Chapter 2.

Corrosion of Metals

1
Learning Objectives
• To gain knowledge of various forms of corrosion occurring
in industrial environments
• To establish understanding of the various mechanisms underlying corrosion
• To develop basic skills in diagnosing the causes of corrosion
• To develop basic concepts of mitigation approaches for corrosion control

Topics and key points

1. Uniform corrosion: corrosion rate measurement
2. Galvanic corrosion: mechanisms, essential conditions, galvanic series
3. Crevice corrosion: waterline corrosion, droplet corrosion, gasket corrosion,
deposit corrosion, filiform corrosion,
4. Pitting: mechanism of differential aeration corrosion
5. Intergranular corrosion: sensitisation of stainless steels, weld decay,
6. Selective leaching: graphitization of cast irons, dezincification of brasses
7. Stress-corrosion cracking
8. Corrosion fatigue; fretting
9. Hydrogen damage: hydrogen blistering, hydrogen attack, hydrogen
embrittlement
10. Oxidation: Pilling-Bedworth ratio, oxide morphology, effect of doping, oxidation
kinetics
2
Types of Corrosion
There are many different ways of looking at real cases of metal corrosion:
• low-temperature corrosion and high-temperature corrosion
• dry (atmosphere, industrial gases) corrosion and wet (aqueous solutions,
liquid chemicals) corrosion
• chemical corrosion and electrochemical corrosion
• types of materials: steels, aluminium alloys, ceramics, etc.
• types of environment: sulphuric acid, alkalis, marine, etc.

One classification considers industrial metal corrosion in 10 categories:

• uniform attack
• galvanic corrosion
• crevice corrosion
• pitting
• intergranular corrosion
• selective leaching
• stress-corrosion cracking
• corrosion fatigue
• hydrogen damage
• oxidation http://corrosion-doctors.org/Forms/FormType.htm
3
1. UNIFORM CORROSION
The corrosion where uniform removal of metal over
the entire surface occurs.
• it is the most common type of corrosion; it is most metal-consuming
• all metals are attacked by uniform corrosion
• it could be either chemical or electrochemical 𝑀𝑀 → 𝑀𝑀 +𝑛𝑛 + 𝑛𝑛𝑒𝑒 −
• steady corrosion over the entire surface exposed to the corroding media
• least concerned in engineering design: easy testing, easy inspection, easy
prediction of failure
Uniform corrosion is dealt with most effectively by
• proper selection of materials (cost of corrosion resistant material vs.
cost of protection of a cheaper and less resistant material)
• application of protective coatings
• addition of inhibitors (to environment)
• cathodic protection
Corrosion rate is an important parameter
for both design and maintenance

https://www.pinterest.com/pin/341569952958765054/ 4
 corrosion products of the http://www.holiday-
detector.com/dc_holi
unprotected rebars day_detector.htm

(reinforcing-bars) expand
in volume and cause
cracking to the concrete

An engineer using
holiday detector to
inspect painting

Coating holidays (holes) cause

localised corrosion
http://www.chemtrend.com/sites/default/files
/fish_eye_paint_defect.jpg

Holiday
Detector 5
Problem solving: Determination of corrosion rate

One way to determine corrosion rate is to measure the

weight loss of a sample coupon.
Example:
A 1040 carbon steel plate sample coupon of 2 × 5 𝑐𝑐𝑐𝑐2
in size is placed in a reaction vessel for 3 weeks. After
cleaning off the corrosion products the sample is
weighed to have lost 1.2 grams. Determine the
corrosion rate of the steel in the medium (in mmpy,
millimetres per year). https://encrypted-
tbn1.gstatic.com/images?q=tbn:ANd9GcSSnQ_0J5ujm7Z
1S2XUrirEhZ9_7joNegiX995dH6EQNLkPAvd2mw

Solution: http://hinmrec.hnei.hawaii.edu/wp-
content/uploads/2010/01/DSCN4757.jpg
Converting weight loss into volume loss:
density of steel: ρ = 7.8 𝑔𝑔/𝑐𝑐𝑐𝑐3
weight loss: 𝑤𝑤 = 1.2 𝑔𝑔
→ volume loss: 𝑣𝑣 = 𝑤𝑤/𝜌𝜌 = 1.2/7.8 = 0.15 𝑐𝑐𝑐𝑐3
Spread the volume over surface to give corrosion depth:
surface area of the coupon: 𝐴𝐴 = 2 × 5 × 2 = 20 𝑐𝑐𝑐𝑐2
corrosion depth: 𝑑𝑑 = 𝑣𝑣/𝐴𝐴 = 0.15/20 = 0.0075𝑐𝑐𝑐𝑐 = 0.075 𝑚𝑚𝑚𝑚
→ this is the depth loss of the coupon, over 𝑡𝑡 = 3 weeks
Work out annual corrosion rate:
Therefore, for 52 weeks in a year, the annual corrosion rate
can be estimated to be:
𝑅𝑅 = 𝑑𝑑/𝑡𝑡 = (0.075/3) × 52 = 1.3 𝑚𝑚𝑚𝑚/𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦 = 1.3 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 6
2. GALVANIC CORROSION
• The corrosion of one metal caused by another in an
electrochemical process driven by the potential difference
between the two metals.
• In this process, the corrosion in one metal is accelerated (the
anode) while corrosion in the other is suppressed (the cathode).
http://www.oldglobewood.com/uploads/3
/6/8/7/3687677/9241203_orig.jpg?235

Conclusion: bimetal corrosion between Fe and Cu

HMS Alarm, the Royal Navy Recommendation: never use Fe in direct contact with Cu in seawater
32 gun frigate in 1763 had a
complete cover of thin copper
sheathing on her hull to
protect wood damage caused Teredo worm
by Teredo woodworms and to
prevent barnacle growth. The
copper sheath was attached
to the wooden hull with
forged iron nails. The
sheathing became detached
after two years in service due
to galvanic corrosion of the
iron nails, making it the first
official record of such
damage. (Trethewey &
Chamberlain )
7
Electrochemical Nature Named after Luigi Galvani, an
Italian physician and physicist,
Three Essential Conditions: who pioneered the study of
• potential difference (Fe/Cu) bioelectricity, in 1870
• presence of an electrolyte (sea water) https://en.wikipedia.org/wiki/Luigi_Galvani
• electrical connection (Fe nails to Cu sheath)

Basic Corrosion Cell: Electrochemical cell can form in one piece

Metal Connection
of metal ...
𝒆𝒆−
M+ H+ H2

e- M e-
Electrochemical
Reaction

𝑵𝑵+ 𝑴𝑴+
+ − + −
𝑁𝑁 ← 𝑁𝑁 + 𝑒𝑒 𝑀𝑀 → 𝑀𝑀 + 𝑒𝑒 Key Terms:
Electrolyte • oxidation reaction, reduction reaction
Factors Influencing Galvanic Corrosion: • anion, cation
• potential difference: electromotive force (emf) • anode, cathode, electrode potential
of elements; galvanic series of alloys • electrolyte
• environment: electrolyte conductivity • emf, galvanic series
• cathode-to-anode area ratio • half cell reaction
• distance effect • galvanic cell, battery 8
Case study: galvanic corrosion

Two UK Royal Navy Sea Harriers suffered nose wheel

collapse because of galvanic corrosion between their
stainless steel bearing and the magnesium wheel hub
during the Falklands War in 1982 (Trethewey &
Chamberlain) – even the most carefully designed
apparatus cannot spare this damage.

