Crevice Corrosion

Forms of corrosion

™ General corrosion (uniform corrosion over the whole anode)

™ Localized Corrosion (corrosion at isolated areas in the anode)
 Galvanic corrosion
 pitting corrosion
 Crevice corrosion
™ Metallurgically Influenced Corrosion (corrosion is related to microstructure)
 intergranular corrosion of stainless steel
™ Mechanically Assisted Corrosion (corrosion is accelerated due to mechanical
factors)
 Erosion corrosion
 Corrosion Fatigue
™ Environmentally Assisted Cracking (corrosion results in cracking)
 Stress corrosion cracking
 Hydrogen damage

2
 Forms of Corrosion

Factors affecting forms of corrosion :

Microstructure ↔ Environment ↔ Stress ↔ Geometry ↔ Time

3
CREVICE CORROSION
Narrow openings, gaps, spaces, pores etc. between metal‐metal components or metal‐
non‐metal components may provoke intense localized corrosion.

NOTE: unintentional crevices (seams, cracks etc.) can also act in the same way

Passive alloys (especially stainless steels) are more vulnerable than more active alloys.

Crevice corrosion at a metal‐to‐metal

crevice site formed between components
of type 304 stainless steel fastener in
seawater

4
5
Â Crevice corrosion is caused by the existence of small volumes of stagnant
(corrosive) solution. Small holes, gasket surfaces, lap joints, bolt or rivet heads,
nuts, washers, surface deposits all can cause C.C. (Crevice Corrosion).

 Type 304 SS sheet can be cut by stretching a rubber band around it, immersing it
in seawater. The crevice between the rubber and the metal acts as the cutting
zone.

6
Mechanism of Crevice Corrosion
Consider a riveted plated section of metal M immersed in aerated sea water.

7
Mechanism

1. Initially, the following anodic and cathodic reactions occurs uniformly on the
entire metal surface, inside and outside the crevice ;
 Anodic reaction : M → Mz+ + ze‐
 Cathodic reaction : O2 + 2H2O + 4e‐ → 4OH‐
2. After induction period, O2 in crevice is used up due to restricted convection ;
 Crevice → low O2 region → low Ea → small anode.
 External surface → high O2 region → high Ec → large cathode

8
Mechanism

3. Electromigration of Cl‐ due to ∆E = Ea – Ec

Anodic reaction in crevice : M → Mz+ + e‐
 Excess positive charge (Mz+) is building up, which is balanced by the
electromigration of Cl‐ and other anions from outside.
 Anion migration : Anions such as Cl‐, OH‐, CO32‐, and SO42‐ diffuse into the
crevice with a velocity depending on its diffusion rate. Among the anions, Cl‐
ion is the most fast.
 Cation migration : the metal ions accumulated in the crevice are transported
slow out of the crevice by diffusion and electromigration.

9
Mechanism

4. Acidification by hydrolysis reaction of metal ion ;

 The abundance of metal ions inside the crevice gives rise to their
hydrolysis with water molecules;
 Mz+ + H2O →M(OH)z↓ + z H+......... This reduces pH in the crevice. The
low pH or acidity prevents passivation and facilitates anodic
dissolution.

Hydrolysis reactions and

equilibrium pHs for metal ions in
an occluded cell in stainless
steels.
10
Mechanism
 In the case of pure metals, the pH values were found to be lower than those
calculated from the metal ion conc., and the experimentally determined pHs were
as follows ;
Fe :4.71, Cr :0.09, Ni :2.93, Mo :0.02, which indicates that Cr and Mo in an alloy
would have the greatest effect in lowering the pH within the crevice or pit.

5. Depassivation
 Passivation does not occur in the crevice when the critical pH and [Cl‐] in
electrolyte of crevice have been achieved.

6. Cathodic protection of external surface

 Cathodic reaction at external surface : O2+ 4H2O +4e‐→4OH‐..........High pH
facilitates passivation of external surface and the external surface is
cathodically protected by the electrons liberated by the anodic reaction.

Low pH, high [Cl-], depassivation lead to an

accelerating or autocatalytic corrosion in the crevice.

11
Prevention of crevice corrosion

1. Use welded butt joints instead of riveted or bolted joints in new equipment.
Sound welds and complete penetration are necessary to avoid porosity and
crevices on the inside (if welded only from one side).
2. Close crevices in existing lap joints by continuous welding, caulking, or soldering.
3. Design vessels for complete drainage; avoid sharp corners and stagnant areas.
Complete draining facilitates washing and cleaning and tends to prevent solids
from settling on the bottom of the vessel.
4. Inspect equipment and remove deposits frequently.
5. Remove solids in suspension early in the process, if possible.
6. Remove wet packing materials during long shutdowns.
7. Provide uniform environments, if possible, as in the case of backfilling a pipeline
trench.
8. Use "solid," nonabsorbent gaskets, such as Teflon, wherever possible.
9. Weld instead of rolling in tubes in tube sheets.

12
FlLIFORM CORROSION
~ Although not immediately apparent, filiform corrosion (filamentary corrosion
occurring on metal surfaces) is a special type of crevice corrosion.
~ In most instances it occurs under protective films, and for this reason it is often
referred to as underfilm corrosion.
~ This type of corrosion is quite common; the most frequent example is the attack
of enameled or lacquered surfaces of food and beverage cans that have been
exposed to the atmosphere. The red‐brown corrosion filaments are readily
visible.
~ Filiform corrosion usually on metals covered with thin organic film (∼0.1 mm)
BUT also reported for:
 steel; magnesium; aluminum; tin; silver; gold; phosphate; enamel
 as well as with organics (lacquer, paper; seen on paper‐backed Al foil,
between metal and paper).
~ Attack usually occurs when relative humidity between 65 and 90%; has been
seen at lower R.H. (Relative Humidity).
~ Average filament width ∼ 0.05 ‐ 3 mm .. depending on coating (thickness,
porosity, etc.), R.H., and corrosiveness of environment (presence of SO2, H2S,
etc.).
~ Filament height ∼ 20 µm. Growth rates observed between 0.01 mm/d and 0.85
mm/d.
~ Filaments are like minute tunnels, full of corrosion products.
13
A lacquered steel can lid exhibiting filiform corrosion showing both large and small
filaments partially oriented in the rolling direction of the steel sheet. Without this 10 x
magnification by a light microscope, the filiforms look like fine striations or minute
tentacles; (often mistaken for biologically – induced corrosion).
14
Mechanism

Head supplied with H2O by osmosis (high concentration of Fe2+ inside) through
coating and from precipitated hydroxide/oxide. Oxygen reduction creates
hydroxide; precipitation creates corrosion product tail. . . . further oxidation to
Fe3+ oxide etc. Hydrolysis of salts in head creates acidic conditions.

Details of mechanism
not understood………….
e.g., why do filaments
“reflect” off other filaments? etc.

15
† Liquid in “head” is typically acidic. . . . pH 1‐ 4.

† IN ALL CASES.... O2 (or air) and water are needed to sustain filiform
corrosion … indicates a form of a DIFFERENTIAL AERATION CELL.

Discuss:

differential aeration cell

concentration cell.

16
An aside on differential aeration . . (differential) concentration cell
remember example: remember Cu ‐ alloy crevice:

(potential ∝ log [Cu+])

Attack usually begins at imperfections in coating e.g., cuts, knicks, pores, etc.
CO2 can stimulate process by dissolving in water → carbonic acid.
Chlorides, SO42-, S2- which can dissolve in condensing atmospheric moisture also increase
attack.
Optimum temperature for filiform attack between 20 & 35°C.

17
Effect of humidity on filiform corrosion of enameled steel
Relative humidity, % Appearance
0-65 No corrosion
65-80 Very thin filaments
80-90 Wide corrosion filaments
93 Very wide filaments
95 Mostly blisters, scattered filiform
100 Blisters
Source: M. Van Loo, D. D. Laiderman, and R. R. Bruhn, Corrosion, 9:2 (1953).

Appearance:
Schematic diagram of a corrosion
filament growing on an
iron surface (magnified).

18
Schematic diagrams illustrating the
interaction between corrosion filaments:

(a) Reflection of a corrosion filament;

(b) splitting of a corrosion filament;
(c) joining of corrosion filaments;
(d) “death trap”.

19
Filiform Corrosion on PVC‐Coated Al Foil

Advancing head and cracked tail of a Gelatinous corrosion products oozing out
filiform cell. of porous tail section.
Scale: 0.125 mm Scale: 1.25 µm

20
Close‐up of the advancing head shown in adjacent
figure. Minute cracks can be seen at the head/tail
interface of a filiform corrosion cell. These cracks
are entry points for water and air to provide a
source of hydroxyl ions and an electrolyte.
Intermediate corrosion products are just
beginning to form in the head, and they undergo
further reaction to form an expanded tail. The tail
region is a progressive reaction zone that
ultimately forms spent corrosion products.
Between the head and porous end, ions gradually
react with water and oxygen and are slowly
transported in the direction of the tail to form
final corrosion products.

