Corrosion

• What is Corrosion???
• Forms of Corrosion
• How to design for Corrosion
METALS WANT TO CORRODE – they want to exist as oxide compounds
because oxides contain less energy and are more stable!!
 What is Corrosion??
• Electrochemical reaction involving an anode and
a cathode.
• Deterioration of a material because of reaction
with the environment.
• Combines many elements of engineering and
impacts ALL engineering disciplines: Chemical
Engineering, Mechanical Engineering, Material
Engineering, Electrical Engineering and Civil
Engineering
 What is Corrosion??
• Corrosion involves the interaction (reaction)
between a metal or alloy and its environment.
Corrosion is affected by the properties of both the
metal or alloy and the environment. The
environmental variables include:
– pH (acidity)
– Oxidizing power (potential)
– Temperature (heat transfer)
– Velocity (fluid flow)
– Concentration (solution constituents)
 Requirements for Corrosion:

Ionic – Current Path

ANODE CATHODE

Where
Electronic Path
Corrosion
Occurs!!!!
 Anodic partial
process (oxidation
of iron)
Fe Fe 2+ + 2e-
Fe + 2H+ Fe 2+ + 2e- = Cathodic partial
+ -
2H + 2e H2 process (reduction
process – H
reduced)
• Previous corrosion was Fe in HCL.
• Can also have Fe corrode in water – most
common form of corrosion (i.e. steel left
outside).
– The anodic corrosion reaction is the oxidation
of iron: Fe Fe2+ + 2e-
– The cathodic or reduction reaction is the
reduction of oxygen: O2 + 2H2O + 4e- 4OH-
Relationship between the rate of corrosion, corrosivity of an
environment and corrosion resistance of a material.
Methods to Control Corrosion

There are five methods to control corrosion:

 material selection
 coatings
 changing the environment
 changing the potential
 design
 Factors Affecting Corrosion

Environment Material
Properties

• Nature of the corrodent • Electrochemical

• Operating Condition Activity of the material
• Polarization Effect • Homogeneity
• Passivity

Physical
Condition

• Design
Corrosion • Stress
• Couples
• External Energy
• Mechanical A
 Key Parameters:
•pH – next slide
•Oxidizing power =
measure of the tendency of a
chemical species to acquire
electrons and thereby be
reduced. Reduction potential is
measured in volts (V), or
millivolts (mV). Each species
has its own intrinsic reduction
potential; the more positive the
potential, the greater the
species' affinity for electrons
and tendency to be reduced

•Oxidizing power = measure of

relative tendency to corrode or
oxidize – a solution of low
oxidizing power will corrode only
those metals at the lower end
(more active) of an emf series.

Description of Environment in terms of oxidizing power (E) and pH

 pH = - log10[H+]

pOH = - log10[OH-]

Pure water has a pH of 7

Strong acids have lower pH’s which

means they have more H+ ions!

Strong alkali’s have low pOH’s

which means they have more OH-
ions!
The more ions, the more “toxic” the
solution. But not that simple – go to
Figure 1. The scales of pH and pOH. materials Pourbaix (potential pH
diagram)!!
 Recall, Corrosion is the degradation of a metal by an electro-chemical reaction.

One half of this is the dissociation reaction of a metal M into a metal ion, M z+ , releasing
electrons e-
M  Mz+ + ze-
where z, an integer of 1, 2, or 3, is the valence of the metal.

Acidic environments, with high [H+] (and thus low pH) stimulate this reaction; thus a metal
such as copper, in sulphuric acid solution, reacts rapidly

Cu  Cu2+ + 2e
H2SO4  2H+ + SO42- Cu2+ + SO42-  CuSO4
  

Some metals are resistant to attack by some acids because the reaction
product, here CuSO4 , forms a protective surface layer; thus lead-lined
containers are used to process sulfuric acid because lead sulfate is
protective.
Most metals are immune to attack by alkalis because their hydroxide,
formed in the reaction, is protective. There are, however, exceptions,
notably aluminum, that forms non-protective aluminum hydroxide,
Al(OH)3.
Metals behavior as function of oxidizing power (E) and pH
The “Right”
material depends
on the
environment.

Polarization can
have a major
effect on metal
stability.
Eight forms of corrosion can be identified based on
appearance of the corroded metal. These are:

• Uniform
• Galvanic, or two-metal
• Pitting
• Crevice or Concentration Cell
• Intergranular
• Stress corrosion cracking
• Erosion-corrosion
• De-alloying
 Uniform Corrosion
• Most common – i.e. steel exposed to environment.
• Uniform in nature – leaves scale or deposit over entire exposed
area – this is called rust which is really iron-oxide – Fe(OH)3 or
Fe2O3
• Fairly predictable and therefore the effects can be minimized!
– i.e. corrosion proportional to current, proportional to time (corrosion rate)
• < 2 mils/yr – necessary for food containment
• 20 mils/yr = conservative estimate for general atmospheric corrosion.
• Really general form of galvanic corrosion – i.e. anode and cathode
random and in same material!
• Prevented by
– Removing electrolyte (i.e. lower relative humidity below 30%)
– Choose material that doesn’t rust in a particular environment – look at
potential-pH diagram!
– Add design “allowance” for rust
Uniform (or general) corrosion of steel in water:
 Uniform Corrosion
• Corrosion penetration rate (mils/yr):
Constant
depending on
desired units

