Chapter 11 Corrosion and Degradation of Materials

CHAPTER 11: CORROSION AND
DEGRADATION OF MATERIALS
Issue to address.
What is corrosion and why is it important?
How does corrosion occur?
What are the forms of corrosion?
How can we suppress or prevent corrosion?
How does degradation occur in ceramics,
polymers and composites?
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Dr. Mohd. Hazwan Hussin, Materials Chemistry (KIT 257) , mhh@usm.my
Corrosion of metals
1.0 Introduction
1.1 Definition of Corrosion
Corrosion is the degradation/deterioration of a material, usually a metal, by
chemical or electrochemical reaction with its environment.
Deterioration by purely physical causes is not corrosion but is described
as erosion or wear.
Corrosion is a spontaneous process.
Free energy is released in the process.
Metals returned to its stable state. Corrosion is extractive metallurgy in reverse.
The driving force for corrosion reaction: chemical energy - energy stored in
chemical bonds of substances -internal energy.
Rust is a term for deterioration processes only applied for iron and its alloy
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Extractives metallurgy in reverse
+ H
- H
Metals extracted from their ores and are in high energy states, thermodynamically, they are
not stable. Corrosion is a natural occurring process, predicted by thermodynamics laws.
It is this tendency of metals to recombine with elements presents in the environments that
leads to the phenomenon known as Corrosion.
Metals corrode because they are not in their natural state

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1.2 The Cost of Corrosion

Direct Cost: ~ 4.2% GNP
Replacement of corroded components
Costs of maintenance/servicing
Costs of rebuilding/construction
Equipment capital
Use of corrosion resistant alloys
Use of coatings or inhibitors
Electrochemical protection measures
Chemical expenses
Environmental regulation
Safety considerations
Indirect Cost
Loss of production during downtime
Loss of products due to leakage
Loss of efficiency due to corrosion
Contamination
Loss of human lives due to explosion, fire etc
Mitigation corrosion is necessary to save costs, time and environment

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1.3 Corrosion can be controlled

Materials selection
Proper design
Electrochemical protection
Environment control
Inhibitors
Paints/Coatings
1.4 Significance of Corrosion Control

Economics
Safety
Environmental concerns
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2.0 The Corrosion Process

Metal corrosion is a chemical reaction between a metal surface and its environment.
Metals react with the environment, producing corrosion products similar to the original
ore from which the metal was obtained. Corrosion can occur in a gaseous (dry)
environment or a damp (wet) environment.
Dry Corrosion
At room temperature, most metals carry a thin oxide layer as a result of the reaction of
metals with oxygen in the atmosphere. Increase of temperature may cause formation of
a heavier layer, or the layer may detach.
Zinc and zinc coatings carry a fairly protective zinc hydroxide or carbonate layer (zinc
patina) which increases in thickness very slowly. Aluminium carries a thin, highly
protective oxide layer.
Corrosion in a gaseous environment produces a surface layer of converted metal. For
example atmospheric corrosion of zinc produces the dull, gray zinc oxide layer seen on
galvanised street light poles. Unoxidised zinc coating fresh from the hot dip galvanisers
is bright and shiny.
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Wet corrosion
Wet corrosion takes place in environments where the relative humidity exceeds 60 %. Wet
corrosion is an electro-chemical phenomenon. When two metals are in contact with water
solution containing salts, an electric potential is formed between two different metals or the
surfaces of the same metal with different surface conditions. This causes the dissolution of
the less noble metal. The more noble metal remains protected but the less noble metal
corrodes.
Wet corrosion is most efficient in waters containing salts, such as NaCl (e.g. marine
conditions), due to the high conductivity of the solution. Chlorides also may increase the
corrosion rate of metals.
Corrosion in a wet environment attacks the metal by removing the atoms on the metal
surface. The metal atoms at the surface lose electrons and become actively charged ions
that leave the metal and enter the wet electrolyte. The metal ions join with/to oppositely
charged ions from another chemical and form a new, stable compound.
Most metal corrosion occurs via electrochemical reactions at the interface between the
metal and an electrolyte solution.
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2.1 Corrosion Reaction

