CORROSION OF METALS

 What is Corrosion?
Corrosion can be defined as the degradation of a material due
to a reaction with its environment.

Why do metals corrode?

 Categories
 Infrastructure 16.5%
 Utilities 34.7%
 Transportation 21.5%
 Production and Manufacturing 12.7%
 Government 14.6%
 Two Main Categories
 Wet
 R.H >60%
 Electrochemical process
 Dry
 Oxidation, tarnishing
 Formation of patinas
 Dry Corrosion ‐ Oxidation
 Dry corrosion, scaling, tarnishing
 Material + Oxygen + Energy  Oxide of Metal
 M + ½O2  MO
  Rate of oxidation is important
 linear or parabolic growth rates
 Type of oxide layer formed is important 
 protecting or not
 Copper Patina
 Weathering Steels
 Cor‐Ten
 Weld‐area corrosion
 Weld material must be compatible
 Trapped water corrosion It is not a rustproof material. If
water is allowed to accumulate in pockets, those areas
will experience higher corrosion rates, so provision for
drainage must be made
 Salt‐Laden Air Environments Weathering steel is sensitive
to salt‐laden air environments like Hawaii.
 Pilling‐Bedworth Ratio
 P‐B ratio < 1
 P‐B ratio > 2‐3
 Wet Corrosion
Electrochemical Processes
A chemical reaction in which there is a transfer of electrons
from one chemical species to another
 metal atoms lose electrons OXIDATION
M  Mn+ + ne‐
 This occurs at the ANODE
CATHODE REACTIONS‐ REDUCTION
 Electrons generated at anode must go somewhere 
CATHODE
 The reaction that occurs depends on pH and is
referred to as REDUCTION
 Acidic:
2H+ + 2e‐  H2
 Neutral or basic:
02 + 2H20 + 4e‐  4(OH)‐
 Any metal ions solution may also be reduced:
Mn+ + ne‐  M 
 Uniform Corrosion KW
 Corrosion Rates C PR 
 Corrosion Penetration Rate (mm/yr) 
At
 where K = 87.6
 W = weight loss after time t (mg)
 A = exposed area (cm2)
 r = density (gcm‐3)
 Classification of corrosion environments
 Environments causing corrosion can be classified in
different categories according to their corrosivity.
 ISO 9223:1992 Corrosion of metals and alloys ‐‐
Corrosivity of atmospheres – Classification
 Prevention or Remedial Action –
UNiFORM CORROSION
 selection of a more corrosion resistant alloy (i.e.
higher alloy content or more inert alloy)
 Utilize coatings to act as a barrier between metal and
environment.
 Modify the environment or add chemical inhibitors to
reduce corrosion rate.
 Apply cathodic protection.
 Replace with corrosion resistant non‐metallic
material.
Concentration Differences
 O2 concentration differences
Crevice Corrosion & Pitting
 Effects of oxygen concentration
 Aeration Cell
 Prevention Or Remedial Action
 redesign of equipment to eliminate crevices.
 close crevices with non‐absorbent materials or
incorporate a barrier to prevent of moisture
penetration into crevice.
 prevent or remove builds‐up of scale or other solids
on surface of material.
 use of one‐piece or welded construction versus
bolting or riveting.
 select more corrosion resistant or inert alloy
 Stress concentration differences
 Electrode Potentials
 Not all metals oxidise to form ions with the same degree
of ease
 Galvanic Series
The (Non‐Aerodynamic) Area Rule
To avoid corrosion, avoid a small anodic area relative to the
cathodic area.
Anode supplies cathode with electrons
 large cathode
 will need large number of electrons
 small cathode
 will need smaller number of electrons
 Galvanic Series
 Pt
 Au
 Ag
 316 s/steel (passive)
 304 s/steel (passive)
 Copper
 Brass
 Tin
 Lead
 316 s/steel (active
 304 s/steel (active)
 Iron & steel
 Al alloys
 Zn
 Mg
 Types of Protection
1. Metals widely separated in the galvanic series must be
protected if they are to be joined.
2. Appropriate measures should be taken to avoid
contact. This can be accomplished by several methods:
 Preventing corrosion
1. For corrosion to proceed there must be an anode, a
cathode and an electrolyte joined by an external
current circuit.
2. To prevent corrosion we have to break this triangle, by
removing one of the legs.
Resistance ‐
1. By painting or coating all surfaces to increase the
resistance of the electrical circuit.
2. Insulation
3. What should we paint?
 Intergranular Corrosion
Preferentially along grain boundaries for some alloys in
specific environments
 net result  macroscopic disintegration
 typical in stainless steels
 "sensitised" 500‐800C for reasonable lengths of
time
 heat treatment process and can be remedied by
heat treatment or alloying additions
 Solving Weld Decay
 Use a low carbon grade of stainless steel
 Use a stabilised grade of steel, which includes a strong
carbide‐forming element (Nb or Ti) to lock up the carbon
 For existing components that have been sensitised, heat
treat to re‐dissolve the carbides (but this is very difficult in
practice)
 other metals
 Intergranular corrosion various alloys require the use of
different environments:
 Aluminum alloys ‐ acidified NaCl/HCl solution or
HNO3solution.
 Magnesium alloys ‐ NaCl/HF solution
 Copper alloys ‐ NaCl solution with H2SO4 or HNO3.
 Lead alloys ‐ Acetic acid or HF solutions

