CHEM ENG 3029_7055

Materials Science and Engineering

 Lecture 10

Selective Attack and Localised Corrosion

 Lecture Structure
Lecture 10 (Selective Attack and Localised Corrosion) is divided into the
following sections:
• L10.1 – Selective Attack Corrosion
– Introduction to Selective Attack and Localised Corrosion
– Crystal Structure
– Surface Structure
– Grain Boundaries
– Inter-Granular Corrosion
– Selective Leaching
• L10.2 – Localised Corrosion
– Introduction to Localised Corrosion
– Differential Aeration
– Pitting
– Crevice
– Microstructure
• L10.3 – Environmentally Induced Cracking (EIS)
– Origin of EIS
– Stress Corrosion Cracking (SCC)
– Corrosion Fatigue Cracking (CFC)
– Hydrogen Induced Cracking (HIC)

Reference Book: W. D. Callister and D. G. Rethwisch, Materials Science and Engineering: An Introduction, John Willey & Sons ISBN:
9781119321590

Complementary Reference Book: R. W. Revie and H. H. Uhlig, Corrosion and Corrosion Control: An Introduction to Corrosion Science and
Enginering, Wiley ISBN: 9780470277270
 Lecture Structure
• L10.1 – Selective Attack Corrosion
– Introduction to Selective Attack and Localised
Corrosion
– Crystal Structure
– Surface Structure
– Grain Boundaries
– Inter-Granular Corrosion
– Selective Leaching
L10.1 – Selective Attack Corrosion
o Learning Objectives

✓ What is selective attack corrosion and how it works in

different scenarios

✓ Mechanisms of selective attack corrosion through

crystallinity, inter-granular corrosion, and selective
leaching

University of Adelaide 5
L10.1 – Selective Attack Corrosion
• Introduction to Selective Attack and Localised Corrosion
– Selective attack and localised corrosion are very common
• Often more difficult to detect than uniform corrosion
– Testing/inspection may miss corroded area
• Potentially more dangerous than uniform corrosion
– Greater depth of material lost more rapidly
» Greater loss of strength with time
» Often occurs in areas already highly stressed (e.g., joints)

University of Adelaide 6
L10.1 – Selective Attack Corrosion
• Introduction to Selective Attack and Localised Corrosion
– Selective attack and localised corrosion
– Potentially very serious consequences for:
• Pressure vessels and pipelines
• Structural parts

– Galvanic corrosion (already discussed) is highly relevant

– Normally applies to dissimilar metals
– However commercial metals are rarely uniform

– Non-uniformity of commercial metals

– Defects in crystal structure
• Can be useful, such as ductility
– Grain boundaries
• Formed on cooling
– Volume defects
• Cracks – always undesirable > reduce the failure stress
• Voids caused by entrapment of air and gases
• Inclusions of impurities (cathode or anode) in the metal

University of Adelaide 7
L10.1 – Selective Attack Corrosion
• Crystal Structure
Defects in crystal structures

Can be useful
– Substitution can increase rigidity or stiffness
• Movement of dislocation gives ductility

University of Adelaide 8
L10.1 – Selective Attack Corrosion
• Crystal Structure
Defects in crystal structure
– Atoms in perfect crystal lattice have the lowest thermodynamic
energy
– Atoms or groups of atoms in defect sites have higher free energy
than in the perfect lattice
• Gives immediate potential for corrosion
– Any resulting corrosion is very localised and results in great loss of
strength (impact on mechanical properties)
– Particularly dangerous in pressure vessels or aircraft structures

University of Adelaide 9
L10.1 – Selective Attack Corrosion
• Surface Structure
Selective attack and localised corrosion are very dependent
on structure and surface of the metal
1 and 2 Grain orientation 5 Depletion of one component in alloy
3 Grain boundary 6 Inclusions
4 Grain boundary precipitation 7 Porosity of oxide film
8 Discontinuities in oxide film

University of Adelaide 10
L10.1 – Selective Attack Corrosion
• Grain Boundaries
• Formed on cooling the metal
from the melt
• Solidification starts in coolest
areas
– Accompanied by release of latent
heat
• Solidification takes place at
~constant temperature
Cooling curve for a pure metal
– Solid areas grow in size and trap
Alloys show similar discontinues at
remaining liquid B and C but not at constant
temperature
These are known as “arrests”

University of Adelaide 11
 L10.1 – Selective Attack Corrosion
• Grain Boundaries
Boundaries between individual crystals
– Micrograph is obtained by etching
• Preferential corrosion at grain boundaries

a) Nucleation of crystals in melt

0.15% carbon steel fully annealed
etched with 2% HNO3 in ethanol
University of Adelaide
b) Growth of crystals into dendrites
(dendrite is skeleton crystal formed of
branches thrown out from nucleus)
c) Complete solidification
d) Final grain structure
12
L10.1 – Selective Attack Corrosion
• Inter-Granular Corrosion
Grain boundary attacked owing to presence of precipitates
and segregates
– Grain boundaries are preferred site for precipitates and
segregates in many alloys
• Precipitates and segregates are physically distinct from the bulk
metal
• Have their own thermodynamic energy
– Two types
• Intermetallics
• Compounds