Most metal corrosion occurs via electrochemical reactions at the interface
between the metal and an electrolyte solution. A thin film of moisture on a metal
surface forms the electrolyte for atmospheric corrosion.
Electrochemical corrosion involves two half-cell reactions; an oxidation reaction
at the anode and a reduction reaction at the cathode. For iron corroding in
water with a near neutral pH, these half cell reactions can be represented as:
Fe2+ + 2e-
Anode reaction:
Fe
Cathode reaction:
1/2O2 + H2O + 2e-
Corrosion reaction: Fe + 1/2O2 + H2O
2OHFe(OH)2
There are obviously different anodic and cathodic reactions for different alloys
exposed to various environments. These half cell reactions are thought to occur
(at least initially) at microscopic anodes and cathodes covering a corroding
surface.
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From the above reaction it should be apparent that there are four fundamental
components in an electrochemical corrosion cell:
An anode.
A cathode.
A conducting environment for ionic movement
(electrolyte).
An electrical connection between the anode and
cathode for the flow of electron curr ent.
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Electrochemical nature of corrosion
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Corrosion Chemistry of Iron

Corrosion of iron consists of the formation of hydrated oxide, Fe(OH)3, FeO(OH), or even
Fe2O3.H2O. It is an electrochemical process which requires the presence of water, oxygen
and an electrolyte. In the absence of any one of these rusting does not occur to any
significant extent. In air, a relative humidity of over 50% provides the necessary amount of
water and at 80% or above corrosion of bare steel is worse.
When a droplet of water containing a little dissolved oxygen falls on an steel pipe, the
solid iron or Fe(s) under the droplet oxidizes:
Fe(s)
Fe2+(aq) + 2e
The electrons are quickly consumed by hydrogen ions from water (H2O) and dissolved
oxygen or O2(aq) at the edge of the droplet to produce water:
2H2O(l)
4e + 4H+ (aq) + O2(aq)
More acidic water increases corrosion. If the pH is very low the hydrogen ions will
consume the electrons anyway, making hydrogen gas instead of water:
2H+(aq) + 2e-
H2(g)
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The equations above tell only a small part of the story.

Hydrogen ions are being consumed by the process. As the iron corrodes, the pH in the
droplet rises. Hydroxide ions (OH-) appear in water as the hydrogen ion concentration falls.
They react with the iron(II) ions to produce insoluble iron(II) hydroxides or green rust:
Fe2+(aq) + 2OH-(aq)
Fe(OH)2(s)
The iron(II) ions also react with hydrogen ions and oxygen to produce iron(III) ions:
4Fe2+(aq) + 4H+(aq) + O2(aq)
4Fe3+(aq) + 2H2O(l)
The iron(III) ions react with hydroxide ions to produce hydrated iron(III) oxides (also known
as iron(III) hydroxides):
Fe3+(aq) + 3OH-(aq)
Fe(OH)3(s)
The loose porous rust or Fe(OH)3 can slowly transform into a crystallized form written as
Fe2O3.H2O the familiar red-brown stuff that is called "rust". Since these processes
involve hydrogen ions or hydroxide ions, they will be affected by changes in pH. With
limited O2, magnetite is formed (Fe3O4).
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Corrosion Reaction of Iron

Fe + O2 + H2O
Fe(OH)2
O2
Fe(OH)3
oxidation
hydrolysis
- FeOOH
- FeOOH
- FeOOH
- FeOOH
Fe3O4
Fe2O3
Fe2O3.nH2O
Etc.
Corrosion products
of Iron
Fe2+
O2
O2
hydrolysis
O2
hydrolysis
Fe(OH)2
Fe2+
Fe(OH)3
Fe
Fe(OH)2
FeOOH
Fe(OH)2
Fe(OH)3
Fe3O4
FeOOH
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2.2 Reaction feasibility
anode :
cathode :
free energy change
is negative meaning that reaction is feasible and spontaneous

must be positive
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2.3 Nernst equation
For hydrogen ion

reduction :
For oxygen reduction :
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2.4 CORROSION RATE DETERMINATION
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CORROSION RATE
Faraday Law :
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Conversion to other unit