9
Case study: galvanic corrosion

A 1986 restoration of the Statue of Liberty (built

in 1875), due to galvanic corrosion damage
The copper skin is attached to the wrought iron structure
using a copper saddle and rivets. To prevent possible
galvanic corrosion, engineers coated the iron structure with
tar just under the saddle brackets, to provide insulation.
However, over the years experiencing hot summers, the tar
vaporized leaving copper in contact with the iron, causing
rust to form. Rust has a larger volume, and the volume
expansion ruptured the riveted joints, causing detachment of
the skin from the structure.

covered
with tar

10
Case study: galvanic corrosion
The storage tanks (right) are made of carbon
steel, protected with surface coating. After
Several years in service, the bottom part
was found to have suffered more corrosion
damage than the walls.
To extend the service life, engineers replaced
the bottom part of the tanks with a more
corrosion resistant solution: to clad the inner
surface of the bottom part with a type 304
stainless steel (18-8) and welded it onto the remaining carbon steel wall. However, after only a
few months, some severe corrosion damage was found along a horizontal line just above the
welding line, causing leakage. This accelerated corrosion of the carbon steel is caused by the
galvanic effect from the stainless steel. Small paint holidays help create a large cathode-to-anode
area ratio, making the situation worse.
http://events.nace.org/library/corrosion/Experiments/
galvanic-rivets.asp

(a) Cu rivets in steel plate,

Coating submerged in seawater.
Severe corrosion How will corrosion occur?
observed
(b) Steel rivets in Cu plate,
Carbon steel submerged in seawater.
How will corrosion occur?
18-8 SS
When Cu/steel (Fe) are paired, steel will corrode. Due to area ratio effect, the steel rivets
in (b) will be corroded much more severely. Due to the distance effect, the steel in the
area around the Cu rivets in (a) will be corroded much more than the areas further away. 11
 Standard electromotive force (EMF) table lists metal
Standard EMF Series elements in order of their electrode potential as an indicator of
their tendency to corrode.
Standard Reduction
Electrode Reaction
Potential Vo (V)
Au3+ + 3e- → Au +1.420
O2 + 4H+ + 4e- → 2H2O +1.229 More about the EMF series:
Pt2+ + 2e- → Pt +1.2 • The series is in reference to Standard
Ag+ + e- → Ag +0.800 Hydrogen Electrode (SHE), whose
Fe3+ + e- → Fe2+ +0.771 potential is defined as 0.000 (V).
O2 + 2H2O + 4e- → 4(OH-) +0.401 • Standard: 25℃, 1.0 M concentration of
Cu2+ + 2e- → Cu +0.340 liquid species, 1 atm partial pressure of
Increasingly
inertness 2H+ + 2e- → H2 0.000 gaseous species.
(cathodic) Pb2++ 2e- → Pb -0.126 • The series is normally listed in
Sn2+ + 2e- → Sn -0.136 reduction (gain electrons) potentials,
Ni2+ + 2e- → Ni -0.250 e.g., 𝐶𝐶𝐶𝐶 2+ + 2𝑒𝑒 → 𝐶𝐶𝐶𝐶
Increasingly Co2+ + 2e- → Co -0.277 • If you have an oxidation half-cell
activity Cd + 2e → Cd
2+ - -0.403 reaction, then the potential is negative
(anodic)
Fe + 2e → Fe
2+ - -0.440 of the value listed in this EMF series!
Cr3+ + 3e- → Cr -0.744 For example:
Zn + 2e → Zn
2+ - -0.763 2+ 𝑜𝑜
𝐶𝐶𝐶𝐶 + 2𝑒𝑒 → 𝐶𝐶𝐶𝐶 𝑉𝑉 = −0.277𝑉𝑉
Al3+ + 3e- → Al -1.662 2+ 𝑜𝑜
𝐶𝐶𝐶𝐶 → 𝐶𝐶𝐶𝐶 + 2𝑒𝑒 𝑉𝑉 = +0.277𝑉𝑉
Mg2+ + 2e- → Mg -2.363
Na2+ + 2e- → Na -2.714 Metal with lower reduction potential has
K +e →K
+ - -2.924 stronger tendency to corroded
Standard EMF Series
– Example: Cu-Fe

Metal 𝑽𝑽𝒐𝒐𝒎𝒎𝒎𝒎𝒎𝒎𝒎𝒎𝒎𝒎 (V)

Au + 1.420
more cathodic

Cu + 0.340
More noble
Pb - 0.126
Sn - 0.136
Ni - 0.250
Co - 0.277
Cd - 0.403
More active
Fe - 0.440
Cr - 0.744
more anodic

Zn - 0.763
Al - 1.662 So… for Cu-Fe,
Mg - 2.363 • Fe is anode & corrodes (𝐹𝐹𝐹𝐹 → 𝐹𝐹𝐹𝐹 2+ + 2𝑒𝑒)
Na - 2.714 • Cu is cathode & protected!
K - 2.924
Electromotive Force Series (𝟐𝟐𝟐𝟐℃ or 𝟕𝟕𝟕𝟕℉)

If a piece of Mn is
attached to a piece of
Pb and the pair is
placed in seawater,
which metal corrodes?

If a piece of aluminum
more anodic

bronze (Al-Cu alloy) is

attached to a 18-8
stainless steel (Fe-
18%Cr-8%Ni) and
placed in seawater,
which alloy corrodes?

Attention:
When using an EMF table,
check (i) if it is listed in
reduction potential, (ii) if it is
listed in increasing or
decreasing orders. Note where
noble metals (Au, Pt …) are in
the series, you will know the
direction of cathodic or anodic!
14
 ← Cathodic Anodic →
Galvanic Series in Sea Water

Passivated
Galvanic series is used in
Activated
industry to evaluate the
tendency of engineering ~ 0.3 V
alloys for galvanic corrosion
←

aluminium bronze centre in

austenitic stainless steel ring
https://www.corrosionpedia.com/an-introduction-to-the-galvanic-series-galvanic-
compatibility-and-corrosion/2/1403 15
http://www.roymech.co.uk/images/corrosion.gif

16
GALVANIC CORROSION
Prevention Techniques
1. select metals of similar electrode potentials to minimise the driving force of
the process
2. protection against moisture condensation to eliminate the chance of forming
an electrolyte
3. insulation between dissimilar metals to avoid electrical connection
4. coating for electrical insulation or isolation of metal from electrolyte
5. installing a third metal which is anodic to both metals
6. designing for easy replacement of the anode metal or thicker section for
longer service life
http://marineinsight.com/wp-
content/uploads/2010/11/DSC01327.jpg

1
3
5
Zn
http://www.carbonepl
us.be/files/insulation/
prod_corflex_001.jpg

2 4
17
GALVANIC CORROSION
Beneficial Applications of Galvanic Corrosion
• Cathodic protection, sacrificial anode protection
• Galvanised steels: Zn coating is anodic to steel, acts as a sacrificial metal
• Cleaning silver
blackened surfaces: silver sulphide
rubbing with an abrasive: bad for silverware
Ag in Al pan in soda solution: cathodic reaction reduces silver sulphide to Ag

http://thegreenists.com/wp-
content/uploads/2010/07/clean3.jpg

18
What could be the possible cause of this corrosion?

Steel pipe,
painted

Rubber cushion
What could be the
Steel beam, possible cause of
painted this corrosion?

http://www.stoprust.com/img/large_nubolt10.jpg

The steel piping is protected by surface coating.