Scale: 15 µm

21
Intergranular Corrosion
Forms of corrosion

General corrosion (uniform corrosion over the whole anode)

Localized Corrosion (corrosion at isolated areas in the anode)
Galvanic corrosion
pitting corrosion
Crevice corrosion
Metallurgically Influenced Corrosion (corrosion is related to microstructure)
intergranular corrosion of stainless steel
Mechanically Assisted Corrosion (corrosion is accelerated due to mechanical
factors)
Erosion corrosion
Corrosion Fatigue
Environmentally Assisted Cracking (corrosion results in cracking)
Stress corrosion cracking
Hydrogen damage

2
 Forms of Corrosion

Factors affecting forms of corrosion :

Microstructure Environment Stress Geometry Time

3
Intergranular Corrosion
INTERGRANULAR CORROSION (Intergranular Attack.. IGA) is localized attack at and
adjacent to grain boundaries, with relatively little corrosion of the grains. The alloy,
sensitive to IGC, disintegrates and/or loses its strength when exposed to
environments.
Metals are usually “polycrystalline” . . . an
assemblage of single crystal grains
separated by grain boundaries.

Grain boundary in a polycrystalline metal (schematic representation & actual).

4
Intergranular Corrosion
The atoms in the grain boundaries are in a distorted lattice (i.e., disordered).

The higher energies of grain boundary atoms make them slightly more reactive than grains.

BUT: difference is NOT NOTICEABLE in general corrosion.

SOMETIMES . . . grain boundaries can become highly reactive by:

concentration of impurity atoms (e.g., Fe in Al has low solubility in metal,
segregates in grain boundaries which corrode more rapidly than grains, and
intergranular attack results);

enrichment of an alloying element (e.g., Zn in brass);

depletion of an alloying element (e.g., Cr in SS).

Causes of intergranular corrosion

5
Intergranular Corrosion
IGA (Intergranular Attack) in Austenitic SS (Stainless Steel)
What is austenite?

The lower-left corner

receives prime attention
in heat-treating of steels.
(In calculations, 0.77 %
is commonly rounded to
0.8 %.)

Fe-Fe3C Phase Diagram.

6
Intergranular Corrosion
Nomenclature

cast iron / CS . . . . > 2%C / < 4% C;

iron ( ferrite not to be confused with ferrite oxides).. is BCC
iron (ferrite) is also BCC;
iron carbide (cementite) is Fe3C, orthorhombic;
iron (austenite) is FCC.

austenite
is non magnetic;
is unstable below 727 C
decomposes on slow cooling to ferrite + pearlite if hypoeutectoid;
pearlite + eutectic if hyperentectoid
(N.B. pearlite is the lamellar mixture of ferrite and carbide that forms on
cooling austenite of eutectoid composition . . . 0.8% C).

7
Intergranular Corrosion

Pearlite.
This microstructure is a lamellar mixture
of ferrite (lighter matrix) and carbide
(darker).
Pearlite forms from austenite of
eutectoid composition. Therefore, the
amount and composition of pearlite are
the same as those of eutectoid austenite.

Pearlite Formation. Carbon must diffuse

from the eutectoid austenite ( 0.8
percent) to form carbide (6.7 percent).
The ferrite that is formed has negligible
carbon.

8
Intergranular Corrosion
AUSTENITE decomposes on rapid cooling below 727 C (i.e., quenching) to:
MARTENSITE a metastable forced solution of C in ferrite that is very hard, has BCT
(body centered tetragonal) structure.

N.B. IN STAINLESS STEELS, THE THREE MAJOR CARBON STEEL PHASES (FERRITE, AUSTENITE,
MARTENSITE) CAN ALSO BE FORMED.
Also: · “ferritic austenitic” (duplex)
· “precipitation hardened”.

Stability and mechanical/physical properties depend on combination of alloying

elements.
austenite stabilizers: C, N, Mn, Ni, (q.v. Ni alloys);
ferrite stabilizers: Si, Cr, Mo, Nb (“Columbium” Cb), Ti.

Selection of a steel/alloy for a particular application depends on mechanical or

physical property considered to be most important.

9
Intergranular Corrosion
COMMON STANDARD WROUGHT AUSTENITIC SS
AISI type UNS Cr Ni Mo C Si Mn Other

304 S30400 18 20 8 10.5 0.08 1.0 2.0

304L S30403 18 20 8 12 0.03 1.0 2.0
304N S30451 18 20 8 10.5 0.08 1.0 2.0 0.10 0.16N
316 S31600 16 18 10 14 2.0 3.0 0.08 1.0 2.0
316L S31603 16 18 10 14 2.0 3.0 0.03 1.0 2.0
316N S31651 16 18 10 14 2.0 3.0 0.08 1.0 2.0 0.10 0.16N
347 S34700 17 19 9 13 0.08 1.0 2.0 (10xC)(Cb+Ta)

COMMON STANDARD WROUGHT FERRITIC SS

AISI type UNS Cr C Mn Si P S Other

405 S40500 11.5 14.5 0.08 1.0 1.0 0.04 0.03 0.1 0.3Al

430 S43000 16 18 0.12 1.0 1.0 0.04 0.03

COMMON STANDARD WROUGHT MARTENSITIC SS

AISI type UNS Cr Ni Mo C Other
403 S40300 11.5 13.0 0.15
410 S41000 11.5 13.0 0.15
10
Intergranular Corrosion
Sensitization:
Cr is added to steels to make them “stainless”. The Cr rich oxide film (based on
Cr2O3) is thin, adherent and very protective. BUT if heated into range 425 815 C, the
steels “sensitize” and become prone to IGA.
Sensitization involves the precipitation of Cr carbide (Cr23C6) at the grain boundaries;
at the high temperature range its solubility is virtually zero.
Sensitization causes IG corrosion in austenitic stainless steel (such as 304 and 316
SS).
Stainless steels corrosion resistance depends on the availability of Cr dissolved in
iron (at least 12 wt. %).
Between 425 815°C, Cr near the GB react with Carbon and form carbides Cr23C6
Heating for stress relief
During welding
Cr concentration at GB drops below 12 wt.% and the metal is said to be sensitized
(sensitive to IG corrosion)
GB will be more anodic than the grain interiors (galvanic action)
Corrosion rates at the GB will be higher than in the grain interiors
11
Sensitization of S. Steel

Above 815oC: Cr-carbides are soluble (so they don’t precipitate) and below 425oC the
diffusion rate of Cr is very low. Sensitization is a pre-requisite for Intergranular corrosion.

12
Effects of Cr content on the anodic Effects of Cr content on corrosion
polarization behavior of Fe Cr alloy rate of Fe-Cr alloy

Effects of % C on senitization time of 304

13
Weld Decay and Knifeline Attack(KLA)

Sensitization of stainless steels is frequently

developed during improper gas welding.
Sensitization frequently occurs in the heat
affected zone during welding, and the
resultant corrosion is called weld decay
The thermal cycle at the heat affected zone in
thick sections can expose the HAZ of the weld
to the range of sensitization temperature
(425 815 C).
Thin sections (<3mm) need single welds
and will cool rapidly and sensitization
can be avoided
Heavy sections (>3mm) need multiple
passes and cool slowly and may be
subject to sensitization and weld decay.

14
Weld Decay and Knifeline Attack(KLA)
An intergranular attack in welded structures. The weld decay zone is within the heat
affected zone(HAZ) somewhat removed from the weld bead itself. At position B in figure
below, the alloy is in the critical temperature range for sufficient time to produce
sensitization. KLA is a highly localized form of IGC that occurs for only a few grain
diameters immediately adjacent to the weld bead in Type 321 and 347 austenitic stainless
steels.

15
Weld Decay and Knifeline Attack(KLA)

16
Control of Intergranular Corrosion

Metallurgical measures :
Solution annealing : heating the alloy to 1050 C where all Cr carbides are
dissolved, followed by rapid cooling.
Low carbon alloy modifications : lower the carbon content to below 0.03%
for austenitic stainless steels(304L, 316L) or to below 50ppm for ferritic
stainless steels.
Stabilization treatment : add strong carbide former (Ti, Nb) in melt:
321 stabilized SS (Ti is added 0.4 0.8%)
347 stabilized SS (Niobium is added)
Environmental measures : lower acidity and less oxidizing conditions will
generally reduce the susceptibility to IGC.

18
Pitting Corrosion
Forms of corrosion

™ General corrosion (uniform corrosion over the whole anode)

™ Localized Corrosion (corrosion at isolated areas in the anode)
 Galvanic corrosion
 pitting corrosion
 Crevice corrosion
™ Metallurgically Influenced Corrosion (corrosion is related to microstructure)
 intergranular corrosion of stainless steel
™ Mechanically Assisted Corrosion (corrosion is accelerated due to mechanical
factors)
 Erosion corrosion
 Corrosion Fatigue
™ Environmentally Assisted Cracking (corrosion results in cracking)
 Stress corrosion cracking
 Hydrogen damage

2
 Forms of Corrosion

Factors affecting forms of corrosion :

Microstructure ↔ Environment ↔ Stress ↔ Geometry ↔ Time

3
PITTING: Extreme localized attack, may perforate metal sheet/plate . . . etc due to
selective attack on area of a metal surface where there is a: (i) surface scratch, (ii)
emerging dislocation, and (iii) compositional heterogeneity.

p
“Pitting factor” = d

d = average penetration from weight loss;

p = deepest penetration

“Undercutting”
pit opening usually < 1 mm.