The following charts provide a simple way to convert data between the most
common corrosion units in usage, i.e. corrosion current (mA cm-2 ) , mass loss (g
m-2 day-1 ) and penetration rates (mm y-1 or mpy) for all metals or for steel.
mA cm-2
mm year-1
mpy
3.28 M/nd
129 M/nd
8.95 M/n
0.306 nd/M
39.4
2.74 d
0.00777 nd/M
0.0254
0.0694 d
0.112 n/M
0.365 /d
14.4 /d
mA cm-2
mm year-1
mpy
g m-2 day-1
g m-2 day-1
where:
mpy = milli-inch per year
n = number of electrons freed by the corrosion reaction
M = atomic mass
d = density
Note: you should read the Table from left to right, i.e.:
1 mA cm-2 = (3.28 M/nd) mm y-1 = (129 M/nd) mpy = (8.95 M/n) g m-2 day-1
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For example, if the metal is steel or iron (Fe), n =2, M = 55.85 g

and d = 7.88 g cm-3 and the Table of conversion becomes:
mA cm-2
mm year-1
mpy
11.6
456
249
mm year-1
0.0863
39.4
21.6
mpy
0.00219
0.0254
0.547
g m-2 day-1
0.00401
0.0463
1.83
mA cm-2
g m-2 day-1
Note: you should read the Table from left to right, i.e.:
1 mA cm-2 = 11.6 mm y-1 = 456 mpy = 249 g m-2 day-1
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Example 11.2
Suppose that in a corrosion cell composed of copper and zinc, the current density at the
copper cathode is 0.05 A/cm2. The area of both the copper and zinc electrodes is 100 cm2.
Calculate (1) the corrosion current, (2) the current density at the zinc anode, and (3) the zinc
loss per hour.
Solution
1. The corrosion current is:
2. The current in the cell is the same everywhere. Thus:
3. The atomic mass of zinc is 65.38 g/mol. From Faradays equation:
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STANDARD EMF SERIES
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GALVANIC SERIES
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Example 11.1
An iron container 10 cm 10 cm at its base is filled to a height of 20 cm with a corrosive
liquid. A current is produced as a result of an electrolytic cell, and after 4 weeks, the container
has decreased in weight by 70 g. Calculate (1) the current and (2) the current density
involved in the corrosion of the iron.
Solution
1. The total exposure time is:
From Faradays equation, using n = 2 and M = 55.847 g/mol:
2. The total surface area of iron in contact with the corrosive liquid and the
current density are:
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3.0 Factors Affecting Corrosion

Material Properties
Chemical composition determines the energy considerations necessary for corrosion to
occur
Metallurgical Factors
In pure metals, anode areas are grain boundaries or small microheterogeneities.
In alloys and metals with impurities:
Chemical segregation
Presence of multiple phases
Inclusions
Defects
Nonuniform stresses
Surface condition
that inhibits electrochemical action between the metal and its environment.
Formation of an uniform oxide film
Film of adsorbed gas
Surface defects
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Cont.
Environment
Chemical nature:
Acids (oxidizing and reducing)
Bases
Salts (acid, neutral, alkaline)
Gases
Solvents
Operating conditions:
Intended service life
Temperature
Velocity
Concentration
Impurities
Aeration
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4.0 TYPES OF CORROSION

Corrosion can be divided into different groups according to their form of occurrence.
4.1. General/ Uniform corrosion

Uniform attack is a form of electrochemical corrosion that
occurs with equal intensity of the entire surface of the
metal. Metal corrodes uniformly all over the surface.
Metal
4.2. Localized corrosion