The only sign of corrosion is found at where the
pipes are supported (with a rubber cushions).

The interior, though directly exposed to the

medium, shows little sign of corrosion. The flange
is of the same material, and is only mildly exposed
http://www.offshoreenergy.dk/Files/Billeder/On-
to the same medium, but severely damaged Off/News23/flange.jpg 19
3. CREVICE CORROSION
Crevice corrosion is a localised attack
occurring within crevices or other shielded
areas where a small volume of stagnated
solution presents.
Crevice corrosion
of pipes caused by
rubber cushions

Crevice corrosion on an18-8 stainless

steel pipe flange which was interfaced
with a gasket. Corrosion on the inside
of the pipe was negligibly. This is also
known as gasket corrosion.

Crevice corrosion
Crevice corrosion of bolts under a bolt head 20
Crevice Corrosion Mechanism
In a seawater environment: 𝐻𝐻2𝑂𝑂, 𝑂𝑂2, 𝑁𝑁𝑁𝑁 + and 𝐶𝐶𝐶𝐶 −
Metal corrodes: 4𝑀𝑀 + 𝑂𝑂2 + 2𝐻𝐻2𝑂𝑂 → 4𝑀𝑀𝑀𝑀𝑀𝑀 ↓
This reaction can be seen to occur in two steps:
𝑀𝑀 → 𝑀𝑀 + + 𝑒𝑒 − the anodic reaction
− − the cathodic reaction
𝑂𝑂2 + 2𝐻𝐻2𝑂𝑂 + 4𝑒𝑒 → 4 𝑂𝑂𝑂𝑂
These reactions consume 𝑂𝑂2 and produce 𝑀𝑀 + inside the crevice. Under stagnant
condition, 𝑂𝑂2 is not replenished and the cathodic reaction is forced to occur outside
the crevice. The positively charged crevice, due to continued production of 𝑀𝑀 + ,
attracts negatively charged ions such as 𝐶𝐶𝐶𝐶 − and 𝑂𝑂𝑂𝑂 − into the crevice.
O2 depleted, crevice
The increased concentration is positively charged
of 𝐶𝐶𝐶𝐶 − in the crevice promotes
production of 𝑀𝑀+ , encourages
𝑀𝑀+ + 𝑂𝑂𝑂𝑂 − → 𝑀𝑀𝑀𝑀𝑀𝑀 ↓, and
more hydrolysis of 𝐻𝐻2 𝑂𝑂,
leading to increased 𝐻𝐻 +
concentration, 𝐻𝐻 + .
Increased 𝐻𝐻+ and 𝐶𝐶𝐶𝐶 −
accelerate the corrosion; thus
crevice corrosion is self-
catalytic. How much 𝑂𝑂2 can
dissolve in water?
21
Characteristics of Crevice Corrosion:
• crevices of 25 - 100 µm in width are most effective
• concentration of 𝐶𝐶𝐶𝐶− in a crevice is found to be 3-10 times higher than that in
surrounding areas in a case of neutral 𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁 solution: pH value drops from pH 7 to
pH 2-3 within the crevice.
• crevice corrosion is characterised by an initiation period with a very slow start and
an ever-increasing corrosion rate after that.
• the oxygen reduction reaction provides cathodic protection in surrounding areas,
making the attack inside the crevice very difficult to inspect.
• it occurs in many media and is most intense in 𝐶𝐶𝐶𝐶 − solutions.
• metals and alloys having corrosion-resistant oxide films or passive layers are
susceptible to crevice corrosion, because:
- films destroyed by high
concentration of 𝐶𝐶𝐶𝐶 − and 𝐻𝐻+
- stainless steels and Al alloys
are typical examples

The key is difference in

dissolved oxygen level, or
differential aeration http://www.cdcorrosion.com/mode_corrosion/
corrosion_image/caverneuse_1_zoom.jpg 22
Typical conditions and various forms of Crevice Corrosion
• gaps underneath bolt head or between lapping parts
• porous mediums: gaskets, wood, fabrics, sand (gasket corrosion)
• deposition of dirt or corrosion product (deposition corrosion)
• water condensation or droplets (droplet corrosion)
• Inlet corrosion, waterline (waterline corrosion)

Corrosion under bolt head

Example: an 18-8 stainless steel tank for a saline solution was
safe in a dyeing plant; but when a stainless steel bolt accidentally
fell to the bottom of the tank, rapid attack developed under the Waterline corrosion
bolt after a brief period, causing leakage.

Stagnated
Solution
Water droplet
corrosion
Severe corrosion is
found to occur just
underneath the
water line.

Can you explain?

23
What happened to this underground pipe?

http://image.shutterstock.com/z/stock-photo-fragments-of-old-large-water-pipes-
after-many-years-of-operation-corroded-metal-pipe-destroyed-282324041.jpg 24
 Would you be able to explain
why most severe corrosion
happened here?

Would you be able to explain

why there is little corrosion
here?

http://image.shutterstock.com/z/stock-photo-fragments-of-
old-large-water-pipes-after-many-years-of-operation-
corroded-metal-pipe-destroyed-282324041.jpg 25
Minimising Crevice Corrosion
• use welded butt joints instead of riveted or bolted joints
• seal crevices: continuous welding/soldering
• regular and thorough cleaning or complete draining to remove deposits or avoid
stagnation
• filter or screen flow to remove solids in suspension
• use non-absorbent gaskets, such as Teflon, whenever possible
• use crevice corrosion resistant alloys

Maximum crevice corrosion resistance is (iii)

achieved in alloys of (i)
• a narrow active-passive transition (i)
• a small critical current density (ii)
• an extended passive region (iii) (ii)

• Titanium and high nickel alloys are

examples of such materials. http://www.emeraldinsight.com/content_images/fig/12805902
02003.png

• Type 430 stainless steel has a large critical current density, a wide active-
passive transition and a limited passive region. It is extremely susceptible to
crevice corrosion. Stainless steels as a family are very poor in resisting crevice
corrosion.
26
Filiform Corrosion
Also known as filament corrosion, is a form
of thin line corrosion undercutting beneath a
surface film. It has a similar working
mechanism and is often regarded as another
form of crevice corrosion.