Pits may overlap to give the appearance

of rough, general wastage.

4
Pits usually occur on upward‐facing horizontal surfaces,
pit growth

and less frequently on vertical surfaces;

pit growth Gravity is involved.

rarely on downward‐facing surfaces;

pit growth
5
Shape of pit

6
Pitting is an insidious and destructive form of corrosion:

 Difficult to detect (pits may be small on surface, but extensive below surface from
undercutting; may be covered with deposit);
 Can cause equipment to fail (by perforation) with very little weight loss;
 Difficult to measure as pit depth and distribution vary widely under (nominally)
identical conditions;
 “Incubation” period may be months or years.

 Metals and alloys can be active (no

Materials Affected

protective passive film) or passive (passive

film 10‐30 nm in thickness)
 Cause due to rapid corrosion penetration at
small discrete areas where passive film
breaks down and appears as small diameter
holes (0.1‐5 mm). The remaining surface is
not attacked.
 Pitting corrosion is common in passive metals
above pitting potential (Ep)
7
Example

 Pitting of stainless steel, Ni alloys, Al

alloys in aerated seawater or acids
containing Cl‐ ions

 Steel buried in the soil corrodes with the

formation of pits.

 Pitting of steels and aluminum in alkaline

solutions containing Cl‐

 Pitting can occur in any alloy that form a

protective film and exposed to stagnant
solution containing Cl‐

 Example: 316 SS centrifuge head

exposed to CaCl2 solution showing deep
pits

8
Â Top: pits in stainless steel valve plate
(stagnant solution).
Ä Bottom: internal pits in steel pipeline carrying
water with dissolved CO2

 Pitting in carbon steel pipe carrying

strong acid.
Ä Deep pits on a carbon steel in HCl.

9
Pitting of 18-8 stainless steel by acid-chloride solution.

Pitting of stainless steel condenser tube.

10
Conditions favors pitting

™ Stagnant solutions
 Pitting occurs during shutdown period more than during normal operation
 During shutdowns, solutions in pipes, pumps, and tubes are stagnant and
allow pits formation.
™ Acidic solutions
™ Presence of Cl‫־‬and Br ‫(־‬halides)
™ High temperature
™ Rough surface finish
™ Commonly occur in passive metals (such as stainless steels)
™ Presence of surface deposits (deposits form localized concentrated environments
around them)
™ Rupture of protective coatings

™ Pits form in gravity direction

11
Stages in Pitting Corrosion

™ Two stages in pitting: initiation and propagation

~ Pits initiation at film break downs due to
 Mechanical scratch
 Localized High Cl‐ concentration
 Localized failure of coatings or paints
 At metal microstructural inhomogenity (e.g., inclusions in SS)
~ Pits initiation at surface deposits or scratches of paints
™ Most initiated pits become unstable and do not grow if the passive film reforms
or the highly concentrated environments are washed off
™ If passive film reformation is not possible (high concentration of Cl‐), then a pit
will grow at faster rate due to autocatalytic effect.

12
 In the propagation stage of pits in aerated salt water (seawater):

 Oxygen is depleted inside the pit and

oxygen reduction takes place around the pit
 Anodic dissolution of the metal produces
M+ ions inside the pit
 Cl‫ ־‬ions diffuse toward the pit to neutralize
cations charge.
 Cl‫ ־‬and M+ inside the pit combine and
produce more H+ by hydrolysis
(M+ + Cl‫ )־‬+ H2O → MOH + H+ + Cl‫־‬
 The electrolyte becomes more acidic inside
the pit and more corrosive because higher
H+ and Cl‫־‬
 Reach autocatalytic stage where pit growth
follows d = ktn
 k is a constant and n ranges from 0.3 to 0.8

13
Pitting

14
 Sequence of events in SS pitting (Epit)
The actual pitting mechanism is still not well understood. however, the following
sequence has been proposed for stainless steels:

This model can be used to

simplify the pitting behavior in
SS.

1- Fe2+ is produced by dissolution of iron Fe Æ Fe2+ + e, will attract negative anions,

i.e. Cl- to the initiation sites where hydrolysis takes place:
Fe2+ + 2H2O + 2Cl- Æ Fe(OH)2 (weak base) + 2 HCl (strong acid)

This will reduce pH at the site. This result in the so called auto-catalytic
mechanism of pit growth.

15
 Sequence of events in pitting (Epit)

2- the acid chloride solution further accelerate anodic dissolution which in turn further
concentrates chlorides in the pit growth.

3- The Fe(OH)3 cap at the pit mouth (as corrosion product) is produced as Fe2+
diffuses out where it is oxidized to Fe3+ and precipitates as Fe(OH)3

4- This cap impede easy escape of Fe2+ but sufficiently porous to permit migration of
Cl- into the pit
The pit interact like anode while surrounding areas at the pit [where O2 and H2O are available]
acts like cathode thus ensuring anodic polarization of the interior of the pit.

5- since oxygen has limited solubility in the solution, then for every pit there should be
a large surrounding area to act like a cathode to support the formation of a central pit
anode: that’s why pits are dispersed away from each other

If an oxidizer (with large solubility in the solution) such as Fe3+ exists Æ then greater rates of
reduction can be achieved and more pits may form within a smaller area.

16
 O2 OH- O2 OH-
M n+

1‐Inside the growing pit the hydrolysis (adding water) of Mn+ lowers the pH and breaks
down the passive film. The cathodic oxygen reduction reaction continues outside the pit.
2‐The presence of chloride is important, as it allows a pH of about 1 to be achieved (HCl
is a strong acid, and does not associate) and the metal chlorides are very soluble.
3‐Other anions (e.g. OH‐ and SO42‐) can inhibit pitting, either by buffering the pH in the
pit or by causing the precipitation of a salt film.

17
Mechanism of pitting corrosion
The more noble is Epit the more resistance is the alloy to pitting. For example in Fe‐Cr
alloys in sea water: as Cr content increases Epit becomes more noble and the alloy
becomes more resistance to pitting.

EPit

eCorr
EPit
NO Pitting
eCorr iCorr
iPit

18
Pitting
~ pits become more stable as they become larger
 for very small pits the acidity will be neutralised by diffusion into the bulk
solution very easily
 as the pits get larger the diffusion distances increase, and it gets harder for
the acidity to diffuse away
~ pitting becomes more likely as the potential becomes more positive
 this provides a greater driving force for the corrosion process, and helps to
stabilize the metastable pits

19
Temperature effect
~ Pitting is strongly influenced by the service Temperature
~ In stainless steels
 there is a critical pitting temperature below which pitting will not initiate for
each stainless steel alloy
 304SS (critical pitting temperature = ‐2.5 C°)
 317SS (critical pitting temperature = ‐0 C°)
 Pitting resistance is improved by increasing Cr (>18%) and Mo (2‐4%).

20
Temperature effect
 Three alloys are tested for pitting resistance by immersion for
24 hr in very aggressive solution.
 All alloys have high resistance to pitting at 25 ̊C
 Alloy G: Ni‐20Fe‐22Cr‐6Mo
& Shows pitting at 70 ̊C
 Alloy 625: Ni‐22Cr‐9Mo
& Shows pitting at 102 ̊C
 Alloy C‐276: Ni‐16Cr‐16Mo‐4W
& No pitting until 102 C

21
Quantification of pitting & control

P = Maximum penetration by microscopy

D = Avarage penetration by weight loss

P / D = pitting Factor

If p / D = 1 Uniform corrosion
22
Weight loss methods are not adequate to evaluate pitting because few long pits with
maximum penetration may show very little weight loss.

- Maximum pit depth is a preferred method for evaluating the degree

of pitting corrosion.

Deep pits

Shallow pits

Pits in Stainless Steel.

23
Measurement of pit depth complicated because of statistical variations.

Relationship between pit depth

and the number of pits
appearing on a corroded
surface.

Average pit depth of little use, since it is the deepest pit that causes failure.

24
MAXIMUM PIT DEPTH can be a useful way of expressing pitting corrosion, and for
comparing pitting resistance of standard test samples.

HOWEVER, statistical nature of pitting means that sample size is important.

Pit depth as a function of

exposed area.

Should never predict lifetime of plant components from tests on small samples.

25
Methods for measuring pit depth
Metallographic:

Section and polish, microscopic examination = time consuming, uncertain

Machining:

Measure depths where no pits remain = destroys sample

Micrometer depth gauge:

Compare readings between surface and pit bottom = pit must have large opening

Microscopic:

Use fine focus to determine depth difference between pit bottom and surface =
Light must reach pit bottom

26
Pitting Evaluation and Control

~ Use of standard charts to

compare and estimate pitting
density (number of pits per cm2
of metal surface), pit size and
depth
~ Pitting evaluation is given
according to standard charts
(i.e., ASTM)
 Example:
Example A pit characterized as
A‐4, B‐3, C‐2 would have:
 Surface pit density = 1X105
pits/m2
 Surface pit opening = 8 mm2
 Pit depth = 0.8 mm

27
Metals Susceptible to Pitting

Most often, passivating metals, especially stainless steels, often in passivating

environments (e.g., containing oxygen) but with agents such as Cl‐ that attack the
passive oxide film.

