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)
What is Corrosion??
Cost? EQUALS 3 5% of GNP/ year or
$700/person based on 2006 estimate = $300
billion US only (corrosion of steel the biggie)
Combination of the material and its environment
- Examples:
No Problem:
Lead in Water
Aluminum in atmosphere
Nickel in hydraulic fluid
BAD:
Steel in marine environment
Cu in Ammonia
SS in chloride (Sea water)
Lead in wine
Definition of Corrosion

Corrosion is the deterioration of materials

by chemical interaction with their
environment. The term corrosion is
sometimes also applied to the degradation
of plastics, concrete and wood, but
generally refers to metals.
Anodic & Cathodic Reactions
Effects of corrosion
Losses are economic and safety:
Reduced Strength
Downtime of equipment
Escape of fluids
Lost surface properties
Reduced value of goods

The consequences of corrosion are many and varied

and the effects of these on the safe, reliable and
efficient operation of equipment or structures are
often more serious than the simple loss of a mass of
metal. Failures of various kinds and the need for
expensive replacements may occur even though the
amount of metal destroyed is quite small.
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
 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


Figure 1. The scales of pH and pOH.
pH = - log10[H+]
pOH = - log10[OH-]
Pure water has a pH of 7
Strong acids have lower pHs which
means they have more H+ ions!
Strong alkalis have low pOHs
which means they have more OH-
ions!
The more ions, the more toxic the
solution. But not that simple go
to 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,
Mz+ , 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
Cu 2+
+ SO42- CuSO4
H2SO4 2H + SO4
+ 2-

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.
Often several approaches to control corrosion

Often several system constraints pertain

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
Dealloying
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 doesnt 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 Question: The tank sees tension
FORM OF CORROSION: General stress due to internal gas pressure,
METHOD TO CONTROL! Surface is painted for protection would this lead to stress corrosion
cracking as well as general??
 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 stagnet.
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 manufacturers
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.
Underground corrosion

Buried gas or water supply pipes can

suffer severe corrosion which is not
detected until an actual leakage
occurs, by which time considerable
damage may be done.
Electronic components

In electronic equipment it is very important that

there should be no raised resistance at low current
connections. Corrosion products can cause such
damage and can also have sufficient conductance
to cause short circuits. These resistors form part
of a radar installation.
Corrosion influenced by flow-1

The cast iron pump impeller shown here

suffered attack when acid accidentally entered
the water that was being pumped. The high
velocities in the pump accentuated the
corrosion damage.
Corrosion influenced by flow 2

This is a bend in a copper pipe-work cooling system.

Water flowed around the bend and then became
turbulent at a roughly cut edge. Downstream of this
edge two dark corrosion pits may be seen, and one
pit is revealed in section.
Safety of aircraft

The lower edge of this aircraft skin panel has

suffered corrosion due to leakage and
spillage from a wash basin in the toilet. Any
failure of a structural component of an
aircraft can lead to the most serious results.
Influence of corrosion on value

A very slight amount of corrosion may not interfere with

the usefulness of an article, but can affect its
commercial value. At the points where these scissors
were held into their plastic case some surface corrosion
has occurred which would mean that the shop would
have to sell them at a reduced price.
Motor vehicle corrosion and safety

The safety problems associated with corrosion of

motor vehicles is illustrated by the holes around the
filler pipe of this petrol tank. The danger of petrol
leakage is obvious. Mud and dirt thrown up from the
road can retain salt and water for prolonged periods,
forming a corrosive poultice.
Corrosion at sea

Sea water is a highly corrosive electrolyte towards

mild steel. This ship has suffered severe damage in
the areas which are most buffeted by waves, where
the protective coating of paint has been largely
removed by mechanical action.
Aluminium Corrosion

The current trend for

aluminium vehicles is
not without problems.
This aluminium alloy
chassis member
shows very advanced
corrosion due to
contact with road salt
from gritting
operations or use in
coastal / beach
regions.
Damage due to pressure of expanding
rust
The iron reinforcing rods in
this garden fence post have
been set too close to the
surface of the concrete. A
small amount of corrosion
leads to bulky rust
formation which exerts a
pressure and causes the
concrete to crack. For
structural engineering
applications all reinforcing
metal should be covered by
50 to 75 mm of concrete.
Corrosion of plastics
Not only metals
suffer corrosion
effects. This dished
end of a vessel is
made of glass fibre
reinforced PVC. Due
to internal stresses
and an aggressive
environment it has
suffered
environmental
stress cracking.
Galvanic corrosion

This rainwater guttering is made of

aluminium and would normally resist
corrosion well. Someone tied a copper aerial
wire around it, and the localised bimetallic
cell led to a knife-cut effect.
Galvanic corrosion

The tubing, shown here was part of an aircrafts

hydraulic system. The material is an aluminium alloy
and to prevent bimetallic galvanic corrosion due to
contact with the copper alloy retaining nut this was
cadmium plated. The plating was not applied to an
adequate thickness and pitting corrosion resulted.
Galvanic corrosion
This polished
Aluminium rim was
left over Christmas
with road salt and
mud on the rim.
Galvanic corrosion
has started between
the chromium plated
brass spoke nipple
and the aluminium
rim.
Galvanic corrosion
Galvanic corrosion
can be even worse
underneath the
tyre in bicycles
used all winter.
Here the corrosion
is so advanced it
has penetrated the
rim thickness.
Corrosion prevention