http://www.dsmtuners.com/forums/appearance-interior-exterior/344223-
possible-fix-alloy-wheel-corrosion.html

http://www.flickr.com/photos/mmm_beer/380209965/

“I had a …new HP Racing Evo Hyperdark Silver 18x8s.....I

stored them in the basement at my parents’ house
and apparently they had put them in their shed and
the bags were left open a little bit so they have
experienced some great Mid Atlantic weather and
now look like this. Do you think its worth salvaging
these or just to get new wheels?” 27
Characteristics of filiform corrosion
• occurs under surface coating when moisture penetrates the coating
• coating can be organic, polymer, paint, or even its own surface oxide layer
• corrosion damage occurs underneath the surface coating in a directional manner

Mechanism of filiform corrosion

Schematically shown here

is the chemical process in a
filament cell during filiform
corrosion of steel.
Active
Head

• Filiform corrosion usually initiates at scratches or other defects in the coating and propagates laterally as narrow (0.05-3 mm
wide) filaments under the coating.
• The filaments consists of an actively corroding head followed by an inactive tail filled with corrosion products.
• For steel, the head is usually blue, blue-green or grey (associated with Fe2+), and the tail is rusty red (associated with Fe3+);
indicating the head is deaerated and the tail is aerated.
• Oxygen is consumed by active corrosion at the head and is accompanied by hydrolysis of acidification to a pH of 1-4.
• Precipitation of rusty red Fe(OH)3 occurs when Fe2+ from the head contacts the aerated conditions in the tail of the filament.
• Essential H2O and O2 migrates to the corroding filament head through porosity or microcracks in the coating over the
filament tail. Fe(OH)3 decomposes to Fe2O3.3H2O as the filament advances. 28
4. PITTING
Pitting is a highly localised form of corrosion. It is
characterised by pits or holes of various sizes:
• small diameters and depth-to-diameter ratio (≫ 1)
• often in clusters
• failure due to perforation with small weight loss
• very destructive
• very difficult to detect
• difficult to evaluate by laboratory tests
• develop and grow in the direction of gravity
• undercut surface as they grow

Pitting

corrosion pits

29
The Mechanism of Pitting
The process of pitting corrosion consists of two stages:
the initiation and the growth.
Initiation:
• Pitting starts with an initiation period of very slow corrosion rate.
• Pitting selectively initiates at areas of surface irregularities  physical, microstructural,
chemical …
- a surface scratch or other mechanically induced break
- an emerging dislocation or slip step
- a compositional heterogeneity such as an
inclusion, segregation or precipitate
• The initiation of pitting is fragile, and young pits
are unstable.

Growth:
• Following the initiation, a pit grows at an ever-
increasing rate with an identical mechanism to
crevice corrosion.
• It is an autocatalytic process.
• The same mechanism implies that alloys that
show pitting attack are also susceptible to
crevice corrosion.

30
Factors Affecting Pitting

• Solutions Chloride 𝐶𝐶𝐶𝐶 −

- solutions containing chloride or chlorine-containing ions such as Hypochlorite 𝐶𝐶𝐶𝐶𝐶𝐶 −
sea water and hypochlorite solution have strong pitting
tendencies. Chlorite 𝐶𝐶𝐶𝐶𝐶𝐶2−
- solutions containing oxidising metal ions with chlorides are Chlorate 𝐶𝐶𝐶𝐶𝐶𝐶3−
extremely aggressive pitters, e.g., cupric (CuCl2) and ferric
(FeCl3) chlorides. Perchlorate 𝐶𝐶𝐶𝐶𝐶𝐶4−

• Flow
pitting is associated with stagnant conditions; increasing flow velocity decreases pitting
attack.

• Alloys
- Ti has excellent resistance to pitting, owing to its protective film being inert to Cl- and H+.
- as a class, stainless steels are more susceptible to pitting corrosion than any other group
of metals or alloys.
- solution-quenched austenitic SS exhibits better pitting resistance.
- cold working increases pitting attack of 18-8 steels, preferentially on edges.
- surface finish affects pitting resistance: polished surfaces are more resistant than etched
or ground surfaces.
- Cr, Ni, Mo and N as alloying elements increase pitting resistance of SS.
 Type 316 SS is more resistant to pitting than type 304 due to the addition of 2%Mo.
 Type 304 is considered unsuitable for applications in seawater whereas type 316 is
sometimes recommended. 31
5. INTERGRANULAR CORROSION
Intergranular corrosion is a localised
corrosion that occurs preferentially along
grain boundaries inside a metal.

Grain Boundary Attack

- Grain boundary regions are generally subjected to a higher
degree of corrosion, because of the relatively higher free Grain boundary attack of brass
https://www.researchgate.net/figure/a-SEM-SE-
energy state, chemical segregation and impurity concentration. secondary-electrons-image-of-sample-9-unetched-
showing-its-grain_fig3_255762881
- However, in most cases grain boundary corrosion does not
impose a serious problem to the performance of a structural
component.

Sensitisation of Austenitic SSs

- Austenitic stainless steels (SSs) tend to form
carbide precipitates (Cr23C6) along grain boundaries
at 400-850°C, causing a local depletion of Cr.
- This sensitised regions are anodic to the grains and
are thus attacked preferentially.
- A common cause of sensitisation is welding, known
as weld decay, see next slide.

Note: steels containing >10.5%Cr are classified

stainless steels. http://www.hindawi.com/journals/ijelc/2013/970835.fig.0010.jpg
32
A bit more about Weld Decay
– a welding caused sensitisation
of stainless steels

http://sassda.co.za/stainless-steel-and-corrosion/

How to avoid weld decay?

• Control heat treatment conditions for austenitic SSs:
- stress relieving at relatively lower temperatures (350-450°C) to avoid sensitisation.
- solution annealing at 1000-1100°C followed by quenching to eliminate effect of sensitisation.
• Control alloying elements in SSs:
- Use L grade (<0.03%C) SSs, including 304L, 317L, 316L; (note:18-8 SS has 0.06-0.15%C).
- Introduce stabilisers, i.e., strong carbide forming elements: Nb, Ta (347 SS); Ti (321 SS).
• Use alternative processes:
- use electric arc welding instead of flame welding: more rapid heating cycle, narrower heat
affected zone, lower tendency to form carbides in heat affected zone (HAZ).
- Use laser cutting instead of oxy-flame cutting. 33
Other Alloys Susceptible to Sensitisation
Some high strength Al alloys are also susceptible to
sensitisation. For example, the strengthening
precipitates CuAl2 in Al-Cu alloys cause local
depletion of Cu, reducing their corrosion resistance.

Accelerated grain boundary Heat affected zones provide a Fusion cutting is

corrosion due to Cr depletion condition for SS sensitisation another case
caused by formation of Cr carbides

34
6. SELECTIVE LEACHING
Selective leaching, also known as de-alloying and
parting, is the selective removal of one elemental
species in an alloy system.

Examples of selective leaching

- dezincification of yellow brass
- dealuminification of aluminium bronze
- graphitisation of grey cast iron
- Dechrominification
Note: Al bronze and Si bronze are attacked by
selective leaching because Al, Si and Zn in the alloys
are anodic to Cu.