SENSITIZED SS particularly vulnerable (its heat treatment has depleted the grain
boundaries of Cr by precipitating chromium carbide).

COLD WORKING increases pitting attack, perhaps dislocation pattern is important.

DISCUSS
ETCHED or GROUND surfaces more likely to pit than polished surfaces.
Stainless Steel more susceptible than Carbon Steel (though CS will have more rapid
GENERAL CORROSION).

28
Some alloys developed especially to resist pitting.

Effects of alloying on pitting resistance of stainless steel alloys

Element Effect on pitting resistance

Chromium Increases
Nickel Increases
Molybdenum Increases
Silicon Decreases; increases when present with molybdenum
Titanium and niobium Decreases resistance in FeCI3, other mediums no effect
Sulfur and selenium Decreases
Carbon Decreases, especially in sensitized condition
Nitrogen Increases

Source: N. D. Greene and M. G. Fontana, Corrosion 15:25t (1959).

29
Pitting Environments

Usually, solutions containing chloride or chlorine‐containing ions (e.g.,

hypochlorites [bleaches]) have strong pitting tendencies.

Bromides are also aggressive, but fluorides and iodides are not.

Cupric, ferric and mercuric ions promote pitting . . . easily reduced cathodically
and do not require dissolved O2; CuCl2 and FeCl3 are extremely aggressive
(latter used as a test solution).

Thiosulphate ion (S2O32-) may also promote pitting.

30
Microstructure Environment Stress Geometry Time
Stress
No SCC

SCC

Strain
 Materials Environment
Composition
Composition
Heat Treatment Corrosion Temperature
Microstructure
Electrode Potential
Surface Condition
Flow rate
SCC
Fatigu Corrosion-
e Fatigue
Stress, Strain
Service Stress
Fit-up Stress
Residual Stress
Strain Rate
SCC Mechanisms

Cathodic reaction on passive surface

sustain anodic reactions within
advancing cracks : 2H2O + 2e- 2OH-
Slip step 1/2O2 + H2O + 2e- 2OH-

H2 Exits O2 OH-

Oxide
H+ Corrosion
Cl- induced localized Productse-
breakdown of passive Cl-
film leads to corrosion pit

M+
Microcrack forms from e-
corrosion pit when
(H+) builds up (as below)

Concomitant cathodic reduction

Anodic reaction within crack leads to
of H+ leads to H entry into alloy :
high (H+) as :
H+ + e- H(Fe)and H2
2Cr + 3H2O Cr2O3 + 6H+ + 6e-

H
General Corrosion
 Forms of Corrosion

Factors affecting forms of corrosion :

Microstructure ↔ Environment ↔ Stress ↔ Geometry ↔ Time

2
UNIFORM ATTACK or GENERAL CORROSION

 This is the most common form of corrosion.

 A chemical reaction (or electrochemical reaction) occurs over entire
exposed surface (or large areas) more or less uniformly.
 Metal thins … fails.
 Not usually serious and is typically predictable from simple tests (e.g.,
coupon or specimen immersion)
 Can be designed “around” by specifying an adequate CORROSION
ALLOWANCE for the expected lifetime of the component.

™ Uniform attack minimized by:

~ specifying proper materials;
~ correctly applying coatings;
~ using corrosion inhibition;
~ protecting cathodically.

3
1800‐year‐old Roman nail shows how iron
and steel can withstand burial
underground.

Note: Environment is crucial!

4
Atmospheric Corrosion
 Usually “uniform”.
 Dry, damp or wet conditions have profound effect on corrosion.
 Dry atmospheres:
~ at ambient temperatures, most metals corrode very slowly;
~ atmospheric oxygen promotes a protective oxide film ... such films are
defect‐free (sort of!), non‐porous (more or less!) and self‐healing;
~ “passivity” of metals like SS, Ti, Cr depends on protective oxide films
(but such passivity extends to other environments, e.g., aqueous).

 EXAMPLE:
~ Ag & Cu tarnish in dry air with traces of H2S (undesirable ‐ aesthetically,
technically ‐ affects electrical contacts, etc.).
~ The S2‐ incorporation in the normally‐protective oxides creates lattice
defects which destroy protective nature of films … tarnishing.
~ Moisture not required for tarnishing, it can actually retard tarnishing of Cu
in presence of traces of H2S.

5
 Damp atmospheres:
~ corrosion increases with moisture content;
~ at critical moisture level (~ 70% RH), an invisible, thin film of moisture forms
on (metal) surface, provides “electrolyte” for current (critical RH depends on
surface condition: cleanliness, presence of oxide or scale, presence of salts
or other contaminants that may be hygroscopic).

 Wet atmospheres:
~ promote puddles, pockets, visible water layers (from dew, sea spray,
rain, etc.);
~ crevices, condensation traps, etc., create water pools, and lead to “wet
atmospheric corrosion” even when rest of surface dry;
~ Corroded weathering steel I‐beam. Note how corrosion has thinned the
bottom of the vertical web where corrosion products have fallen and
formed a moist corrosive deposit. soluble corrosion products increase
wet corrosion (dissolved ions increase conductivity, sustain higher
electrical currents);
~ insoluble corrosion products may retain moisture during alternate wet
and dry conditions, lead to continuous wet corrosion.

6
} Corroded weathering steel I‐
beam.
} Note how corrosion has thinned
the bottom of the vertical web
where corrosion products have
fallen and formed a moist
corrosive deposit.

7
 Corroded steel framework on the ceiling of a parking garage. The seams in this
corrugated structure act as condensation traps and lead to wet atmospheric
corrosion.

8
Corroded weathering steel gutter.

9
Rusting of iron and steel, formation of patina on copper, examples of
damp → wet corrosion.

Corroded regions of a painted highway bridge.

10
Corroded weathering steel highway bridge girder.
11
ATMOSPHERIC CONTAMINANTS
 Wet atmospheric corrosion is often governed by level of contaminants.
& e.g., marine salts vary drastically with distance from the sea: steel at 25 m
from the sea will corrode 12x faster than same steel 250 m away.
 Industrial atmospheres are generally more corrosive than rural, mainly because of
sulfur compounds produced by burning fuels.

~ SO2 selectively adsorbs on metals – under humid conditions metal oxide corrosion
products catalyze oxidation to SO3:
SO2 + 1/2 O2 → SO3 (with a catalyst)
H2O + SO3 → H2SO4
~ Small additions ( ~ 0.2%) of Cu, Ni or Cr increase resistance of steel to sulfur
pollution by enhancing the formation of a tighter, more protective rust film.

NOTE: longevity of ancient Fe probably due to SO2 ‐ free environments rather than
high degree of corrosion resistance.

12
 ~ Nitrogen compounds promote atmospheric corrosion ‐ from fuel burning
(NOx as well as SOx), as well as by thunderstorms.
N2 + x O2 → 2 NOx;
nitrogen‐based fertilizers (from NH3) increase nitrogen pollutants in
atmosphere.

~ H2S promotes atmospheric corrosion (e.g., Ag, Cu tarnishing)

} from industry (oil & gas, pulp and paper , etc.);
} from decomposition of organic S compounds;
} from sulfate‐reducing bacteria (SRB) in polluted rivers etc.
H2O
SRB + SO42‐ → H2S

~ Dust particles detrimental (stick to metal surfaces, absorb water, H2SO4 etc., may
contain Cl‐ … WHICH IS BAD … since it breaks down protective oxide films).
~ CO2 dissolution in water can give pH ~ 5.6 (in equilibrium with normal atmosphere
containing CO2) … BUT … CO2 is not significant in atmospheric corrosion, in fact
sometimes can inhibit it (if SO2 is present).

13
Atmospheric variables
~ Surface temperature very important ‐ as T rises, corrosion rate rises ‐ though
damp and wet corrosion stop when moisture driven off;
~ Metal surfaces that retain moisture generally corrode faster than rain‐washed
surfaces; rain flushes impurities off surfaces, removes particles, etc. that
promote differential aeration, etc.;
~ Winter exposure generally more severe (more combustion products in
atmosphere, temperature inversions, etc.), though summer gives higher surface
temperatures.
~ Relative humidity very important: for clean Fe, critical RH ≈ 60%
 above this, rust begins to form slowly from deposited water film.
At 75 ‐ 80% RH, corrosion rate increases rapidly (probably because
of capillary condensation within the rust layer).
 if corrosion product rust is microporous, moisture will condense at
different RHs depending on pore size:
& 1.5 nm ‐ diameter pore (capillary) condenses water at 50% RH;
& 36 nm ‐ diameter pore at 98% RH.

