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MEC281

MATERIALS SCIENCE

CHAPTER 5
CORROSION & PREVENTION METHODS

Rasdi bin Deraman


Fakulti Kejuruteraan Mekanikal
UiTM Pulau Pinang
CORROSION
What is the corrosion process?
Corrosion- Deterioration / destructive of a metal or its
alloys by oxidation.
Metals will corrode if they come in contact with; moist
atmosphere, air, water, salt solutions, acids, or alkalines.

Example: the tarnishing of silver, iron


rusting, dissolution of metal in acid solution

Disadvantage: economic terms higher expense to spent


for corrosion prevention and maintenance/ replacement
Advantage: etching, dry cell batteries
ELECTROCHEMICAL
CONSIDERATION
• Corrosion process is normally electrochemical process.
• Involve chemical reaction.
• ē transfer from one chemical species to another.
ELECTROCHEMICAL
CONSIDERATION
• 3 important process in corrosion
– Electrolyte (any solution that contains ion)
– Anode (oxidation)
– Cathode (reduction)
Anode
• Oxidation process occurs
• Oxidation –metal atom lose/give up ē
– M  M n+ + n ē
– i.e ; Fe  Fe 2+ + 2 ē

• Negative electrode
Cathode

– Reduction reaction occurs


– Gains of ē (ē from metal atom that is
oxidized)
– The reaction at cathode
• M n+ + ē  M n-1
• Or M n+ + nē  M
• i.e Mg 2+ + 2ē  Mg
– Positive electrode
The Standard EMF series
• Measured cell voltage

• Represent only diff. in electrical


potential from reference cell

• Reference cell : using standard


hydrogen electrode
Standard EMF series
Electrode potential
• Not all metallic materials oxidize to form ions
with the same degree of ease
• two half-cell reactions for Fe and Cu
Fe  Fe2+ + 2ē half-cell reactions
+ (oxidation)
Cu2+ + 2ē  Cu half-cell reactions
(reduction)
Fe + Cu2+  Fe2+ + Cu Overall reaction

Overall cell potential


ΔV = V + V2
1

=
0.340 + 0.440
= 0.780 V
• Example:
• One half of an electrochemical cell consists of
a pure nickel electrode in a solution of ions;
the other is the cadmium electrode immersed
in the solution. Write the spontaneous overall
reaction and calculate the voltage that is
generated.

• Solution:
Galvanic series- represents the relative
reactivity of a number of metals and
commercial alloys in seawater
TEST 2 MEC
281
• 4 APRIL 2009
• 2.00 – 4.00 PM
• CHAPTERS: 3, 4, 5 & 6
Corrosion rate
• The rate of material removal as a
consequence of the chemical action

• the weight loss can be converted to


corrosion rate in units
– mm/yr
– mpy (mils per year)

• Corrosion current is used to generate


a corrosion rate
Q =(nFW)/M ………………..(1)
But Q = It
(nFW)/M = It ………….……(2)

W= (ItM)/nF ………….…....(3)

But W is mass = (density, ρ ) x (volume)


where Volume = (area, A) x (thickness, H)
Thus, W = ρAH and substitute in eq (3)

ρAH = (ItM)/nF ………….…(4)


H/t =(IM)/(nFρA) ……….....(5)
where H/t is corrosion rate, CR in unit cm/S
I
Current density, corr = current flow/ Area, A/cm2
Icorr = I/A

I
From eq. (5), Corrosion rate, H/t = {( corr)(M)}/(nFρ) ……….....
(6)
where this rate is in unit cm/s.
The normal practice, unit of Corrosion rate, CR are in mpy and
mm/yr.
CR = { (128,704.7 x Icorr x M)/ n ρ } unit mpy

CR = { (3269 x Icorr x M)/ n ρ } unit mm/y


n = no. electrons involved in half cell reactions
Icorr = ampere/cm square 
M =atomic weight in grams/mol
ρ = Density in grams/cm cubic
6 Factors Influence Corrosion Rate 

Factor Condition Corrosion Rate


Concentration of solution High
Stress intensity High
Temperature High
Oxygen High
Flow rate of liquid High
Surface contact area High
Experiment 1:
Specimens Steel and Copper immersed in
an agar-agar electrolyte. Steel act as anodic
site and Copper act as cathodic site.
Experiment 2:
Place the straight nail and the bent nail in
one of the petri dishes. Be sure the nails
do not touch each other. Pour the
lukewarm agar-agar over the nails until
they are covered.
FORMS OF CORROSION
General (Uniform) Corrosion

This is the most common form of corrosion.