Part of the structure corrodes at a considerably higher than average rate. The
categories of local corrosion are:
Pitting corrosion
Crevice corrosion
Galvanic corrosion
Intergranular corrosion
Selective corrosion
Filliform corrosion
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Pitting corrosion
The formation of small pits on the
surface of a metal or alloy. The
corrosion effect is concentrated on
localised areas and leads to
pitting. Downward propagation of
small pits & holes where
passivating layer fails.
Crevice Corrosion
Crevice corrosion is a consequence of
concentration differences of ions or
dissolved gases in an electrolytic solution.
proceeds at locations covered by a
corrosion product and other deposits (dirt
or trash). Crevice corrosion typically
occurs in small cavities, gaps, recession,
etc
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Galvanic Corrosion
Galvanic corrosion occurs when two metals having different
composition are electrically coupled in the presence of an
electrolyte. The more reactive metal will experience severe
corrosion while the more noble metal will be quite well
protected.
2 different metals
Electrically connected
In same electrolyte
Fe
Cu
(less noble)
Intergranular Corrosion
Corrosion along grain boundaries, often where
special phases exist.
precipitation of chromium carbide

makes the low Cr austenite in the
grain boundaries anodic
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Selective corrosion
When one element or constituent of a metal
is selectively corroded out of a material it is
referred to as selective leaching. The most
common example is the dezincification of
brass. After leaching has occurred, the
mechanical properties of the metal are
obviously impaired and some metal will begin
to crack.
Filiform corrosion
Surface corrosion where the paint film
remains intact but adhesion to the
substrate is destroyed causing trails or
underfilm corrosion to form, like worm
tracks.
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4.3. Combined effect of mechanical factors and corrosion

Mechanical wearing as well as static or dynamic stresses often act in combination with
corrosion. The main categories for combined effect of mechanical factors and corrosion
are:
Stress corrosion
Corrosion fatigue
Erosion corrosion
Fretting corrosion
Stress Corrosion
Stress corrosion can result from the
combination of an applied tensile stress
and a corrosive environment. In fact,
some materials only become susceptible
to corrosion in a given environment once
a tensile stress is applied.
stress
corrosion occurs when a metal in a
corrosive environment is exposed to
static stress that results in fracture
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Corrosion fatigue
Corrosion fatigue is caused by the combined effect
of corrosive environment and varying state of stress.
The fatigue fracture is brittle and the cracks are most
often transgranular, as in stress-corrosion cracking,
but not branched
Fretting corrosion
Caused by the rubbing of two contacting
surfaces under load, which leads to a steady
erosion of material.
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Erosion-Corrosion
Erosion-corrosion arises from a
combination of chemical attack and
the physical abrasion as a
consequence of the fluid motion.
Cavitation corrosion
Cavitation corrosion is erosion caused by the
combined effect of corrosion and the pressure
caused by the breaking of gas bubbles formed in
liquid (cavitation).
Micro-biological corrosion is caused by an

accumulation of micro- organisms (eg.
bacteria) which are found in contaminated
fluids and is normally confined to the internal
surfaces of integral fuel tanks.
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5.0 CORROSION PROTECTION

Controlling Corrosion
Corrosion control involves hindering the natural chemical reactions
that occur between the metal and its environment. The common
methods used are to:
Materials selection (modify the properties of a metal)
Modify the environment
Install a protective coating over the metals
Impose an electric current to supply electrons
Proper design
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5.1 Materials selection

Corrosion of metals in service environment are dependent on :
the types of metal
chemical composition of the metal.
A. Marine environment
Fe/ Fe alloys
Cu
Cu Zn alloy
[ 70% Cu 30% Zn]
Titanium
poor/unsuitable
good
better
much better
B. High pressure gas

Stainless steel(SS]
[18% Cr, 8% Ni, Fe]
[18% Cr, 8% Ni, 3% Mo, Fe]
good
better
C. Damp environment
Fe, Zn
Aloi Fe-Zn
Fe-Ni aloy
unsuitable
good
much better
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D. Modify the Properties of the Metal

