated or reduced by reducing the stress on the
component (by design by stress relieving heat treatments of by shot penning
the surface to induce compressive stresses). Corrosion fatigue resistance can
be improved by coating such as electrodeposited zinc, chromium, nickel,
copper and nitride coatings. (When elecctrodeposited coatings are applied,
plating techniques should not produce tensile stresses in the coating or charge
hydrogen into the metal). Inhibitors are also effective in some cases. Increasing
the tensile strength of a metal or alloy is detrimental to corrosion fatigue
resistance (though it improves ordinary fatigue resistance).
Fretting Corrosion [2,12]
The rapid corrosion that occurs at the interface between contacting highly
loaded metal surfaces when subjected to slight relative (vibrating) motions is
termed fretting. Fretting is usually distinguished by surface discoloration and
deep pits in regions where slight relative movements has occurred. Thee
detritus is highly oxidized. Fretting attack arises through high loading and
subsequent deformation. The concentrated pressure at the contact points
causes the metals to elongate, deform, yield and tear. The intense work
generates heat locally and leads to oxidation and high pressure welding. The
corrosion product is a mixture of oxide and metal particles which vary in size
(0.01 um to 0.05 um) The damage varies from large shallow depressions with
roughered surfaces to smaller and deeper pits. Since fretting corrosion affects
loaded surfaces, its effect is catastrophic. Ir ia problem of considerable
importance because,
1.

it increases the susceptibility of fatigue failures of dynamically loaded

machine parts.

2.

it destroys the dimensional accuracy of closely fitted parts

3.

it ruins the bearing surfaces.

Fretting cases are found in many aircraft engine parts (bolted assemblies).
Fretting corrosion cause malfunctioning of bearing support, splined shaft, etc.,
Electrical switching gear, riveted structures, press and taper fits also are

18
affected. In railways, fretting
service problem.

of clamping bolts at each rail joint creates a

The relative motion necessary to produce fretting is extremely small (as little
as 10-8cm). Repeated relative motion is a necessary requirement.
It does not occur in surfaces in continuous motion. The two major mechanisms
proposed for fretting corrosion (Fig.6) are
1.

the wear oxidation theory based on the concept that cold welding or
fusion occurs at the interface between metal surfaces under pressure
and during subsequent relative motion, these contact points are
ruptured and small fragments of metal are removed and immediately
oxidised due to frictional heat.

2.

the oxidation wear theory based on the hypothesis that wen metal are
placed in contact under load and subjected to repeated relative motion,
the oxide layer is ruptured at high points and results in oxide debris. It is
assumed that the exposed metal reoxidises and the process is repeated.

Fretting corrosion can be minimised or eliminated by one or

following methods.

more of the

1.

lubricate with low viscosity, high tenacity oils and greases

2.

Increase the hardness of one or both of the contacting materials

(choose a hard material or increase surface hardness by shot peening or
cool working).

3.

Use gaskets to absorb vibration and to exclude oxygen

Increasing the friction between mating parts by roughening the surface may be
helpful in certain cases.
Cavitation Erosion and Impingement [12,15]
Cavition is primarily the wearing away of metal due to repeated impacted blows
by the formation and collapse of voids within a fluid. The voids form when the
static pressure decrease to a value below the vapour pressure of liquid
because of separation and eddie formation in the flow system. The voids are
usually considered to be at very low pressures sometimes approaching
vaccum. When the voids collapse with high frequncy and violence, a hammer
like affect is produced by the metal surface and consequently
1.

the metal is severely deformed

19

2.

in some areas the metal is torn away from the matrix

3.

any corrosion resistant film previously formed is rapidly removed. If the

environment is corrosive, cavitation increases corrosion rate. Discharge
side of turbines, suction side of impeller of flow pumps, discharge side of
regulating valves, high speed marine propellers are mostly affected . The
appearance of caitation damage is somewhat similar to pitting, except
that pitted areas are closely spaced and the surface is usually
considerably roughened.

Prevention
For reducing cavitation effect, a metal should have a high corrosion
resistance to the action of medium, must be had enough to resist the
mechanical attack and must be fine grained rather than coarse grained (design
aspect is dealt with elsewhere). Chipping of eroded surface and application of
resilient material coating (e.g neoprenes, thickol) can slow down the cavitation
damage. Affected areas can also be welded or coated with a dense high tensile
material (chromium - stainless steels).
Erosion corrosion is the aceleration or increase in rate of attack on a metal
because of the relative movement between a corrosive fluid and the metal
surface. Metal is removed and surfaces dissolved ions or it forms soiled
corrosion products which are mechanically swept from the metal surface.
Erosion corrosion is characterised in appearance by groves, gullies, waves,
rounded holes and valleys and usually exhibits a directional pattern (Fig.7).
Many types of corrosive mediums could cause erosion corrosion (gases,
aqueous solutions, organic systems liquid metals, etc). The nature and
properties of the protective films that form on some metals or alloys are very
important from teh standpoint of resistance to erosion corrosion. Stainless steels
depend on passivity for resistance to corrosion. Consequently these materials
are vulnerable to erosion corrosion. Erosion corrosion can occur on metals
and alloys that are competely resistant ot a particular environment at low
velorate. Many erosion-corrosion failures occur because turbulence or
turbulent flow conditions exist. Turbulence results in more intimate contact
between the environment and the metal. The galvanic effect may be nil under
static conditions but may be greatly increased when movement is present.
The erosion failures of steam - turbine
bends, tees,external components of
attributed to impingement attack.

blocks, entertainment separators,

aircraft, cyclones, etc. are directly

20

REFERENCES
1.

Laque F.L., and Copson H.R., Corrosion resistance of metals and alloys,
Second edition, Reinhold publishing Corpn., Newyork , 1963.

2.

Fontana, Mars G., and Greena Norbert D.,

McGraw Hill Book Co., New York, 1967.

3.

Godard H.P., Jepson W.P.,Bothwell M.R. and Kane R.L., The corrosion
of light metals John, Wiley & Sons Inc., New York, 1967.

4.

Levin I.A., Intercrystalline corrosion and corrosion

stress : leonard Hill (books) ltd., London 1963

5.

Anticorrosion , 19-10 (1972) 8

6.

Avan Loo M., Liderman D.D., Bruhin R.R., Corrosion, 1953, 9 (8), 277

7.

Slabaugh W.H., Morris Grother, Industrial

1954, 46 (5) 1014.

8.

Symposium on Stress Corrosion Cracking - ASTM Publication (1945)

9.

Uhlig H.H.Proceedings of Conference - Fundamental Aspects of Stress

Corrosion Cracking - Published by NACE , 1969 , 86.

10.

P.D.Doinovan, protection of metals form corrosion in storage and transist

Ellis Horwood Ltd., New York (1988).

Corrosion Engineering

of metals under

Engineering Chemistry,