Microbiologically Influenced Corrosion (MIC)

1. MIC is the term used for corrosion influenced by
microbes in the water.
2. The primary concern is that the influence of these
microbes is often an extremely accelerated rate of
corrosion.

Selective Leaching (Dealloying)

Alloy containing one noble element and one base element
(e.g. brass, Cu + Zn)
Base element can dissolve leaving a matrix of the noble
element
 dezincification of brass
 graphitization of grey cast iron
 Causes loss of mechanical strength without obvious
change in shape
 Dezincification corrosion of an Admiralty brass exchanger
tube in cooling water service.
 Stress Corrosion Cracking (SCC) E
 Combined action of environment and tensile stresses ‐
NEED BOTH!!
 e.g. most stainless steels and solutions containing
chloride ions
 Stress can be external or residual
Erosion corrosion Current, i
 Erosion Corrosion, or flow‐enhanced corrosion, usually
occurs in areas where the diameter of the pipe or
direction of flow is changing. Severe metal loss can quickly
occur.
 Fretting corrosion is damage at contact surfaces rubbing
against each other (under load and in repeated relative
surface motion, as induced for example by vibration).
 The protective film on the metal surfaces is removed by
the rubbing action and exposes fresh, active metal to the
corrosive action of the atmosphere
 Prediction of Corrosion Rates
 Polarisation
 when there is a short circuit between anode and
cathode
 displacement of electrode potential from equilibrium
value
 anode becomes more cathodic and cathode more anodic
 Zn polarisation (in an acid solution)

Passivation

 Preventing corrosion
 For corrosion to proceed there must be an anode, a
cathode and an electrolyte joined by an external current
circuit.
 To prevent corrosion we have to break this triangle, by
removing one of the legs.
There are basically five methods of corrosion control:
 Change to a more suitable material
 Modifications to the environment with the use of
inhibitors
 Use of protective metallic or organic coatings
 The application of cathodic or anodic protection
 Design modifications to the system or component
 Coatings
 Metallic
 e.g
 galvanising
 tinplate
 chrome
 Ceramic
 e.g. glass, enamel
 Plastic
 e.g. PVC, epoxy, paint
 Plastics
 often classified by a curing mechanism,
 Nonconvertible
 cure solely by evaporation of the solvent with no
chemical change in the resin matrix
 can be re‐dissolved in the solvent
 Convertible
 cure primarily by a polymerization process in
which the resins undergo an irreversible chemical
change
 Metallic coatings
 More anodic – galvanising, zincalume
 55% aluminium, 43,5% zinc and 1,5% silicon.
 AZ150 (150 g/m2 minimum coating mass)
 AZ200 (200 g/m2 minimum coating mass).
 More cathodic
 chrome
 nickel
  copper  Inhibitors
 design
 tin
 Galvanising
 Example
 Galvanising
 Zinc coated steel

 Ceramic Coatings
 Glass
 Enamel
 Flame sprayed coatings
 Cathodic protection

 Cathodic protection

 Sacrificial
 Attaching a more anodic material to the material to be
protected,
 e.g. Mg blocks attached to pipelines
 By applying to the cathodic member a sacrificial coating
having a potential similar to or near that of the anodic
member.
 Inhibitors
 a substance which, when added in a small concentration
to an environment, effectively reduces the corrosion rate
of a metal exposed to that environment.
 In most cases, inhibition is achieved through interaction or
reaction between the corrosion inhibitor and the metal
surface, resulting in the formation of an inhibitive surface
film.