Alloying the metal to produce a more corrosion resistant alloy, e.g. stainless steel, in
which ordinary steel is alloyed with chromium and nickel. Stainless steel is protected by
an invisibly thin, naturally formed film of chromium sesquioxide Cr2O3.
From the galvanic series we can see that the more noble metals are less likely to corrode.
When these metals are metallurgically combined with those from lower in the series, the
resulting alloy takes on corrosion resistant properties. The resistance can come from the
development of a protective oxide film on the outside surface or because the new alloy has
a different voltage potential which acts to make it behave more noble.
PASSIVITY: ALLOYING EFFECTS
Passive oxide film can inhibit
aqueous corrosion as well!
E.g. Stainless steel
Alloying Fe with >12% Cr results in formation
of protective Cr-rich passive film, large increase
in corrosion resistance
304 SS: 18% Cr + 8% Ni
316 SS: further addition to 18-8 SS of about
2% Mo, increases corrosion resistance yet more
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5. 2 Modify the environment

Controlling the environment
Use of inhibitors
A. Controlling the environment
Controlling the relative humidity %RH < 50% most metal such as Al, Cr and Ni
will less corrode.
Removal of oxygen - By the removal of oxygen from water systems in the pH
range 6.5-8.5 one of the components required for corrosion would be absent.
The removal of oxygen could be achieved by the use of strong reducing agents
e.g. sulphite and hydrazine
N2H4 + O2
N2 + H2O
Controlling pH, pressure, ionic contaminants and etc.

Iron would be corroded at pH > 13.00. The presence of 5 ppm Cl-1 may induced
corrosion in many metals.
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B. Use of inhibitor
A corrosion inhibitor may be defined, in general terms as a substance which, when added in
a small concentration to an environment, effectively reduces the corrosion rate of a metal
exposed to that environment.
Corrosion inhibitors may combine with the corroding metal (anode) or the protected metal
(cathode) to form a barrier layer that reduces the flow of ions and electrons across it to very
low values and virtually stops the corrosion.
Some of the mechanisms of its effect are formation of a passivation layer (a thin film on the
surface of the material that stops access of the corrosive substance to the metal), inhibiting
either the oxidation or reduction part of the redox corrosion system (anodic and cathodic
inhibitors), or scavenging the dissolved oxygen.
Anodic inhibitor - forms a passivation layer on aluminium and steel surfaces which
prevents the oxidation of the metal. e.g. Chromate, nitrit , borate , molybdates, etc.
2Fe + NaNO2 + 2H2O
-Fe2O3 + NH3 + NaOH
Cathodic inhibitor - retards the corrosion by inhibiting the reduction of water to hydrogen
gas (inhibit the reduction processes). e.g.zinc salts, Magnesium salts, amine etc.
Mixed inhibitor - An inhibitor that acts both in a cathodic and anodic manner.e.g. chromate/
polyphosphate
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The role of corrosion inhibitors

React with corrosive agents such as Na2SO3 dan N2H4
forms a passivation layer
forms of adsorption film /protection layer on the metal surfaces
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5.3 Protective coating

To isolate the metals from the corrosive environments
coating/covering with more noble metal or better corrosion resistant proprties
non-metallic coating (inorganic and organic coatings)
A. Metallic coating
coating with more noble metals
eg. Iron coated with Cr, Ni and Sn for decoration purposes
Coating of Zn in galvanized steel
Coating of Sn on iron for containers
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B. Non metallic coatings

Non-metallic coatings put over a metal can be of two types. They can act as a physical
barrier and bar access to the metal surface or they can introduce a very high resistance
into the corrosion cell circuit and drastically reduce the flow of electrons. The barrier type
coatings protect the metal as long as there are no cracks. If a crack occurs corrosion
becomes intense at the metal surface. Resistance type coatings include additives that
breakdown in the presence of water and oxygen into inhibiting agents.
Inorganic coatings - concrete, silica and ceramics
Organic coatings - tar, paint, plastics and etc.
Paint coatings are considered the most practical and economical means
for the corrosion protection.
There are several mechanisms by which paint coating systems provide corrosion
protection:
Barrier: limiting the access of chemical species involved in electrochemical corrosion
reactions, notably oxygen in the cathodic reaction.
Barrier: maintaining a high electrical resistance at the substrate interface, restricting the
access of ionic species.
Inhibition: corrosion inhibitors in the primer, passivating the underlying metal surface.
Cathodic protection: Sacrificial protection of the underlying substrate, a galvanic effect (for
example, steel protection by zinc).
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Binder (resin PV, PU, epoxy, alkyd etc.)