} Note: dust, particles, etc. on surfaces create crevices that can condense moisture at various RHs.
} Salt or soluble corrosion products will form electrolytes in condensed moisture ‐ lower critical RH,
also increase corrosion.
14
Galvanic Corrosion
Galvanic corrosion
A Galvanic cell is formed when two dissimilar metals are connected electrically while
both are immersed in a solution electrolyte. The more active metals or alloys of the two
is corroded preferentially by galvanic corrosion.

Galvanic and concentration cell corrosion

A Galvanic Cell occurs when two dissimilar metals are connected electrically with both are immersed
in a solution electrolyte.
A Concentration cell occur when the same metal is in contact with solutions of different
concentrations.

Galvanic series:
Any metal has a unique corrosion potential ( eCorr ) when immersed in a specific solution.
When two metals are coupled ( in the electrolyte) then the one with more negative
potential ( more active eCorr ) has an excess activity of electrons which are lost ( given ) to
the more positive metal.
So, for two coupled metals : M and N
M → Mn+ + ne- the metal M is anode in a galvanic series (i.e. Giving electrons e- to the
more noble metal), so anodic dissolution rate increases.
The metal N ( more positive alloy) is a cathode as its anodic dissolution rate N → Nm+ +
me- will decrease due to excess electrons drown from M
2
 Galvanic Series

It shows ranges of measured potentials (

Less noble
eCorr). ( in sea water) Versus standard
Calomel Electrode SCE More noble

SCE

eCorr
Log i
More active

Less active

3
Important
The galvanic series should not be confused with the emf series. Which is a list of half cell
potentials , proportional to ∆G, of reversible half cell reactions at standard conditions.

4
Comparison between the emf series and the Galvanic series
~ Potentials in the emf series are listed versus SHE, while potentials in the Galvanic
series are measured with respect to a reference electrode ( like SCE).
~ In the Galvanic series, potentials are measured in real or simulated service conditions,
while in the emf series potential are ONLY determined at unit activities of reactants
and products
~ Changes in electrolyte composition and temperature can produce a significant change
in the position of potential in the Galvanic series. Every new change require a change
in the galvanic series (new galvanic series)
~ The galvanic series provide a qualitative indication of the likelihood but not
quantitative prediction

5
Fundamental aspect of Galvanic Corrosion
Corrosion of a galvanic couple between a corroding and an inert metal:
Zn ‐ Pt couple in deaerated acid
i ) shifts the corrosion potential of Zn from Ecorr to Ecouple.
ii ) increases the corrosion rate from icorr(Zn) to icorr(Zn‐Pt).
iii) decreases the rate of hydrogen evolution on Zn from iH2(Zn) to iH2(Zn‐Pt).

io,H2(Zn)=10-10 A/cm2
io,H2(Pt)=10-3 A/cm2

e-

Zn2+
Zn Pt
H2

6
 Effect of exchange current density by comparison of Zn‐Pt and Zn‐Au galvanic couples.

E°Au3+/Au = 1.498 V io,H2(Au) = 10‐6 A/cm2

E°Pt2+/Pt = 1.2 V io,H2(Pt) = 10‐3 A/cm2
icorr(Zn‐Pt) < icorr(Zn‐Au) < icorr(Zn)
Ecorr(Zn‐Pt) > Ecorr(Zn‐Au)

In emf series :Au has higher noble

potential than Pt, BUT in Galvanic series
the order is reversed (ept >eAu) because
the exchange current density io for H
reduction on Pt is higher than that on
gold

In the fig: ecouple for Zn‐Au is more active
than ecouple for Zn‐pt .
The reason why gold produces a less
severe galvanic effect is not related to
its reversible potential but rather to the
fact that it has a lower hydrogen
exchange current density than platinum.

7
Effect of area ratio of cathode to anode in galvanic couple

e- e-

Zn Pt Zn
Pt

Earlier we always assumed that the area of cathode is equal to the area of anode and
hence ia = ic
But if the area of the anode is ( say) smaller than the area of cathode:

I
Anode : ianode = Anode area ( small)
eCorr
(The same I )
ianode
I
Cathode: iCathode = iCath
Cathode area ( large)
Therefore : ia >> ic Log i 8
 (+)

Anode : ianode = I
Anode area ( small)
eCorr
(The same I) Pot.

Cathode: iCathode = I
(-)
Cathode area ( large)
Log i

Hence
 If the area of the anode is smaller than the area of the cathode then the rate of
corrosion ( of anode of course) is high.
 If the area of the anode is larger than the area of the cathode then the corrosion
attack will be spread over a large area and reduces the possibility of penetration.

9
Effect of surface area on Galvanic
Corrosion: io H2 (Zn) io H2 (pt,1cm2) io H2 (pt,10cm2)
eH+/H2 3

On
On
2H cm

2H c m
10
1
+ +22 pt s

+ +2 2 pt
+

2H Zn

e- ur

e- su
On
+ +2
Increasing surface area of 2

e rface

H2 e
H2 e
-

fac
cathode will increase io for

rfa
su

c
cathodic reactions, because
e

H2
it provide more surface for
reduction, thus increase 1
the number of electrons io Zn(1cm2)
Which Increase the iB iC
corrosion rate. - iA Zn/Pt couples
Total reduction rates

Log i
In the above example : Zn is coupled with Pt:
Point (1) : represent the corrosion rate of Zn (iA)

10
 io H2 (Zn) io H2 (pt,1cm2) io H2 (pt,10cm2)
eH+/H2 3

On
On
2H cm

2H c m
10
1
Point(2): represent Corrosion

+ +22 pt s

+ +2 2 pt
rate of Zn (iB) which is coupled +

2H Zn

e- ur

e- su
On
+ +2
with Pt: Both surface areas of 2
Zn and Pt are 1cm2. The

e rface

H2 e
H2 e
-

fac

rfa
su
reduction reaction occur on

c
surface of Pt ( 1 cm2) and e

H2
hence higher corrosion rate 1
and more noble ecorr io Zn(1cm2)
iC
iB
- iA
Point (3): Same as point (2) Zn Total reduction rates
coupled to 10cm2 Pt cathode
and hence highest corrosion Log i
rate and more noble ecorr

Larger Cathode Area provide more surface for the reduction reaction which increase the #
of electrons, which increase the rate of anodic dissolution which increase Corrosion rate.

11
Corrosion of a galvanic couple between two corroding metals
Zn - Fe couple in a deaerated acid solution

Coupling of Fe to Zn with equal area :

i ) Corrosion rate of Fe is reduced from icorr(Fe) to icorr(Zn‐Fe).
ii) Corrosion rate of Zn increases from icorr(Zn) to icorr(Fe‐Zn).
& This principles is applied to galvanizing where Fe is cathodically protected by coupling
with Zn

io,H+/H2 (Zn) io,H+/H2 (Fe)

ErH+/H2 Fe→Fe2+ +2e-

Zn→Zn2+ +2e-
icorr(Fe - Zn)
icorr(Fe)

e-
Er,Fe
icorr(Fe - Zn)
icouple
io,Fe2+/Fe
Er,Zn icorr(Zn) Zn Fe
io,Zn2+/Zn
Zn2+
10-10 10-8 10-6 10-4 10-2 10-0 log |i|

12
} General conclusions on the galvanic corrosion
1) If two corroding metals are galvanically coupled, the corrosion rate of more active
potential (ie. with more active corrosion potential) is accelerated, and that of the
other metal is retarded.
2) The polarity of electrode for galvanic couple should be defined on the basis of
corrosion potential.
3) The corrosion behavior of a galvanic couple is determined by the following
parameters Er, io, B and the relative areas of the two metals.
4) Galvanic corrosion behavior can not be predicted accurately on the basis of EMF
series. Use galvanic series to predict corrosion behavior of galvanic couple

13
Corrosion of galvanic couple containing active ‐ passive metal

Case 1 : Epp < EH+/H2

ex) Ti ‐ Pt, Cr ‐ Pt in acid solution

¨ Coupling of Ti to Pt leads to spontaneous

passivation of Ti without oxidizers.

14
Case 2 : Epp > EH+/H2
ex) Fe ‐ Pt couple in acid solution.

e-

Pt
e-
Fe Fe

15
Development of corrosion resistant alloy based on galvanic corrosion
1) Noble metal alloying
Alloying of Ti or Cr with a noble metal such as Pt, Pd, Rh and Ir with low hydrogen
overvoltage produces spontaneous passivation in hot concentrated oxidizer‐free acid.
Homogeneous solution of Pt in Ti

Preferential dissolution of Ti
¨Enrichment of Pt on surface of alloy
¨Spontaneous passivation

16
2) New Al alloy : Al‐1%Ni‐6%Fe
Intergranular attack of 1100 Al alloy in acid solution results from a hydrogen
uptake(hydrogen blistering). The low exchange current density for hydrogen
evolution on Al, io,H+/H2(Al), produces high cathodic polarization, resulting in an
increase in equilibrium hydrogen uptake(PH2). By adding Ni to Al, the hydrogen
uptake problem is removed.
ie. 2Al + 3Ni2+ → 2Al3+ + 3Ni

ηH2,Ni
ErH2+/H2
Al is preferentially dissolved.
ηH2,Al Ni is enriched on surface.