In fact, all metals are attacked by uniform
corrosion, but to different grades. It
proceeds by a chemical or electrochemical
reaction over a large surface area, effectively
thinning and eventually consuming the entire
thickness of the metal.

Electrochemical reactions occurs at more or less, the same


rate over the entire surface.
General (Uniform) Corrosion (Cont…)
Failure caused by uniform attack
can be easily and accurately
predicted. Timely visual
examination, if possible, of
selected points at the thinnest
parts of a component or a
structure is often sufficient, or
some simple tests, e.g. immersing
a sample in the solution involved,
will provide accurate corrosion
data for the prediction of the
service life of a component.
Galvanic corrosion

◆ Occurs when 2 metals


having different
compositions are
electrically coupled and
exposed to an electrolyte

◆ The more electro-positive = cathode,


◆ The least electropositive = anode
Mechanism of galvanic
corrosion
Three conditions must be present:
• Electrochemically dissimilar metals must be present;
• These metals must be in electrical contact; and
• The metals must be exposed to an electrolyte.
• When a galvanic couple forms, one of the
metals in the couple becomes the anode and
corrodes faster than it would all by itself,
while the other becomes the cathode and
corrodes slower than it would alone.

• It is this potential difference that is the


driving force for galvanic current flow

• area ratio of metal also influence the


galvanic corrosion rate

• Normally occurs at joining i.e fastener,


welded
• When a galvanic couple forms, one of the
metals in the couple becomes the anode and
corrodes faster than it would all by itself,
while the other becomes the cathode and
corrodes slower than it would alone.

• It is this potential difference that is the


driving force for galvanic current flow

• area ratio of metal also influence the


galvanic corrosion rate

• Normally occurs at joining i.e fastener,


welded
Steel pipe has
corroded near where
it was in contact
with a gate valve
Copper alloy.

Aluminum helicopter
blade has corroded near
where it was in contact
with a steel
counterbalance.
Stress Corrosion Cracking (SCC)
• The SCC occurred because of the
simultaneous effects of tensile stress and
corrosion. Stress may be internally or
externally applied. Internal stresses are
produced by non-uniform deformation during
cold working, by unequal cooling from high
temperatures, and by internal structural
rearrangement involving volume changes.
Stresses induced by press and shrink fits, and
those in rivets and bolts are internal stresses.
Stress Corrosion Cracking
(SCC)

◆ Intergranular ...
Stress Corrosion Cracking
(SCC)

◆ Transgranular ...
Erosion-corrosion
• Corrosion accelerated by impact by solid
particles
• These may remove metal, or they may just
remove oxide and allow metal to corrode more
quickly
• Erosion corrosion is commonly found in
piping, especially at bends, elbows and
abrupt changes in pipe diameter-
position where the fluid changes
direction or flow suddenly becomes
turbulent. Propellers, turbine blades,
valves and pumps are also susceptible to
this form of corrosion.
Pitting Corrosion
• As the name suggests, pitting is an
extremely localised attack that results in
pits, i.e., holes of various sizes. They are
called holes because that the diameter of the
attack is generally small and that the depth-
to-diameter ratio is often greater than 1.
They may sometimes cluster together to give
a look of rough surfaces.