University of Adelaide 13
L10.1 – Selective Attack Corrosion
• Inter-Granular Corrosion
– Intermetallics
• Species formed from metal atoms and having distinct formula
– Can be anodic or cathodic to the metal
– Compounds
• Formed between metallic and non-metallic elements
– Hydrogen, carbon, silicon, nitrogen and oxygen
– Iron carbide and manganese sulphide
– Both are important constituents of steel
– Both are cathodic to ferrite
– Any metal with intermetallics or compounds is susceptible to inter-
granular corrosion
• Common in austenitic stainless steels (e.g., 18/8 series )
• Also occurs in ferric and two-phase stainless steels
• Nickel-based corrosion resistant alloys

University of Adelaide 14
L10.1 – Selective Attack Corrosion
• Inter-Granular Corrosion
Aluminium alloys
– High strength aircraft alloys rely on control of precipitates
• At the grain boundaries and within grains
– Determines material strength
– Can cause minute corrosion cells
– Copper and Iron based precipitates (e.g., CuAl2 and FeAl3)
• Cathodic to surrounding metal
– Magnesium and zinc based precipitates (e.g., Mg5Al8 and MgZn3)
• Anodic to surrounding metal
– Presence of electrolyte leads to corrosion
• Anodic precipitates dissolve to leave porous metal
• Cathodic precipitates lead to corrosion of main metal
– Both lead to serious weakening of structure, hence the need for
regular inspections of airframes

University of Adelaide 15
L10.1 – Selective Attack Corrosion
• Inter-Granular Corrosion
– Austenitic stainless steels
• A304 (Cr 18% Ni 8%)
– Significant problem from an
engineering viewpoint
• Sometimes called weld decay
– Applies to any system with
precipitation at grain boundaries
– Dependent on the carbon content of
the steel
• For carbon > 0.03% 2 stable phases: g and a mixed
carbide called chromium carbide (FeCr)23C6
• Fast quench from over 1000 oC in oil or water
minimises carbide formation
• Slow cooling maximises carbide formation (two
phases – anode and cathode, not good ) Simplified diagram of
carbon solubility in A304

University of Adelaide 16
L10.1 – Selective Attack Corrosion
• Inter-Granular Corrosion
Austenitic stainless steels
– Main risk occurs in re-heating
• Especially 600–850 oC
– Chromium carbide precipitation
occurs at grain boundaries
• Chromium metal content is effectively
reduced (<12%)
• Not enough Cr to create local oxide
layer
• Very dangerous from corrosion view
point Intergranular decay in
• Material said to be sensitised – no A304 stainless steel
longer “stainless”
– Whole grains can become detached

University of Adelaide 17
L10.1 – Selective Attack Corrosion
• Inter-Granular Corrosion
Austenitic stainless steels
– Main risk occurs in re-heating
• 600–850 oC is common industrial temperature
• e.g., furnaces or welding
– Do not use A304 in applications where it may be heated
• In use or during fabrication e.g., welding
– Welding is feasible provided
• Material heat treated afterwards to dissolve precipitate
– Alternatively use A304L (low carbon version)
– Below 600 oC low risk
• Diffusion of Cr too slow for carbon precipitation to occur

University of Adelaide 18
L10.1 – Selective Attack Corrosion
• Inter-Granular Corrosion
Alternative materials to A304
– A304 L
• Low carbon content < 0.03%
• Must not use oily rags during welding!
(C pick-up)

– Stabilised stainless steel

• Add titanium or niobium
• These elements form carbides in
preference to Cr
• Grain boundary areas are then not Cr
depleted

University of Adelaide 19
L10.1 – Selective Attack Corrosion
• Selective Leaching
Net removal of one element from
an alloy
– Also known as dealloying or
demetallification
Very common with brass
– Dezincifaction
• Often accompanied by
characteristic patterning
– Also involves loss of nickel and
aluminium alloys

University of Adelaide 20
L10.1 – Selective Attack Corrosion
• Selective Leaching
Types of brass
– Single phase brass
• (Cu 70% + Zn 30%)
• Used where malleability is important (e.g., tubes)
• Dezincification overcome by adding 0.05% arsenic
– Two phase brass
• (Cu 60% + Zn 40%)
• Poor cold working characteristics
• Restricted to castings
• All attempts to overcome dezincification have failed

University of Adelaide 21
L10.1 – Selective Attack Corrosion
• Selective Leaching
• Aluminium bronze sea-water
valve
– Wasted by erosion but not de-
alloyed
• Repaired by plating with
60/40 brass along shank and
along sealing surface
– Deposited brass areas have
suffered dezincification Example of dezincification
Note the clear grain structure

University of Adelaide 22
L10.1 – Selective Attack Corrosion
• Selective Leaching
• Brass casting for water supply system
– Dark inner areas dezincified
– Component seriously weakened
• Broken off at left hand end

• Brass bolt
– 12 mm diameter
• Corrosion penetrated to depth of 3 mm
• Note layered microstructure

University of Adelaide 23
L10.1 – Selective Attack Corrosion
• Selective Leaching
60/40 Brass
– Two phases a and b
• Ecorr
– a = –230 mV SCE
– b = –285 mV SCE
• Would expect b to be more anodic
than a

University of Adelaide 24