PAINT
Solvent (organic , water)

Pigment/colouring
Additives (anti-corrosive, anti-fungal etc.)
Decorative / top-coat
Primer / anti-corrosive paint
Metal / alloy
Metal
top coats
intermediate
Anti-rust / anti-corrosive
Wash primer
Wash primer : adhesion

Anti-corrosive paint : corrosion protection
Intermediate : thicken the paint layer
Decorative : decoration and barrier to the environment. For immersed structure in
seawater must be replaced by anti-fouling paint which prevent the attachment of
marine fouling such as barnacles, algae and etc.
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5. 4 Impose an Electric Current

A. Cathodic Protection
B. Anodic Protection
A. Basic Theory of Cathodic Prevention
Corrosion occurs at areas on a metal surface where current leaves the metal and passes into
the adjacent electrolyte. Such current discharge areas are termed "anodic", where anodic
chemical reactions, Fe = Fe++ + 2e proceed, and iron is oxidised to an ionic state. To prevent
such corrosion occurring we need to reverse the direction of electric current flow, such that
the above reaction cannot proceed and the iron remains in its metallic state.
Such a reversal of current flow at anodic sites can
be achieved by superimposing a reverse flow to
overpower any corrosion current. When there is a
net current flow on to all points on the metal
surface, the entire surface is cathodic and
protection from corrosion is complete.
This
technique of corrosion protection is termed
"cathodic protection".
Cathodic protection (CP) is a technique to
control the corrosion of a metal surface by
making that surface become cathodic to the
environment or the cathode of the corrosion cell.
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Cathodic protection can be achieved in two ways:

By connecting a more anodic metal into the corrosion circuit than the metal to be protected.
(galvanic protection or sacrificial anodes)
By passing of an electrical dc current so that all areas of the metal surface become cathodic
and therefore do not corrode
The principle of cathodic protection is in connecting an external anode to the metal to be
protected and the passing of an electrical dc current so that all areas of the metal surface
become cathodic and therefore do not corrode. The external anode may be a galvanic
anode, where the current is a result of the potential difference between the two metals, or it
may be an impressed current anode, where the current is impressed from an external dc
power source.
Galvanic protection or Sacrificial anodes

Galvanic anode systems employ reactive metals as auxiliary anodes that are directly
electrically connected to the steel to be protected. The difference in natural potentials
between the anode and the steel, as indicated by their relative positions in the electrochemical series, causes a positive current to flow in the electrolyte, from the anode to the
steel. Thus, the whole surface of the steel becomes more negatively charged and becomes
the cathode. The metals commonly used, as sacrificial anodes are aluminium, zinc and
magnesium.
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GALVANIC PROTECTION
44
Galvanic protection / sacrificial anode
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Impressed-current systems
For larger structures, galvanic anodes cannot economically deliver enough current to provide
complete protection. Impressed Current Cathodic Protection (ICCP) systems use anodes
connected to a DC power source (a cathodic protection rectifier). Impressed-current systems
employ inert (zero or low dissolution) anodes and use an external source of dc power
(rectified ac) to impress a current from an external anode onto the cathode surface.
Anodes for ICCP systems are tubular and solid rod shapes or continuous ribbons of various
specialized materials. These include high silicon cast iron, graphite, mixed metal oxide,
platinum and niobium coated wire and others.
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B. ANODIC PROTECTION
In circumstances where cathodic protection is not practical, such as in strongly alkaline or
acidic environments, anodic protection is a useful corrosion control technique. Specifically,
in metal-environment conditions where active-passive behaviour is demonstrated, anodic
protection is usually effective. In practise, the metal-environment potential is held in the
passive region by polarizing the structure in the electropositive direction (where the passive
layer is most stable). Historically, anodic protection has the widest application in the
process industries and in particular on mild or stainless steel equipment use for
concentrated sulphuric acid storage. Equipment, such as pulp and paper mill digesters and
recausticizing (white, green & black) liquor clarifiers and storage tanks have also been
effectively protected. Here the metal potential is shifted to the passive zone from the active
region by the application of a direct current.
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Cathodic Protection
Advantages:
Limitation:
can be used for all metals

installation cost is low
corrosion rate can be reduced to zero
can only be used in weak to moderate environment
operating conditions must be determined by empirical testing
Anodic Protection
Advantages:
can be used in extremely aggressive environment
applied current is direct measure of corrosion rate
operating conditions can be easily controlled
operation cost low
Limitation
only applicable to active-passive metals

installation cost is high
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5.5 Proper Design