• Pitting is one of the most destructive forms


of corrosion; it causes equipment to fail
because of perforation with only a small
percent weight loss of the entire structure.
Most pits develop and grow in the direction
of gravity, starting from horizontal surfaces
and growing downwards.
Pitting corrosion
◆ Caused by Chlorides (halides)
◆ Passive metals & alloys = susceptible

Mechanism …
Crevice corrosion
Crevice corrosion is a localized form of corrosion
usually associated with a stagnant solution on the
micro-environmental level. Such stagnant
microenvironments tend to occur in narrow crevices
such as those formed under gaskets, washers,
insulation material, fastener heads, surface deposits,
disbonded coatings, threads, lap joints and clamps,
under porous deposits and in many other similar
situations.
Example of Crevice
corrosion
Introduction
The easier technique to prevent corrosion occurred:
i. Understand the theory of all types of corrosion.
ii. The factors influenced corrosion rate.
Revision: 

Type of Corrosion Cause


Galvanic corrosion Dissimilar metals are in electrical
contact.
Stress corrosion cracking Stress + Susceptible materials +
(SCC) Corrosive environment
Erosion corrosion Suspended particle in fluid motion

Crevice corrosion Narrow crevices associated with a


stagnant solution.
6 Factors Influence Corrosion Rate 

Factor Condition Corrosion Rate


Concentration of solution High
Stress intensity High
Temperature High
Oxygen High
Fluid flow rate High
Surface contact area High
Corrosion prevention and
protection
• 5 general techniques to consider:

– Material selection and treatment


– Environmental alteration
– Design consideration
– Coating
– Cathodic protection
1. Material selection and

treatment
Selection of material depends on the corrosion environment:

For example;
Application in fresh water
• Suitable metal: cast iron, steel, Al alloys, Cu alloys and
some stainless steel.

Application for seawater environment


• Titanium, brass, some bronzes, cooper-nickel alloys,
nickel-chromium-molybdenum alloys.

Suitable metal for atmospheric application


• Al alloys, cu alloys, galvanized steel.
1. Material selection and treatment (Cont..)

• Heat treatment for relieve the residual stress


induce in metal that formed into finished shapes
by bending

• Another factors that will be consider


– Mechanical properties
– Material cost
– Material fabrication
– Availability of materials
a) Mechanical properties
– When operation condition become aggressive,
material from combination 2/3 metal are needed
– Effect of temp. will influence the mechanical
properties i.e application of plain carbon steel is
limited to 316-343oC due to loss of strength and
susceptibility to oxidation and corrosion. Highly
alloyed Ni-Cr-Fe alloy are adequate to corrosion
resistance at elevated temp. compare to 18Cr-12Ni.
18Cr-12Ni sustain oxidation resistance at temp. up
to 816oC and strength reduce above 650oC.
b) Material cost
– Life cycle cost or cost effectiveness rather than
initial cost.
c) Material fabrication
– Material should be selected on the basis of
their maintainability as well as their fabrication
ability.
– Need to consider the ease of modification or
repaired after exposure to operating condition.

d)Availability of materials
– Consideration for future availability for repairs
or replacement or alternative replacement
materials.
2. Environmental alteration
• Decrease the velocity of corrosive fluid
• Use lower temperature
• Remove O2 from water solution by deaerated process
• Reduce the concentration of corrosive ions in a solution
• Adding inhibitors in system
– Scavengers type- react with and virtually eliminate a
chemically active species in solution such as dissolved O2

– Absorption type- attach themselves to the corroding surface


and interface with either oxidation/reduction reaction or
form a very thin protective coating
3. Design consideration
• Prevent the formation of galvanic cell by using
similar metal or alloys or using non metallic
connector ( fitting, gasket) to electrically insulate
the two dissimilar metal.

• Weld rather than rivets. Or choose rivets that are


cathodic to the materials being joined.

• Make the anode area larger than the cathode


area.
• Avoid sharp bends in piping system when flow occurs.
Erosion corrosion will occur at areas in which the fluid
direction changes sharply, for example Cavitations.

• Design components so that fluid system are closed to


avoid continuously dissolve gas.

• Easy removal and replacement of parts that are


expected to fail rapidly in service, must be design

• The design should allow for complete drainage and


easy washing
4. Coating
• Physical barrier applied on surfaces in the form
of films.

• Used to isolate anode and cathode region.