Dezincification of yellow brass

- refers to zinc dissolves in pure water by a
hydrolytic reaction. ↑ Dezincified yellow brass
showing red Cu color
To prevent dezincification:
- alloying: "inhibitors", such as Sn, As and P
- red brass (85-15%Zn) has better resistance
to dezincification
35
Graphitisation
Graphitisation is the selective removal of iron from the surface of grey cast iron due
to a galvanic reaction between the graphite and iron. It is the most costly damage
of large-diameter underground water mains.
- graphite is cathodic to iron, forming excellent galvanic cells
- moist soil under the ground and aqueous solution it carries inside provide the
environment for selective leaching
- graphitization reduces the strength of the cast iron component, earth movement
may cause failure as a result
- use of nodular or malleable iron is effective in avoiding graphitisation

http://www.testing-engineers.com/case1.html

36
This is the body of a large water
pump, made of nodular cast iron. The
pump shows graphitization damage.
Metallographic examination reveals
that the nodular treatment of the cast
iron was not done properly, leading to
the poor performance against the
selective leaching attack. 37
7. STRESS CORROSION CRACKING (SCC)
Stress corrosion cracking is a cracking failure of materials
caused by the combined action of tensile stresses and
corrosive environments.

• SCC occurs to many different materials, including carbon

steels, stainless steels, Al alloys, Cu alloys, Mg alloys,
Ti alloys and plastics.
• It occurs only with specific material-environment combinations:
- carbon steels in caustic solutions
- stainless steels in 50-60°C chloride-containing solutions
- Al alloys in chloride solutions
- Cu alloys, particularly brasses, in ammonia atmosphere

Note:
• The environments in which SCC occurs are
sometimes not highly corrosive to the metals
concerned.
• The stress that induces SCC is also often much
lower than the failure stress of the metal.
• It is the combination of the two that causes the
attack. Aluminium alloy roof structure of a swimming
• When SCC happens the metal may be virtually pool. Parts of the structure are constantly under
unattacked over the rest of its surfaces. tensile stress due to gravity. Condensation of
http://www.libart.ru/static/project_images/thumbs/60003-
chloride-containing vapour from the pool
Libart%20AmpliSpan%20Olympic%20Pool%20-%20(2)_jpg_425x425_q85.jpg provides perfect condition for SCC. 38
 SCC always occurs at
the tensile stress site

Transgranular SCC Intergranular SCC

In SCC, cracks
may propagate in
either transgranular
or intergranular
manner. The
intergranular type
is more
catastrophic.

39
The Process of Stress Corrosion Cracking
The exact mechanism of SCC remains unclear – it is a complex interplay
of metal, environment, stress states and interface properties. Nevertheless
it involves the following steps:

• Initiation (a relative slow process)

- corrosion is the primary reason for crack initiation - cracks are observed to start at the base
of a corrosion pit.
- a tensile stress assists break-up of protective films by enhance the elastic energy of
surface atoms.

• Propagation
- in the intermediate stages, SCC proceeds by the conjoint action of stress (note significant
stress concentration at crack tips) and corrosion at crack tips.
- cracks have been observed to propagate in discontinuous steps, emitting acoustic waves
when jumping. The contribution of corrosion to crack propagation is evident in experiments
when acoustic waves are stopped at the application of cathodic protection and resumed
after the removal of the cathodic protection.
- preferential attack at crack tips, due to local plastic deformation (increased defect density)
and emerging slip steps (decreased resistance to chemical attack).

• Cracking (instantaneous, can be of catastrophic consequence)

- the final failure is in brittle fracture manner caused by unstable propagation of cracks; it is
basically a mechanical process.
- the presence of corrosive chemicals and water molecules at the crack tips, however, lowers
the critical stress for cracking.
40
Factors Affecting Stress Corrosion Cracking
• Metallurgical Factors
- generally speaking, pure metals have lower tendency towards SCC than alloys.
- single phase structures are better against SCC than multiphase structures.
- a soft phase inclusion, however, such as ferrite domains in austenite stainless steel
matrix, may relax the stress concentration at crack tips and slow down their propagation.
- precipitates raise the susceptibility to SCC.

• Stress
- residual stresses: welding, cold working, heat treatment, casting, etc.
- applied stresses: gravitation, mechanical assembling stresses, temperature variation, etc.
- a critical stress seems to exist for SCC for each metal-environment combination.

• Environment
- no general rules to what environments cause SCC → specific metal - environment
combinations.
- can refer to the list of established data for known combinations.
- need to conduct new tests for unknown combinations.

Note:
Materials fail by SCC in a brittle fracture manner by mechanical cracking, thus
unpredictable. Short time SCC testing may not reveal the whole process, and it is difficult to
predict when instability of crack propagation may set in to cause final cracking.
41
Prevention of SCC

• Avoid dangerous metal-environment combinations by using a different metal.

- Carbon steels sometimes are used in preference to stainless steels due to their higher
resistance to stress corrosion cracking.
- Inconel (NiCrFe alloy) is used to replace type 304 SS for the same reason.

• Eliminate the tensile stress component whenever possible

- more often than not, a tensile stress is from residual sources; thus stress relieving heat
treatment is commonly recommended.
- create a compressive surface residual stress condition is highly effective in suppressing
stress corrosion cracking. A compressive surface stress state may be achieved by various
means including thermal treatment, blasting, ion implantation.

• Reduce the corrosiveness of environment

- to change the pH of a fluid
- to eliminate oxygen or chloride from a solution
- introducing inhibitors, cathodic protection and design modification may also
render the environment less harmful.
• Cathodic protection is effective way to prevent SCC
- it may be applied either with an external power supply or consumable anodes.
- precautions must be taken when applying cathodic protection to guard for hydrogen
embrittlement.

42
Summary of SCC

• Stress corrosion cracking is an electrochemical-mechanical process. It initiates

at small but chemically active areas, such as a stress induced film rupture, a
high energy grain boundary, or a chemical segregation site.
• Stress corrosion cracks propagate in discontinuous steps. The slow motion of
corrosion builds up stress concentration at a crack tip until a critical moment
when the crack propagates to a new location and stops when the stress
concentration is relaxed.
• Stress corrosion cracks may follow intergranular and transgranular paths. In
materials having complex slip systems or high stacking-fault energies, cracks
propagate along intergranular paths.
• The role of corrodant in the mechanism of stress corrosion cracking is the least
understood.

43
8. CORROSION FATIGUE (CF)
• The presence of a corrodant, or the action of corrosion,
tends to reduce the fatigue life, or decreases the fatigue
limit, of a metal.
• Little is known about corrosion fatigue beyond the
knowledge of stress corrosion cracking.
• Corrosion fatigue is characterised by transgranular cracks
that do not show much branching. The final cracking is
largely a mechanical process.

Factors Affecting Corrosion Fatigue

• Fatigue life in the case of pure mechanical loading is determined by the number
of cycles, and the effect of cycling frequency is negligible.
• In the case of corrosion fatigue, however, stress cycle frequency has a strong
influence on the fatigue life of a metal.
• Corrosion fatigue is more pronounced at lower stress frequencies. Low
frequencies allow a more persistent contact of corrodant and metal at crack
tips.