ErAl3+/Al

ioAl3+/Al
log |i| Al – 1%Ni – 6%Fe

17
Galvanic Protection by a Coating

Zn2+ Zn2+

• CASE I OH- O2
Zn Zn
: large anode & small cathode. e- e-
Steel

OH- O2 OH- O2

Sn e- e- Sn
• CASE II Fe2+
Steel
: small anode & large cathode.

18
Galvanic Corrosion : Area Effect

 The localized pinhole corrosion has Coating

developed through the coating.
 All coatings have defects in the form
of pinholes and mechanical damage. Carbon steel Localized corrosion occurred

 Anodic dissolution and galvanic Weldment

corrosion of the carbon steel were
concentrated at coating defects by a
large cathode (stainless steel)/anode 18-8 stainless steel

(steel) surface area ratio.

Painted steel storage tank

19
7.9 Corrosion in a Weld

• Unmixed Zone
Grain boundary segregations and 2nd phase
precipitations occur due to nonequilibrium filler metal
cooling. 308L SS (20Cr-11Ni)
347 SS (18Cr-11Ni-Nb)
• Heat Affected Zone (HAZ)
Formations of precipitations and phases which
cause bad effects to the mechanical properties
and corrosion resistance.

As a filler metal, Select more resistive one to

corrosion than base metal. (ie. With higher
Ecorr)

base metal
304L SS (18Cr-8Ni)

20
7.10 Prevention against galvanic corrosion

1) Select combinations of metals as close together as

possible in the galvanic series.
2) Avoid the unfavorable effect of a small anode and large cathode.
3) Insulate the components from each other.
4) Apply coatings with caution.
5) Add inhibitors into solution.
6) Install a third metal that is anodic to both metal in the galvanic series.

21
 College of Engineering
Department of Mechanical Engineering

Corrosion Engineering Semester: Fall 2019/20

MEEN 4341

2nd Midterm Exam Date: 24/Nov/2019

Time: 60 min

Name: ID:

Section: 101

siei curteGr lareneG

1. Answer all the questions.
2. The exam is closed book closed notes.
3. Read each question carefully.
4. Be neat and clear in your presentation and sketches, and show all work for full credit.
5. Cellular Phones are strictly prohibited in the examination hall.
6. CHEATING penalty will result in an F in the course.

Question Assessed Assessed Maximum Obtained

Number PLOs CLOs Marks Marks
Q1 MEEN1A 2.3 10
Q2 MEEN1A 2.3 3
Q3 (a) MEEN1A 2.3 1
Q3 (b) MEEN1A 2.3 2
Q4 MEEN1B - 2
Q5 (a) MEEN1A - 1
Q5 (b) MEEN1A 2.4 1
Question 1: Choose the correct answer for each of the following questions. [10 Points]

1. Rusting of iron and steel, formation of patina on copper are the examples of
(a) Dry Corrosion (b) Damp Corrosion (c) Wet Corrosion (d) Both (b) and (c)
2. Uniform corrosion can be minimized by
(a) Specifying proper materials (b) Coatings
(c) Cathodic Protection (d) All of the above
3. The rate of galvanic corrosion is high if
(a) Aanode > Acathode (b) Aanode < Acathode
(c) Aanode = Acathode (d) Does not depend on area
4. Which of the following is a localized form of corrosion?
(a) Crevice (b) Erosion Corrosion (c) Hydrogen Damage (d) Intergranular
5. Pitting corrosion is a selective attach of the area of a metal where there is a
(a) Surface Scratch (b) Emerging Dislocation
(c) Compositional Heterogeneity (d) All of the above
6. Corrosion pits become more likely as the potential becomes
(a) More Negative (b) More Positive
(c) both (a) and (b) (d) Independent of potential
7. Filiform corrosion normally occurs at a relative humidity range of
(a) 30% - 40% (b) 45% - 60% (c) 65% - 90% (d) 90% - 100%
8. Which one of the following is not a cause of intergranular corrosion?
(a) Sensitization (b) Higher energy in grain boundaries
(c) Heat affected zone in welding (d) low acidity and less oxidizing conditions
9. Which of the following corrosion types are related to flow of electrolyte
(a) Erosion-corrosion (b) Cavitation (c) Fretting (d) All of the above
10. Which one of the following is not a component of stress corrosion cracking?
(a) Tensile stress (b) Specific environment
(c) Compressive stress (d) A susceptible alloy/microstructure
11. Hydrogen sulfide H2S promotes atmospheric corrosion.
(a) True (b) False
12. In the Galvanic series, the potentials are measured in real or simulated service conditions.
(a) True (b) False
13. The Galvanic series provides a quantitative prediction of corrosion.
(a) True (b) False

1
14. Galvanic corrosion can be controlled by installing a third metal that is anodic to both metals in the galvan-
ic series.
(a) True (b) False
15. For pitting corrosion, incubation period could be months or years.
(a) True (b) False
16. Corrosion pits become more stable as they become larger.
(a) True (b) False
17. Active alloys are more vulnerable to crevice corrosion than passive alloys.
(a) True (b) False
18. Stainless steels corrode if Cr in dissolved iron is dropped below 12%.
(a) True (b) False
19. Hard, dense, adherent, continuous films give good corrosion resistance provided that they are not brittle
and easily removed under stress.
(a) True (b) False
20. Compressive stress promotes stress corrosion cracking in metals.
(a) True (b) False

Please write the answers of Q1 to Q20 in the table below.

1. 6. 11. 16.

2. 7. 12. 17.

3. 8. 13. 18.

4. 9. 14. 19.

5. 10. 15. 20.

2
Question 2: Identify the type of corrosion in each of the figures below. [3 Points]

3
Question 3 (a) What are the conditions which favors crevice? [1 Point]

(b) In what ways are crevice corrosion and pitting similar? In what ways are they differ-
ent? [2 Points]

4
Question 4 In Case A below, two steel plates are joined with a Monel bolt. In Case B, the reverse is
done. Both systems are to be immersed in seawater, for which

E (steel) = –0.61 V

E (Monel) = –0.08 V.

Thus, there is a galvanic effect in which the steel member of the couple will be attacked. In Case A, the
steel plates will be galvanically attacked. In Case B, the steel bolt which keeps them together will be
galvanically attacked. One case is much worse than the other. Which case is it? Why? [2 Points]

5
Question 5: (a) Explain sensitization with reference to the figure shown below. [1 Point]

(b) List any two methods of controlling crevice corrosion. [1 Point]

6
Formula Sheet
Galvanic Series

7
 College of Engineering
Department of Mechanical Engineering

Corrosion Engineering Semester: Spring 2021

MEEN 4341

2nd Midterm Exam Date: 5/April/2021

Time: 75 min

Name: ID:

Section: 103

General Instructions
1. Answer all the questions.
2. The exam is closed book closed notes.
3. Read each question carefully.
4. Be neat and clear in your presentation and sketches, and show all work for full credit.
5. Cellular Phones are strictly prohibited in the examination hall.
6. CHEATING penalty will result in an F in the course.

Question Assessed Assessed Maximum Obtained

Number PLOs CLOs Marks Marks
Q1 MEEN1A 2.3 3
Q2 (a) MEEN1A 2.1 1
Q2 (b) MEEN1B 2.3 1.5
Q2 (c) MEEN1C 2.3 1
Q2 (d) MEEN1C 2.3 1.5
Q3 MEEN1B 2.3 2
Q4 (a) MEEN1A 2.3 2
Q4 (b) MEEN1B 2.1 2
Q5 (a) MEEN1A 2.1 2
Q5 (b) MEEN1A 2.1 2
Q5 (c) MEEN1A 2.3 2
Question 1: Identify the type of corrosion in each of the figures below. [3 Points]

1
Question 2 (a) Identify and briefly describe mechanism of the type of corrosion shown in the figure.
[1 Points]

(b) Formulate an expression for pitting ratio using the figure. What does p and d represent?
What will be the value of pitting factor if a surface is experiencing uniform corrosion?
[1.5 Points]

(c) If the average penetration by weight loss is 2.2 mm and the pitting factor is estimated
to be 3.8, what will be the maximum penetration experienced by the plate due to pitting?
[1 Points]

2
(d) A pit is characterized as A-4, B-2, C-3. Using the chart below, Evaluate

(i) Surface Pit Density

(ii) Surface Pit Opening
(iii) Pit Depth [1.5 Points]

3
Question 3 In Case A below, two steel plates are joined with a Monel bolt. In Case B, the reverse is done.
Both systems are to be immersed in seawater, for which

E (steel) = –0.61 V

E (Monel) = –0.08 V.