• Important condition:
– coating must be nonreactive in the corrosive
environment.
– Resist to mechanical damage that exposes
the bare metal to corrosive environment.
• Types of material for coating:
– Metals (Metallic coating); Ceramic (Inorganic
coating) & Polymers (Organic coating)

• Metallic coating
– Acts as sacrificial anodes instead of coated
metal.
– i.e: steel are coated with Zinc-plated or tin-
plated.
– Metal coating are plated by electro plating
process.
– metal./ part to be plated is made as cathode.
The electrolyte is a solution of a salt of the
metal to be plated and direct current is
applied.
• Inorganic coating/ceramic coating
– i.e reaction vessels can also be lined with
corrosion-resisitant teflon.
– Stable, adherent, nonporous, noconducting oxide
layer.
– i.e glass fused coating a steel.

• Organic coating
– Polymeric material, pints, varnish.
– Cheaper.
5. Cathodic protection
• Generally, Cathodic protection can be applied to
all types of corrosion but involve highly coast.
• The principle of cathodic protection is
connecting the metal (body) to be protected with
an external anode or (to the electrical DC
current) so that all areas of the metal surface
become cathodic and therefore do not corrode.

• Two types of Cathodic protection:


i. Sacrificial anode
ii. Impressed current
Passivity?
Caused by thin
hydroxide layer
forming on
metal surface,
protecting the
metal from
anodic
dissolution
However, oxide
will itself
corrode under
certain
conditions
a) Sacrificial anode
• Employ reactive metals as auxiliary anodes that are
directly electrically connected to the metal to be
protected.

• The sacrificial anode corrodes, supplies electron to


the metal and thereby prevents an anode reaction
at metal.

• The metals commonly used, as sacrificial anodes


are aluminium, zinc and magnesium.
Eg. Aluminium,
Magnesium & Steel structure
Zinc anode
• The current has to flow in a loop and therefore the surface
of structure that can be protected is the submerged surface
that are received protection current from anodes.

STEEL PROTECTED
PIPE SURFACE
UNPROTECTED
SURFACE
• Structures that are commonly protected by cathodic
protectionare the exterior surfaces of:
– Pipelines
– Ships’ hulls
– Storage tank bases
– Jetties and harbour structures
– Steel sheet, tubular and foundation pilings
– Offshore platforms, floating and sub sea
structures
• Cathodic protection is also used to protect the
internal surfaces of:
– Large diameter pipelines
– Ship’s tanks (product and ballast)
– Storage tanks (oil and water)
– Water-circulating systems.
Criteria for sacrificial anodes
• A corrosion potential that is sufficiently
negative for the specific application; in
general, alloying additions are made to
make the potential more negative than that
of the unalloyed basis metal

• A high anode efficiency, which means that


impurities that result in self corrosion
must be absent or minimum.

• An ability to remain active and to corrode


uniformly and not to become passive
b)WhysImpressed
houlduseICCP? current Cathodic
Protection
•Steelstructurethatwillbeprotectedislarge
•Protectioncurrentrequirementishigh
•Coatingqualityvariesinalargerange
•Resistivityofsoilishigh
•Sourceofelectriccurrentisavailable
•Fieldforgroundbedareavailable
ICCP Method (Cont…)
• Obtained from a DC power supply connected
between anode and the metal to be protected.

• A connection from a current source to make


electron flow to metal, to cause the metal to be
cathode.

• Anode is usually surrounded by high conductivity


backfill material ( “groundbed”) such as gypsum
or bentonite which improve the electric contact
between anode and surrounding soil.

• Add: it will protected large area.


ICCP Method (Cont…)
•The source of electrons is an impressed current from an
external power source for an underground tank.

•Negative
terminal of
powers source
is connected to
the structure to
be protected.
•Positive
terminal is
joined to an
inert anodic
(i.e. graphite)
•The anode is usually surrounded by high conductivity
backfill material such as coke breeze, gypsum or
bentonite which improve electric contact between the
anode and surrounding soil.
CORROSION &
PREVENTION METHODS

TQ