Design awareness and the life-cycle Good control of corrosion requires the awareness
and co-operation of the entire design team, including engineers and
designers not only in each specialised discipline but in project management and cost
control. Adequate means for collecting, reporting and recording corrosion information
from operational situations must also be planned.
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MINIMIZING OR PREVENTING CORROSION

Use more corrosion-resistant material, e.g. metal that passivated
Remove aggressive species from environment
Add chemical to environment that inhibits corrosion
Separate the metal from the environment with a barrier
layer, e.g. paint
Remove crevices from design
Prevent galvanic corrosion by using compatible materials or
electrically insulating dissimilar materials
Reduce T (slow kinetics of oxidation-reduction reactions)
Use cathodic / sacrificial protection or anodic protection
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6.0 Deterioration of Ceramics

Generally thought to be immune from most corrosion and deterioration mechanisms
Not totally true although they are as good as anything in resisting environmental changes in
the material with aging
Corrosion of fillers, impurities within a ceramic
If corrosion and loss, flaw initiation points from the formed void
The primary means by which ceramics and glass objects deteriorate is through accidental
cracking and breaking due to improper handling, shipping, storage, or display.
Other sources of deterioration for ceramics and glass can include deterioration of the clay
body or the glass as result of poor manufacturing methods or materials.
Porous ceramics can also deteriorate due to the presence of. soluble salts deep within the
ceramic body itself The salts dissolve and re-crystallize as the relative humidity fluctuates.
When the salts re-crystallize they expand in size and crush the surrounding ceramic
structures. For example, a flowerpot that has become saturated with fertilizer salts over
time may exhibit this effect.
Leaving liquids inside vessels for long periods of time can damage glass. Some
constituents of the glass dissolve into the liquid, making the interior of the vessel appear
cloudy or to have residue inside
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7.0 Deterioration of Polymers

Things that make polymers more brittle:
UV Aging (crosslinking)
High Temperatures (crosslinking and volatilization of plasticizers)
Oxidation environments: bond scission due to oxygen attack
Things that make polymers softer:

solvent absorption ( Armor All)
water absorption and attack (hydrolysis)
enhanced by acids and bases
Degradation can change MW of the polymer

Consider Primary Bond Fracture vs Secondary Bond Fracture
Other factors:
Creep and Dimensional Stability
Orientation relaxation (shrinkage
Remember the link between molecular architecture and environmental

sensitivity (heterochain backbones are more susceptible)
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Deterioration of Polymers - Chemical Effects

Linear polymers can be attacked through:
Random scission - breaking of random molecular bonds
Depolymerization - shortening of average molecule length
Both act to reduce the average molecular weight
Cross-linking can either be induced or damaged by chemical attack Induced cross-linking

occurs in low density polyethylene makes stiffer material. Damage of cross-links in
polyisoprene rubber results in a brittle material
Change in bond structure can result in different compound with very different properties.
e.g: Polyvinyl acetate + water --> water soluble polyvinyl alcohol + acetic acid
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Deterioration of Polymers - Sterilization Effects