Prevention of Corrosion Fatigue

• In addition to those applicable to stress corrosion cracking, vibration should be
avoided to prevent corrosion fatigue, for instance, by design.
44
Corrosion Fatigue Behaviour (a) Fatigue in air (b) Corrosion Fatigue

(a) Fatigue in air or inert environment:

Log (cyclic crack growth rate)

Log (cyclic crack growth rate)
• Crack grows at above the threshold value of stress
intensity factor amplitude (∆Kth) for fatigue.
• Below ∆Kth the crack growth rate is zero, meaning
the material will not never fatigue.
• Crack growth rate (log) increases with increasing
value of ∆K (log).
• KIC is the critical stress intensity factor (fracture
toughness) for instantaneous fracturing.

(b) Corrosion fatigue in corrosive environment:

∆Kth,CF
• Crack growth rate is higher, thus shorter fatigue life.
• Critical ∆Kth, CF is lower compared to non-corrosive (c) Stress corrosion Cracking (d) SCC & CF
mechanical condition.

Log (cyclic crack growth rate)

Log (crack growth rate)
(c) Stress corrosion cracking:
• It occurs within KISCC - KIC.
• It is easier to fracture than in pure mechanical
condition, KISCC< KIC.

(d) Combined SCC and CF:

• This is the worst case of all.
• The rate of crack propagation is faster at a given
stress intensity factor.

Log (maximum stress intensity factor or amplitude) 45

Supplementary Information

Three Modes of Fracture

• Three basic modes of fracture, referred to as mode I, II, III.

• Load applied to a fracturing sample is measured as “stress intensity factor” K.
• “Strength” of a material against fracture is measured in the critical value of K for
these three modes, i.e., KIC, KIIC, KIIIC.
• Fatigue is fracture under repeated cyclic load; thus the “strength” in fatigue is
measured in critical stress intensity factor amplitude: ΔKIC, ΔKIIC, ΔKIIIC.

46
Fretting corrosion
It is caused by repeated small amplitude
rubbing against the surface, facilitating the
break down of surface protective films and
resulting in corrosion. It is a special form of
corrosion fatigue.

Car transportation over the sea is a typical case

for fretting corrosion, particularly on the bearings.

http://www.sescocp.com/img/frettingcorrosion.gif

http://www.underhoodservice.com/Content/Site308/Articles/
03_01_2009/69769fretting1L_00000028109.jpg
http://www.emersonbearing.com/images/tt-rust-
http://corrosion.ksc.nasa.gov/fretcor.htm corrosion.jpg

47
9. HYDROGEN DAMAGE
• Hydrogen in environment is damaging to metals. The
damage is associated with hydrogen absorption.
• Forms of hydrogen damage include
- hydrogen blistering
- hydrogen embrittlement
- decarburisation and hydrogen attack
hydrogen
Source of atomic hydrogen blisters
• corrosion process
• application of cathodic protection
• welding
• electrolysis & electroplating

https://www.researchgate.net/publication/275220945_Survey_of_Dama
ge_Investigation_of_Babbitted_Industrial_Bearings/figures?lo=1

48
Hydrogen Blistering
• Hydrogen blistering is caused by the formation of micro-bubbles of high
pressure hydrogen gas inside the metal.
• The most damaging fact is that the equilibrium pressure between H2 and H is
very high - several 100,000 atm, sufficient to rupture any known engineering
material.
• Hydrogen blistering is most prevalent in
petroleum industry. It occurs in storage tanks
and in refining processes.

• Reduction of 𝐻𝐻 + → 𝐻𝐻;
• Small H atoms can penetrate metal
surface;
• H atoms are unstable, thus try to
combine to form 𝐻𝐻2 gas where
possible;
• Defects within the materials are
preferential sites for 𝐻𝐻2 formation;
• High equilibrium pressure of 2𝐻𝐻 → 𝐻𝐻2
enables building up of 𝐻𝐻2 ;
• High 𝐻𝐻2 pressure causes underneath
blistering.
http://faculty.kfupm.edu.sa/ME/hussaini/Corrosion%20Engineering/04.07.03.htm 49
Hydrogen Embrittlement
Hydrogen embrittlement is the brittle cracking of metals caused
by hydrogen absorption. The actual embrittlement mechanism is
unclear.

• Hydrogen embrittlement occurs in many alloys and is a more

serious problem in high strength materials, including
- high strength low alloy (HSLA) steels
- high strength grades of carbon steels
- Ti alloys (forming of Ti hydrides)
- Cu alloys

50
Prevention of Hydrogen Blistering and Embrittlement
• "Clean" steels:
rimmed steels: high % microvoids, not clean
killed steels: voids-free structure, clean
• Coating & lining:
impervious to hydrogen penetration
electroplating
cladding with austenitic stainless steels or Ni
porous materials such as brick lining
• Resistant alloys:
Ni-containing steels & Ni alloys (due to low
diffusion rate of H in Ni)
• Baking: The electrochemical process of metal
baking at 100-150°C removes H in steels (as plating generates hydrogen
absorption of H in metals is reversible)
• Process control:
pickling, plating and welding can all create H
source for potential hydrogen damages, thus
need to be properly managed; e.g., employ low-
H or H-free welding techniques.

Porous materials provides sites for 2𝐻𝐻 → 𝐻𝐻2 (g). This

prevents H to reach the surface of metal.
51
(i) Drying of welding rods and (ii) Baking of steels to eliminate
absorbed hydrogen increase the fracture resistance of steels:
Portable drying oven for welding rods

52
Decarburisation and Hydrogen Attack
• Decarburization: refers to the removal of C in C-containing alloys at high
temperatures via [𝐶𝐶] + 4[𝐻𝐻] → 𝐶𝐶𝐶𝐶4 (gas).
• Hydrogen Attack: refers to the CH4 formed by decarburisation in microvoids
exerts a high pressure to the matrix of steels, causing embrittlement.

• Hydrogen attack occurs in

- petrochemical plants
- oil refineries
- processing lines for ammonia & methanol synthesis
- conventional power stations

• Environmental factor
Temperature (T) and partial pressure of hydrogen (𝑝𝑝𝐻𝐻2 ) have strong influences
on hydrogen attack of carbon steels:
- Hydrogen attack occurs at 250 - 600°C and 1 -75 MPa of 𝑝𝑝𝐻𝐻2 ;
- Increasing T decreases the 𝑝𝑝𝐻𝐻2 required for hydrogen attack;
- At below 200°C, no hydrogen attack even under relatively high 𝑝𝑝𝐻𝐻2 .

53
• Metallurgical Factors
Carbon Content: the sensitivity of carbon steels to hydrogen attack increases with
carbon content:
- commercial pure iron (0.004%C) resisted attack at 540°C/4.8MPa for 500 hrs
- steel (0.009%C) was attacked under the same conditions

Alloying: alloying with carbide-forming elements (Ti, V, Cr, Mo and W) improves

resistance to hydrogen attack. These elements stabilise C in the matrix, mostly by
forming complex alloy carbides, such as (Fe,M)3C or M7C3.