Thus, there is a galvanic effect in which the steel member of the couple will be attacked. In Case A, the
steel plates will be galvanically attacked. In Case B, the steel bolt which keeps them together will be
galvanically attacked. One case is much worse than the other. Which case is it? Why? [2 Points]

4
Question 4: (a) Explain sensitization with reference to the figure shown below. [2 Point]

(b) Type 304 steel is unstabilized because of absence of Niobium (NB) or Titanium (Ti).
If this steel is heated to 1230 °C and rapidly cooled to room temperature, will there be
any intergranular corrosion due to sensitization? Yes, or NO? Why? [2 Point]

5
Question 5: (a) Pure copper is immune to stress corrosion cracking than Brass. Why? [2 Point]

(b) Why would pitting corrosion be much more prone to provoke a catastrophic failure than
uniform corrosion generally does? [2 Points]

(c) Discuss any two factors which effect cavitation damage in pumps and impellers? [2
Points]

6
Formula Sheet
Galvanic Series

7
Erosion Corrosion
Forms of corrosion

General corrosion (uniform corrosion over the whole anode)

Localized Corrosion (corrosion at isolated areas in the anode)
Galvanic corrosion
pitting corrosion
Crevice corrosion
Metallurgically Influenced Corrosion (corrosion is related to microstructure)
intergranular corrosion of stainless steel
Mechanically Assisted Corrosion (corrosion is accelerated due to mechanical
factors)
Erosion corrosion
Corrosion Fatigue
Environmentally Assisted Cracking (corrosion results in cracking)
Stress corrosion cracking
Hydrogen damage

2
 Forms of Corrosion

Factors affecting forms of corrosion :

Microstructure Environment Stress Geometry Time

3
Flow Assisted/Induced/Accelerated Corrosion

Three forms of corrosion related to flow of electrolyte:

Erosion corrosion
Impingement
Cavitation

High flow rate of electrolyte may:

remove deposited corrosion products and keeps the metal surface clean and
therefore the metal becomes more active which increases corrosion rate (see
Nernst’s equation).
mechanically remove protective oxides.
increase oxygen transport and supply to the metal surface:
increases the rate of dissolution of active metal
enhances passivating passive metals
increase ions supply to the metal surface

4
Erosion Corrosion

An increase in corrosion brought about by a high relative velocity between the

corrosive environment and the surface.

Removal of the metal may be:

as corrosion product which “spalls off” the surface because of the high fluid shear
and bares the metal beneath;
as metal ions, which are swept away by the fluid flow before they can deposit as
corrosion product.

N.B. Remember the distinction between erosion and erosion corrosion:

erosion is the straightforward wearing away by the mechanical abrasion caused by
suspended particles . . . e.g., sand blasting, erosion of turbine blades by droplets . . .
erosion corrosion also involves a corrosive environment . . . the metal undergoes a
chemical reaction.

5
Erosion Corrosion

Erosion corrosion produces a distinctive surface finish:

grooves, waves, gullies, holes, etc., all oriented with respect to the fluid flow pattern . . .
“scalloping”...

Erosion corrosion of stainless alloy pump

impeller.
Erosion corrosion of condenser
tube wall. Impeller lasted ~ 2 years in oxidizing
conditions;
after switch to reducing conditions, it
lasted ~ 3 weeks!

6
Erosion Corrosion

Most metals/alloys are susceptible to erosion corrosion.

Metals that rely on protective surface film for corrosion protection are particularly
vulnerable, e.g.: Al, Pb, Stainless Steel, Carbon Steel.
Attack occurs when film cannot form because of erosion caused by suspended particles
(for example), or when rate of film formation is less than rate of dissolution and transfer to
bulk fluid.

7
Erosion Corrosion

Erosion Corrosion found in: aqueous solutions;

gases;
organic liquids;
liquid metal.
If fluid contains suspended solids, erosion corrosion may be aggravated.
Vulnerable equipment is that subjected to high velocity fluid, to rapid change in
direction of fluid, to excessive turbulence . . .
viz. equipment in which the contacting fluid has a very thin boundary layer
high mass transfer rates.
Vulnerable equipment includes:

pipes (bends, elbows, tees); flow measuring orifices, venturies;

valves; turbine blades;
pumps; nozzles;
blowers; baffles;
propellers, impellers; metal working equipment (scrapers, cutters,
stirrers; grinders, mills);
stirred vessels; spray impingement components;
HX tubing (heaters, condensers); etc.

8
Erosion Corrosion

Surface film effects

Protective corrosion product films important for resistance to erosion corrosion.
Hard, dense, adherent, continuous films give good resistance, provided that they are not
brittle and easily removed under stress.

Lead sulphate film protects lead against DILUTE H2SO4 under stagnant conditions, but not
under rapidly moving conditions.

Erosion-corrosion of hard
lead by 10% sulphuric acid
(velocity 39 ft/sec).

9
Erosion Corrosion

pH affects films in erosion corrosion of low alloy steel.

Effect of pH of distilled water on

erosion corrosion of carbon steel at
50 C (velocity 39 ft/sec).

Scale generally granular Fe3O4 (non protective). But at pH 6 & pH 10, scale Fe(OH)2/Fe(OH)3 . .
. hinders mass transport of oxygen and ionic species.
10
Erosion Corrosion

N.B. Dissolved O2 often increases erosion corrosion . . .

e.g. copper alloys in seawater. . . BUT . . . on steels, dissolved O2 will inhibit erosion
corrosion . . . utilized in boiler feedwater systems.

Effects of temperature and dissolved O2 on the weight-loss of AISI 304

stainless steel exposed for 800 hours in flowing water at 3.7 m/s.
11
Erosion Corrosion

Good resistance of Ti to erosion corrosion in:

seawater;
Cl solutions;
HNO3;
and many other environments.
Resistance depends on formation and stability of TiO2 films.

13
Erosion Corrosion

Chromium imparts resistance to erosion corrosion to: steels;

Cu alloys.

Effect of chromium additions on

seawater impingement-corrosion
resistance of copper-nickel alloys.
36-day test with 7.5 m/s jet velocity;
seawater temperature: 27 C.

Such tests have led to the marketing of a new alloy for condenser tubes . . “CA 722” . .
. previously “IN 838” . . . with constituents . . . Cu 16Ni 0.4Cr.

14
Erosion Corrosion

Velocity Effects

Schematic showing the

effect of flow velocity on
erosion-corrosion rate.

N.B. Turbulent flow regime for V < Vc is sometimes called

Flow Assisted Corrosion regime.

15
Erosion Corrosion

Erosion Corrosion in Carbon Steel and Low Alloy Steels

N.B. these materials are used extensively in boilers, turbines, feed water heaters in
fossil & nuclear plants, CANDU feeders.

High velocities occur in single phase flow (water) and two phase flow (wet steam).

Single phase E C seen in H.P. feedwater heaters, SG inlets in AGRs, feedwater pumps,
and CANDU feeders.

Two phase E C more widespread . . . steam extraction piping, cross over piping (HP
turbine to moisture separator), steam side of feedwater heaters, and CANDU feeders.

17
Erosion Corrosion

Material effects – low alloy steel . . .

Cr additions reduce E-C.

Erosion-corrosion loss as a function of time for mild steel and 1 Cr 0.5 Mo

steel in water (pH at 25 C = 9.05) flowing through an orifice at 130 C.
18
Erosion Corrosion

Prevention of Erosion Corrosion

design (avoid impingement geometries, high velocity, etc.);

chemistry (e.g., in steam supply systems . . . for CS or low alloy steel add
O2, maintain pH > 9.2, use morpholine rather than NH3);

materials (use Cr containing steels);

use hard, corrosion resistant coatings.

23
Cavitation

CAVITATION DAMAGE

Similar effect to E-C: mechanical removal of oxide film caused by collapsing

vapour bubbles.

High-speed pressure oscillations (pumps, etc.) can create shock waves > 60,000
psi. Surface attack often resembles closely-spaced pitting.
24
Fretting Corrosion

FRETTING CORROSION
Similar to E C but surface mechanical action provided by wear of another
surface . . . generally intermittent, low amplitude rubbing.
Two theories . . . with same overall result . . .

25
Fretting Corrosion

Effects in terms of materials COMBINATIONS

Fretting resistance of various materials

Poor Average Good

Aluminum on cast iron
Aluminum on stainless steel
Magnesium on cast iron
Cast iron on chrome plate
Laminated plastic on cast iron
Bakelite on cast iron
Hard tool steel on stainless
Chrome plate on chrome plate
Cast iron on tin plate
Cast iron on cast iron with
coating of shellac
Cast iron on cast iron
Copper on cast iron
Brass on cast iron
Zinc on cast iron
Cast iron on silver plate
Cast iron on silver plate
Cast iron on amalgamated
copper plate
Cast iron on cast iron with
rough surface
Magnesium on copper plate
Zirconium on zirconium
Laminated plastic on gold plate
Hard tool steel on tool steel
Cold rolled steel on cold rolled
steel
Cast iron on cast iron with
phosphate coating
Cast iron on cast iron with
coating of rubber cement
Cast iron on cast iron with
coating of tungsten sulfide
Cast iron on cast iron with rubber gasket
Cast iron on cast iron with
Molykote lubricant
Cast iron on stainless with
Molykote lubricant

Source: J.R. McDowell, ASTM Special Tech. Pub. No. 144, p. 24, Philadelphia, 1952.

26
Fretting Corrosion

Prevention of Fretting Corrosion

lubricate;

avoid relative motion (add packing, etc.);

increase relative motion to reduce attack severity;

select materials (e.g., choose harder component).