Dry sterilization - occurs at temperatures between 160 and 190C
Affects microscopic and geometric structure of material
Oxidation can also occur for some polymers (ex. nylon) during dry sterilization,
even though it is below the melting temperature
Only teflon and silicon rubber should be dry sterilized
Steam sterilization (autoclaving): Occurs at high pressure under relatively low temperatures
(120 - 135C)
If a polymer is susceptible to attack by water, the water vapor will cause
degradation during sterilization
Polyvinyl chloride, polyacetals, low density polyethylenes, and polyamides should
not be steam sterilized
Chemical sterilization: At low temperatures, uses Ethylene or propylene oxide gas, phenolic
or hypochloride solution
Chemical agents can sometimes cause deterioration even at room temperature
Due to overnight time required (relatively short exposure to chemicals), can be used
for most polymers
Radiation sterilization: Uses 60Co isotope
Can cause deterioration of high polymers at high doses
Polymer chains can be broken and recombined
Polyethylene becomes hard and brittle
54
Deterioration of Composites
The environment can affect each component of a composite material separately
If the properties of a single component are degraded, the properties of the whole
composite will also be affected
The bond between the matrix and the reinforcing elements may be subject to attack in
addition to the materials themselves
55
SUMMARY
Corrosion occurs due to:
the natural tendency of metals to give up electrons.
electrons are given up by an oxidation reaction.
these electrons then are part of a reduction reaction.
Metals with a more negative Standard Electrode Potential are more
likely to corrode relative to other metals.
The Galvanic Series ranks the reactivity of metals in seawater.
Increasing T speeds up oxidation/reduction reactions.
Corrosion may be controlled by:
using metals which form a protective oxide layer
reducing T
adding inhibitors
painting
using cathodic protections.
56

Chapter 11 Corrosion and Degradation of Materials

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Chapter 11 Corrosion and Degradation of Materials

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CHAPTER 11: CORROSION AND

Extractives metallurgy in reverse

Metals corrode because they are not in their natural state

1.2 The Cost of Corrosion

Mitigation corrosion is necessary to save costs, time and environment

1.3 Corrosion can be controlled

1.4 Significance of Corrosion Control

2.0 The Corrosion Process

2.1 Corrosion Reaction

1/2O2 + H2O + 2e-

Corrosion reaction: Fe + 1/2O2 + H2O

Electrochemical nature of corrosion

Corrosion Chemistry of Iron

Dr. Mohd. Hazwan Hussin, Materials Chemistry (KIT 257) , mhh@usm.my

The equations above tell only a small part of the story.

Corrosion Reaction of Iron

Dr. Mohd. Hazwan Hussin, Materials Chemistry (KIT 257) , mhh@usm.my

2.2 Reaction feasibility

free energy change

is negative meaning that reaction is feasible and spontaneous

2.3 Nernst equation

For hydrogen ion

For oxygen reduction :

2.4 CORROSION RATE DETERMINATION

Conversion to other unit

For example, if the metal is steel or iron (Fe), n =2, M = 55.85 g

3. The atomic mass of zinc is 65.38 g/mol. From Faradays equation:

STANDARD EMF SERIES

From Faradays equation, using n = 2 and M = 55.847 g/mol:

3.0 Factors Affecting Corrosion

4.0 TYPES OF CORROSION

4.1. General/ Uniform corrosion

4.2. Localized corrosion

precipitation of chromium carbide

4.3. Combined effect of mechanical factors and corrosion

Micro-biological corrosion is caused by an

5.0 CORROSION PROTECTION

5.1 Materials selection

B. High pressure gas

D. Modify the Properties of the Metal

5. 2 Modify the environment

Controlling pH, pressure, ionic contaminants and etc.

2Fe + NaNO2 + 2H2O

-Fe2O3 + NH3 + NaOH

The role of corrosion inhibitors

5.3 Protective coating

B. Non metallic coatings

Binder (resin PV, PU, epoxy, alkyd etc.)

Solvent (organic , water)

Wash primer : adhesion

5. 4 Impose an Electric Current

Cathodic protection can be achieved in two ways:

Galvanic protection or Sacrificial anodes

Galvanic protection / sacrificial anode

can be used for all metals

only applicable to active-passive metals

Dr. Mohd. Hazwan Hussin, Materials Chemistry (KIT 257) , mhh@usm.my

5.5 Proper Design

MINIMIZING OR PREVENTING CORROSION

6.0 Deterioration of Ceramics

7.0 Deterioration of Polymers

Things that make polymers softer:

Degradation can change MW of the polymer