Processing:
- Cold worked steels embrittle easily in high-temperature and high-pressure H2
- Surface stresses accelerate H absorption and cause hydrogen attack
- HAZ in a weldment is more susceptible to hydrogen attack
- Quench and tempered steels are more resistant than normalised ones
- Spheroidising improves resistance to hydrogen attack
Fe3C

54
10. OXIDATION
• It is a reaction between a metal and O2 at the absence of water.
• Dry oxidation is only a process of appreciable rate at elevated
temperatures for most metals.

55
The Pilling-Bedworth Ratio Metal Oxide PB
K K2O 0.47
It is suggested that oxidation resistance of Li Li2O 0.57
The oxide layer is
a metal depends on the properties of the Ca CaO 0.64
not able to cover the
metal oxide on the surface, as determined metal surface, thus Ba BaO 0.67
by the Pilling-Bedworth (PB) Ratio: non-protective. Mg MgO 0.81
𝑉𝑉𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜 𝑀𝑀𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜 � 𝜌𝜌𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 Al Al2O3 1.28
𝑃𝑃𝑃𝑃 = =
𝑉𝑉𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑛𝑛 � 𝑀𝑀𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 � 𝜌𝜌𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜 Pb PbO 1.40
Zr ZrO2 1.51
𝑀𝑀𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜 : molar mass of oxide
𝑀𝑀𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 : molar mass of metal The oxide layer is Zn ZnO 1.58
𝜌𝜌𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜 : density of oxide protective
Ni NiO 1.66
𝜌𝜌𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 : density of oxide
Cu CuO 1.68
n: number of metal atoms per molecule of oxide
Fe FeO 1.70
Ti TiO2 1.77
Requirements on oxide protective film: Fe Fe3O4 1.90
- good adherence, coherent to base metal Co CoO 1.99
- good mechanical properties: strength, Cr Cr2O3 2.01
ductility and toughness, no rupture under Si SiO2 2.14
applied or thermal stresses Fe Fe2O3 2.14
- high melting temperature Nb Nb2O5 2.69
- similar thermal expansion coefficient to
V V2O5 3.18
metal The oxide layer
W WO3 3.40
- low diffusion coefficient for oxygen & buckles, thus non-
metal ions protective Mo MoO3 3.40

56
Oxidation Mechanism → Electrochemical
Oxidation process of metals in gaseous oxygen is effectively an
electrochemical process rather than a simple chemical reaction,
in analogy to aqueous galvanic process.
For example, oxidation of Cu: 2𝐶𝐶𝐶𝐶 + 𝑂𝑂2 → 𝐶𝐶𝐶𝐶𝐶𝐶
𝐹𝐹𝐹𝐹2 𝑂𝑂3 : PB=2.14
• Anodic reaction at metal-scale interface: 𝐶𝐶𝐶𝐶 → 𝐶𝐶𝐶𝐶2+ + 2𝑒𝑒 − 𝐹𝐹𝐹𝐹3 𝑂𝑂4 : PB=1.90
• Cathodic reaction at scale-gas interface: 𝑂𝑂2 + 4𝑒𝑒 − → 2𝑂𝑂2− 𝐹𝐹𝐹𝐹𝐹𝐹: PB=1.68
• Most metal oxides conduct electrons
and ions to some extent 𝐹𝐹𝐹𝐹2 𝑂𝑂3
𝐹𝐹𝐹𝐹3 𝑂𝑂4

Metal Oxide Scale Atmosphere

𝐹𝐹𝐹𝐹𝐹𝐹

𝐹𝐹𝐹𝐹
57
http://image.club.china.com/twhb/271616765/2010/12/18/1292650890254.jpg

“Blueing” is an easy and common

surface treatment by heating a steel
product to encourage formation of thin
and impermeable surface oxide (mainly
Fe3O4) for corrosion protection.

http://cdn4.explainthatstuff.com/thin-
film-interference.png

http://www.firearmsworld.
net/usa/handgun/m1911s/
colt/0724806r.jpg

58
Formation of Oxide Scales
Oxide Formation is dictated by the diffusion of either metal ions or oxygen ions
through the oxide scale:
• Fe, Ni, Cu, Cr, Co: oxides grow preferentially at the scale-gas interface by
outwards diffusion of cations (i.e., metal ions), leaving ‘pores’ at the metal-
oxide scale interface region, can weaken the bonding of scale to the metal
surface.
• Ti, Ta, Zr, Hf: oxides grow inwards at the metal-scale interface by diffusion of
anions (i.e., oxygen ions), imposing stress at the interface region, can result
in scale fracturing.

59
Nature of Oxide Scales

• Oxide types:
Cation deficient oxides: p-type oxides
Anion deficient oxides: n-type oxides
• Alloying with lower valence metals reduces cation vacancy concentration of
p-type oxides & reduces the rate of diffusion-controlled oxidation. (see NiO
example)
• Alloying with higher valence metals reduces anion vacancy concentration of
n-type oxides & reduces the rate of diffusion-controlled oxidation (see ZrO2
example)

Attention:
• Cation vacancies can only be occupied or created by cations, they only support cation
𝑀𝑀𝑛𝑛+ diffusion.
• Similarly, anion vacancies can only be occupied or created by anions, thus support
anion 𝑂𝑂2− diffusion.

60
Doping Effect • NiO is naturally a p-type oxide having
cation vacancies (from missing Ni2+).
• Alloying Ni (valence 2+) with Li
(valence 1+) decreases cation
vacancy concentration, thus improving
oxidation resistance.
• Alloying Ni with Cr (valence 3+)
increases cation vacancy
concentration, thus reducing oxidation
resistance.
• Ni oxide is Ni-deficient (because of Ni3+, but
charge still neutral), thus contains cation
vacancies.
• If we dope it with Li+, to maintain charge neutrality,
we need to put in 2Li+ for every Ni2+ taken out.
One Li+ will fill in the vacated Ni2+ position (site),
and the second Li+ will need to fill in an existing
cation vacancy, thus reducing the vacancy
concentration in NiO.
• If we dope it with Cr3+, then to maintain the charge
neutrality, for every 2 Cr3+ we put in, 3 Ni2+ will be
taken out. 2 Cr3+ fill in two vacated Ni2+ sites,
leaving one such site unoccupied, thus increasing
the cation vacancy concentration in NiO.

61
Doping Effect
• Zr oxide is naturally an n-type oxide, having anion (𝑂𝑂2− ) vacancies.
• Alloying Zr (valence 4+) with Ca (valence 2+) increases anion
vacancy concentration, thus reducing oxidation resistance.
• Alloying Zr with Ta (valence 5+) decreases anion vacancy
concentration, thus improving oxidation resistance.

• ZrO2 is n-type, thus contains anion vacancies.