27
 College of Engineering
Department of Mechanical Engineering

Corrosion Engineering Semester: Spring 2021

MEEN 4341

2nd Midterm Exam Date: 5/April/2021

Time: 75 min

Name: ID:

Section: 102

General Instructions
1. Answer all the questions.
2. The exam is closed book closed notes.
3. Read each question carefully.
4. Be neat and clear in your presentation and sketches, and show all work for full credit.
5. Cellular Phones are strictly prohibited in the examination hall.
6. CHEATING penalty will result in an F in the course.

Question Assessed Assessed Maximum Obtained

Number PLOs CLOs Marks Marks
Q1 MEEN1A 2.3 3
Q2 (a) MEEN1A 2.1 1
Q2 (b) MEEN1B 2.3 1.5
Q2 (c) MEEN1C 2.3 1
Q2 (d) MEEN1C 2.3 1.5
Q3 (a) MEEN1A 2.3 1
Q3 (b) MEEN1B 2.3 1
Q4 (a) MEEN1A 2.3 2
Q4 (b) MEEN1B 2.1 2
Q5 (a) MEEN1A 2.1 2
Q5 (b) MEEN1A 2.3 2
Q5 (c) MEEN1A 2.1 2
Question 1: Identify the type of corrosion in each of the figures below. [3 Points]

Fretting corrosion Intergranular corrosion

Erosion corrosion Galvanic corrosion

Pitting corrosion Uniform corrosion

1
Question 2 (a) Identify and briefly describe mechanism of the type of corrosion shown in the figure.
[1 Points]

From the figure it is clear that it is an example of pitting corrosion. In pitting corrosion

localized corrosiveness produces pits or holes in the metal.

Pitting starts with a time of initiation and it always grows in the direction of gravity and in

this failure occurs suddenly because the pits are hidden in materials.

M+ is pitted by aerated NaCl solution. Rapid dissolution occurs within pit while O2 reduction

take place in adjacent surface.

Rapid dissolution of M+ causes excess ‘+ve’ charge in pit which causes migration of Cl-

High concentration of M+ Cl- and H+ in pit.

(b) Formulate an expression for pitting ratio using the figure. What does p and d represent?
What will be the value of pitting factor if a surface is experiencing uniform corrosion?
[1.5 Points]

From the figure, we can have the expression,

2
 Pitting ratio = P / d
Here,

Pitting ratio = Deepest metal penetration / Average metal penetration

For, uniform attack means corrosion rate is uniform.

➔ Pitting ratio = 1

(c) If the average penetration by weight loss is 2.2 mm and the pitting factor is estimated
to be 3.8, what will be the maximum penetration experienced by the plate due to pitting?
[1 Points]

Pitting factor = P/d

Here,

P = maximum possible penetration

d = average penetration from weight loss

Given,

Pitting factor = 3.8

Average penetration from weight loss (d) = 2.2mm

P = (Pitting factor)*d

P = (3.8*2.2)mm

➔ Maximum possible penetration (P) = 8.36mm

3
 (d) A pit is characterized as A-3, B-2, C-5. Using the chart below, Evaluate

(i) Surface Pit Density

(ii) Surface Pit Opening
(iii) Pit Depth [1.5 Points]

Given that,

A-3, B-2, C-5

We have,

1. Surface pit density = 5 x 104 / m2

2. Surface pit opening = 2.0 mm2
3. Pit depth = 6.4 mm

4
Question 3 (a) For a metallic coating of type 430 stainless steel on mild steel, what happens if an imper-
fection or a break develops in the coating, as shown below? [1 Point]

If there is metallic coating of 430 stainless steel on mild steel and if there is imperfection or break in coating
due to which there will be corrosion on the mild steel due to sea water. Because of this crack the sea water
will penetrate into mild steel. Which contains salt in it due which the electron transfer rate increases. So, the
corrosion occurs rapidly which leads to weakens the strength of metal.

This imperfection acts as an anode and the remaining area acts as cathode. Hence, generation of galvanic
potential takes place where the anode is to supply the electrons to large cathode area. So, degradation takes
place very fast.

(b) Suggest a third metal for protection against Copper-Aluminum galvanic couple. Provide criteria for
your selection. [1 Point]

For the protection of copper and aluminum galvanic couple, the third metal that can act as a shield against
corrosion is Zinc. This is because it gets isolated due to more electronegative nature of Zinc and thus acts as
a sacrificial anode for the Copper-Aluminum galvanic couple.

5
Question 4: (a) Explain sensitization with reference to the figure shown below. [1 Point]

With austenitic stainless steels, intergranular attack is usually the result of chromium
carbide precipitation (Cr23C6) at grain boundaries, which produces a narrow zone of
chromium depletion at the grain boundary. This condition is termed sensitization and it is
shown in Figure above in the question. Sensitization involves the precipitation of chromium
carbides at grain boundaries, which results in a narrow zone of chromium depletion at the
grain boundary.

Because the chromium is the primary alloying element that makes stainless steel corrosion
resistant, the chromium-depleted regions are susceptible to preferential corrosion attack. It is
believed that this occurs because the chromium content immediately adjacent to the carbide
may be below that required for the stainless-steel alloy. If the carbides form a continuous
network on the grain boundary, then corrosion can produce a separation or gap at the
boundary and possible grain dropping or loss.

(b) Type 321 steel is stabilized because of presence of Niobium (NB) or Titanium (Ti). If
this steel is heated to 1230 °C and rapidly cooled to 815 °C, will there be any intergranu-
lar (IGC) corrosion? Yes, or NO? If yes, what will be the form of IGC?
[2 Point]

Chromium carbides can be precipitated if the stainless steel is sensitized in the temperature
range 550–850°C (1020–1560°F), for example during heat treatment or welding. If the
temperature lies in the critical range for too long, chromium carbides will start to form in the
grain boundaries, which then become susceptible to intergranular corrosion. The area
adjacent to the grain boundaries becomes depleted in chromium (the chromium reacts with
carbon and forms carbides) and this zone, therefore, becomes less resistant to intergranular
corrosion.

But materials with less than 0.05% carbon normally have sufficient resistance against
intergranular corrosion after welding. ELC (extra low carbon content) steels, i.e. steels with
maximum 0.030% carbon, have very good resistance to intergranular corrosion. The same
applies to steels stabilized with titanium (Ti) or niobium (Nb), since these types of steel
6
 form niobium or titanium carbides instead of chromium carbides, thus avoiding the critical
decrease in the chromium content.

Question 5: (a) Why does corrosion of water filled steel tanks occur below the waterline? [2 Points]

Corrosion of not only steel but iron also occur below the waterline. Corrosion needs both air
and water to be present. Just below the waterline water and air are present in the right
amounts to trigger a corrosion. Too much below the waterline air(oxygen)will not be present
in sufficient quantities. Well above the water line, water itself will not be present.

(b) Many water contacting metals depend on an adherent oxide film to protect them from
corrodents like oxygen and sulfur (called “passivation”). However, passivating oxide lay-
ers sometimes accelerate the failure of the metal. Why is this? [2 Points]

As metals are exposed to the surrounding environment, if left unblocked by paint or powder
coating, they will corrode naturally, creating the skin, or seal layer. Most passive films are
made of oxides, combinations of metal and oxygen, so are called passive oxide layers.

One of the biggest benefits to passive oxide layers is that when they arise naturally, they will
also, naturally “heal” if the surface of the metal is scratched or otherwise damaged, as the
next layer of molecules will then bond with the environmental elements.

The effectiveness of passive oxide layers depends on the type of elements involved. Not all
oxide layers are protective: If the oxide is porous enough for oxygen to get through, then no
seal will be formed, and the metal beneath will continue to corrode. For example, magnesium
oxide forms a layer with high surface porosity that does not halt corrosion. Oxygen molecules
still flow through and react with the magnesium underneath.

Likewise, the elements in the surrounding environment also matter. Stainless steel, for
example, can be challenged by salt or iron deposits. If the overall chemistry of the surface no
longer passivates naturally, rust will set in.

(c) Discuss the various types of stresses that can lead to SCC? [2 points]

Stress corrosion cracking (SCC) is the growth of crack formation in a corrosive environment.
It can lead to unexpected and sudden failure of normally ductile metal alloys subjected to a
tensile stress, especially at elevated temperature. SCC is highly chemically specific in that
certain alloys are likely to undergo SCC only when exposed to a small number of chemicals
environments. The chemical environment that causes SCC for a given alloy is often one
which is only mildly corrosive to the metal. Hence, metal parts with severe SCC can appear
bright and shiny, while being filled with microscopic cracks. This factor makes it common
for SCC to go undetected prior to failure. SCC often progresses rapidly, and is more
common among alloys than pure metals. The specific environment is of crucial importance,
and only very small concentrations of certain highly active chemicals are needed to produce
7
catastrophic cracking, often leading to devastating and unexpected failure.

The stresses can be the result of the crevice loads due to stress concentration, or can be

caused by the type of assembly or residual stresses from fabrication (e.g., cold working); the

residual stresses can be relieved by annealing or other surface treatments.

8
Formula Sheet
Galvanic Series