Weight loss after

KW exposure time t

CPR 
At
Exposure time

density
Exposed area
 Uniform Corrosion:
• Corrosion rate in
terms of current:

i
r r = rate in terms of mol/m2-s

nf i = current per unit surface area of

material corroding
N = # of electrons associated with
ionization of metal ion
F = constant = 96,500 C/mol
 A rate of less than 2 MPY is necessary for food
containers
A rate of less than 20 MPY for many industrial
applications
 EXAMPLE 1:
MIG Welding tank

METAL: Carbon Steel

ENVIRONMENT: Industrial en
FORM OF CORROSION: General
METHOD TO CONTROL! Surface is painted for protection
 EXAMPLE 3:
Machine Shop Table

METAL: Carbon Steel

ENVIRONMENT: Industrial en
FORM OF CORROSION: General
METHOD TO CONTROL! Surface is painted for protection. Aggressive environment (molds dragged across
surface) led to scrapping off of paint. Note corrosion where paint is scraped off in line.
 EXAMPLE 4:
Dumbbell

METAL: Cast Iron

ENVIRONMENT: Indoor (exercise room)
FORM OF CORROSION: General
METHOD TO CONTROL! Surface is painted for protection. Note, portion of dumbbell where paint was
abraded off due to handling shows significant corrosion while areas that are better protected from abrasion
retained paint and therefore show little corrosion.
 EXAMPLE 5:
House Drain and
Drain Cap

1 year old
cap

30 year old
cap
METAL: Cast Iron
ENVIRONMENT: Residential basement – water exposure
FORM OF CORROSION: General
METHOD TO CONTROL! Surface is painted for protection. Note the 1 year old cap shows significant
corrosion already!
60 YEAR OLD OIL
PUMP
Kinzua Viaduct – see photos!! (1882/1900)
 Crevice or Concentration Cell
• Local attack (corrosion) in crevice due to change
in chemistry of electrolyte making it more
aggressive – i.e. stagnant fluid = lower oxygen
concentration = decrease in pH.
• Can be between metal surfaces or non-metal
surfaces in contact with metal.
• Very destructive since highly localized!
• How design around?
– Leak proof weld
– Better gasket design
– Avoid stagnant water
 Crevice or Concentration Cell
• Good example – crevices and recesses or
under deposits of dirt or corrosion
products where the solution is stagnant.
– Crevice must be wide enough to allow
solution to penetrate yet narrow enough for
stagnancy (i.e. few thousandths of an inch).
Crevice or Concentration Cell
Depending on the environment developed in the crevice and the nature of
the metal, the crevice corrosion can take a form of:

pitting (i.e., formation of pits),

filiform corrosion (this type of crevice corrosion that may occur on an
aluminium surface underneath an organic coating),
intergrannular attack, or
stress corrosion cracking.
KEY – In crevice there
are high
concentrations of H+
and Cl- ions which are
especially corrosive!

WHY? Low oxygen

levels (stagnant) means
ions have nothing to
react w/ except the
metal!!
Crevice corrosion between
pipe and I-beam: Rubber pads just accelerated
the attack – why???
 EXAMPLE 2:
Track Fastener -
Taipei

A manufacturer’s
nightmare!!

METAL: Ductile Cast Iron per ASTM D412

ENVIRONMENT: Corrosive Salt Water (Salt Spray)
FORM OF CORROSION: Crevice Corrosion + General
METHOD TO CONTROL! Surface is degreased, sand blasted and phosphatized for corrosion protection
Surface is then painted with Chemlock elastomer primer and bonding adhesive.

Note: Salt water trapped between elastomer and steel led to crevice corrosion which led to underbond
corrosion. The adhesive to metal bond then failed causing the elastomer to delaminate. Resulted in return
of several million dollar worth of product + replacement costs (labor and components).
 Pitting Corrosion:
• Extremely localized corrosion that leads to the creation
of small holes in the metal surfaces
• The driving power again is the lack of oxygen around a
small area. This area becomes anodic while the area
with excess of oxygen becomes cathodic.
• More of a problem in stagnant solutions.
• Very destructive since highly localized.
• Prevention?
– Material selection
– Avoid stagnant flow
 Pitting Corrosion:
• Similar in chemistry to crevice corrosion except it
happens in pits.
• Occurs in “pits” of metal surfaces where again,
electrolyte is aggressive (stagnant).
• More of a problem in stagnant solutions.
• Very destructive since highly localized – may go
undetected until failure occurs.
• Gravity causes pit to grow downward – corrosion
rate can increase with time
 Pitting Corrosion:
• A pit can be initiated by a localized surface
defect, scratch or slight variation in
composition.
• Stainless steels are especially susceptable
to this form of corrosion.
• Prevention?
– Material selection
– Avoid stagnant flow
– Alloy SS with about 2% molybdenum.