• In such case, the key is to remember that as there
are no cation vacancies, only same number of
cations can be introduced when replacing Zr4+,
you thus need to deal with the resulted charge
imbalance by adjusting anion vacancies.
• In the case of Ca2+, for every Ca2+ in, we need to
take out 1 Zr4+ for Ca2+ to reside in. Consequently,
1 anion vacancy is created to enable charge
neutrality.
• In the case of Ta5+, for every 2 Ta5+ in, we take
out 2 Zr4+ for the 2 Ta5+ to reside in. Consequently,
1 anion vacancy has to be removed to enable
charge neutrality.

62
Oxidation Kinetics
• Rate of oxidation is dictated by the rate of diffusive migration of ions through the oxide.
• The migration rate is dependent on the concentration of vacancies.
• Increase in vacancy concentration increases oxidation rate.

Different metals show different oxidation kinetic

behaviour (i.e., corrosion weight loss vs. time):
• Linear: 𝑊𝑊 = 𝑘𝑘𝑘𝑘
Metals with non-protective surface films
Na, K PB ratio ~0.5
Ta, Nb PB ratio ~2.5
• Parabolic: 𝑊𝑊 2 = 𝑘𝑘𝑘𝑘 + 𝐶𝐶
Metals having protective surface films
Fe, Co, Cu, Ni
• Logarithmic: 𝑊𝑊 = 𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘(𝐶𝐶𝐶𝐶 + 𝐴𝐴)
thin oxide layers at low temperatures
Al, Cu, Fe
• Catastrophic: continuously increasing rate
self-sustained combustion of metal (powders)
Mg, Al, Zn
63
Oxidation Resistance of Fe-Ni-Cr Alloys
Fe-Ni-Cr alloys are the Corrosion Rate (in/year)
most commonly used alloys Cr
for general purpose high
temperature oxidation
resistance applications, Ni
largely due to their
relatively low costs, good
oxidation resistance, and
high mechanical properties.

For Fe-35Ni-13Cr at
1900℉, the oxidation
rate is 0.1 in/year

For a Fe-35Ni alloy at 1800℉ and

maximum oxidation rate of 0.05 in/year,
the Cr needs to be at least 11.5%.
64
Concluding the Chapter
• At the end of this chapter, please go back to the original learning
objectives and have a self check to see if you have achieved them.
• To help your revision and self checking of learning in this chapter, I have
designed the following tools: (1) The “I know” checklist; (2) Cloud of
keywords.

I know I can
“I know” checklist (the main causes of (general approaches to
corrosion) controlling corrosion)
1 uniform corrosion
2 galvanic corrosion
3 crevice corrosion
4 pitting corrosion
5 intergranular corrosion
6 selective leaching
7 stress-corrosion cracking
8 corrosion fatigue
9 hydrogen damage
10 oxidation
65
Cloud of Keywords
• Use this only as a suggestion list to invite for more keywords and
phrases from you.
• Share with your friends so to maximize the coverage.
• Use this list to test your own mastery of the breadth and depth of
the knowledge learnt.

Waterline corrosion Sensitisation

Droplet corrosion
Differential aeration Active-passive
Galvanic series corrosion transition
Reduction
Type 304L Anodic potential Hydrogen Deposit
embrittlement Brass
corrosion
Pilling Bedworth ratio Hydrogen
Dezincification
blistering
graphitization Weld decay
Filiform corrosion Type 316
Oxide doping Low carbon Gasket
effect grade SS Area effect of corrosion
Distance effect of
galvanic galvanic corrosion
Stabilized corrosion 18-8 steel
Blueing emf Fretting
grade SS
Cathodic corrosion
Standard conditions Austenitic stainless
for emf steel Type 304
Bronze
66
 Beyond this slide are some
supplementary information we have
used on lectures.
These are not examinable.

67
Supplementary Information

To test for the strength of piece of

material, we apply a load (stress), 𝜎𝜎.
The stress it takes for the material to
fail (deform of rupture) is called
strength.
𝜎𝜎𝑦𝑦 𝜎𝜎𝑈𝑈𝑈𝑈𝑈𝑈

If the sample contains a notch, or a

small crack, the failure of the material
is no longer only determined by the
load (stress), but also how large the
crack is. In this case, the “strength” of
the material against fracture is not
measured just by stress, but “stress
intensity factor”, 𝐾𝐾; the critical value of
𝐾𝐾 for failure is called 𝐾𝐾𝐶𝐶 .

𝐾𝐾𝐼𝐼𝐼𝐼 𝐾𝐾𝐼𝐼𝐼𝐼𝐼𝐼 𝐾𝐾𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼

68
Supplementary Information

Three Modes of Fracture

• Three basic modes of fracture, referred to as mode I, II, III.

• “Strength” of a material against fracture is measured in critical value of “stress
intensity factor” for these three modes, KIC, KIIC, KIIIC, respectively.
• Fatigue is fracture under repeated load; thus the “strength” in fatigue is
measured in critical stress intensity factor amplitude; ΔKIC, ΔKIIC, ΔKIIIC.

69
Supplementary Information

Microstructure of mild steel plate

http://practicalmaintenance.net/wp-
Optical micrograph of the cross section of a low carbon steel content/uploads/Resulfurized-and-
plate produced by rolling. The white grains are the soft and Rephosphorized-AISI-1213-Steel.jpg

malleable ferrite. The dark regions are the harder and stronger
pearlite. Because of this difference in hardness and malleability
among the different phases (including impurities like MnS),
rolling deformation produces such laminar texture in the
microstructure of mild steels. These later provide the condition
for hydrogen blistering in the plate plane. (figure below: 3D
reconstruction of the microstructure)

Steel rolling

http://www.dansteel.dk/data/files/IMG_1726.jpg
http://www.scielo.br/img/revistas/mr/v17n5/a17fig04.jpg 70
Supplementary Information

Examples microstructures of metals

71
Supplementary Information

Some examples of uses

of type 316 stainless
steel, which can be seen
as an improved version of
type 304 specifically for
marine environment
applications

72
Supplementary Information

How has it survived corrosion on seabed

for more than 70 years?
March 6, 2018 news

USS Lexington wreckage was found 3,000

m below surface and >800 lm off the east
coast of Australia in March 2018
73
 Supplementary Information
Electric arc welding techniques

Shielded Metal Arc Welding (SMAW) Submerged Arc Welding (SAW)

https://i.ytimg.com/vi/tFjGMdff3WM/maxresdefault.jpg https://phys.org/news/2017-10-neutrons-weld-
underwater-turbine-foundations.html

Tungsten inert gas welding (TIG) Metal inert gas welding (MIG)
http://mechanicalinventions.blogspot.com.au/2012/12/gas-tungsten-arc- https://sites.google.com/site/gobanengineeringnotes/welding/
welding-gtaw-or.html mags-mig-welding

74
 Salinity of Indian Ocean:
32~37 (parts per
thousand), or 3.2~3.5 wt%

Seasonal variation of temperature and dissolved https://qph.fs.quoracdn.net/main-qimg-

oxygen in water https://www.fondriest.com/envir 42acf20a9e26cd8cc1243a64f54de0a8.webp
onmental-
measurements/parameters/wat Dissolved oxygen vs water depth
er-quality/dissolved-oxygen/
Solubility of oxygen in water

75