92536206

Mechanics of Nanomaterials
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Score
Final 40%
Quiz 10 %

Contents
1. Corrosion and degradation of materials
2. Experimental techniques for Nanoscale mechanics and
materials
3. Energy, temperature and the Boltzmann distributionh
4. Maxwell speed distribution and the equipartition of
energy
5. Thermal properties of solid

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1.Corrosion and degradation of materials

Definition of Corrosion
History

Types of Corrosion
Galvanic

Rate of Corrosion

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Corrosion is the gradual destruction of materials (usually
metal) by chemical reaction with their environment.
The term corrosion is sometimes also applied to the
degradation of plastics, concrete and wood, but generally
refers to metals.

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Metal Corrosion
The destruction of a material by
electrochemical reaction to its environment

chemical

or

Typically a transfer of electrons from one metal to another

through an Oxidation-Reduction Reaction.
In metals, corrosion is produced by the loss of actual
material, which leaves the piece as an ion in solution, and is
carried away by an electrolyte.

Rust is a symptom of this problem in steel, but there can be

corrosion without it.

Effect of corrosion
Reduced Strength.
Downtime of Equipments
Lost Surface Properties

Reduced Value of goods

Losses are economic and safety

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Oxidation - Reduction Reduction

Anodic metal gives up electrons (oxidation)
Fe Fe 2 2e
Al Al 3 3e

Cathodic metal accepts electrons (reduction)

Cu 2 2e Cu

Or gases accept electrons (reduction)

2 H 2e H2 ( gas)

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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General Reactions
Anode: (Metal basically dissolves in the electrolyte.)

M M

ne

Cathode: (This is a very common reaction!)

2 H 2O O2 4 e

4 OH

Surfaces near high O2 concentration are cathodic!

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Steel Corrosion
Initial Oxidation Reaction

2 Fe O2 2 H2 O 2 Fe ( OH ) 2
Secondary Oxidation Reaction

1
2 Fe(OH ) 2 O2 H2 O 2 Fe(OH ) 3
2
Rust

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Types of Corrosion
Uniform - common surface effect.
Galvanic - dissimilar metals.
Crevice corrosion.
Pitting.
Intragranular.
Erosion corrosion.
Stress corrosion.
Hydrogen embrittlement

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Uniform Corrosion
This one is common in steel that is unprotected by
any surface coating. Most noticeable. Surface effect,
leaving rust on the surface.
The good thing about this, if there is one, is that the
corrosion is widely spread around.
The more dangerous forms
of corrosion are:
1. Highly
localized,
concentrated.
2. Hidden.
Electrolyte?

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Galvanic Corrosion

Steel screws and brass

Steel screw in Mg
Dissimilar metals, the damage occurs at
the anode.

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Crevice Corrosion

This is a concentration cell in action. Notice how the damage

occurs in out of sight places.

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Pitting
This is similar to crevice corrosion. It is based on
low oxygen concentration at the bottom of the pit.
This is very common in materials that protect
themselves with a passive layer, i.e. stainless. Also,
aluminum.
Highly localized.
deep into the metal.

Goes

Chloride ions find their way into

the pits, exacerbating the situation.

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Intergranular Corrosion
This is a segue from the previous. It is closely
related.
Again, stainless steel is the ideal victim here.
The problem is triggered by improper heating, and
often this comes with welding. Carbides of
chromium form in the grain boundary regions.
The chromium is tied up in the carbides. It cant
protect by forming the passive layer.
PLUS, there is a dissimilarity in metals
producing a small but definite galvanic corrosion.

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More intergranular
Exfoliation corrosion in Aluminum that has been
heavily worked, such as in extrusion.
Corrosion products start to build up in between the
long elongated grains, separating them and leadin to
increased corrosion propagation through the metal.

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Erosion Corrosion
This is caused by the impingement of a high
velocity turbulent flow on a surface.
The flow is often multi-phase. This means
there can be entrained solid particles, or even
gas bubbles, as in cavitation of a propeller.
The flow will carry away any protective layer
that was intended to protect the material, and
even abrade the flow surface.

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Stress Corrosion
Sometimes called stress corrosion cracking.
Ingredients: (1) tensile stress in the metal (2)
corrosive (electrolyte) environment.
Accelerators: presence of Chloride ion and high
temp.
Victims: Stainless steel is unsafe in water above
50C and over a few ppm of chloride, if any tension
exists. Others: mild steel in alkaline environment,
copper alloys in ammonia env.
The anode is the stresses region.

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Stress Corrosion in Stainless Steel

Failure is along grain boundaries.

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Hydrogen Embrittlement
This is not exactly galvanic corrosion, but it
definitely is a form of environmental attack.
Hydrogen atoms diffuse into the metal from
outside. Deep in the metal, they combine to form H2
gas or combine with C, if present to form CH4.
The pressure in this internal pockets of gas is
enough to initiate cracking.
The metal is already seeing a lot of tensile stress.
Normally ductile high strength metals, particularly
steels, are not so ductile anymore because of these
internal cracks.

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Where does the Hydrogen come from?

Arc welding can a source.
Hydrogen might be released
from the electrode.
Galvanic corrosion can
produce hydrogen in a
reduction reaction.
Sour gas wells
Hydrogen storage (You just
dont use high strength
steel!)

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Corrosion Protection
Protection of the Anode. (Passivation)
Reduce the activity of the cathode and or
electrolyte. (Polarization)

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Passivation of the anode

We have two examples already. Stainless and
aluminum.
A thin oxide layer forms on the surface and isolates
the metal from the environment.
Zn, Mg, Cu and Ti are also capable of passivation
under normal conditions of operation.
Steel will also passivate in the presence of an
alkaline environment, such as rebar in concrete.
Corrosion inhibitors. Some of these, such as the
chromates, are capable of coating a steel and
passivating it.
Coatings, paints, etc.

Passivation

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Iron dissolves in dilute nitric acid, but not in concentrated nitric acid
The concentrated acid oxidizes the surface of iron and produces a thin protective
oxide layer (dilute acid is not able to do so)
potential of a metal electrode in current density (I/A)
On current density reaching a critical value fall in current density
(then remains constant) Passivation

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Polarization
This is an effect which reduces the actual
chemical potential driving the cell.
If the
thermodynamic force driving the ion into solution
is reduced, this is polarization.
Easy example. By lowering the electrolyte
temperature, we find that it is usually less
corrosive. Diffusion of ions is slowed.
Inhibitors are chemicals which slow corrosion.
Some of them do this by promoting the
polarization of the cathode.

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Polarization

Anodic and Cathodic reactions lead to concentration differences near the

electrodes
This leads to variation in cathode and anode potentials (towards each other)
Polarization

Potential (V)

Vanode

IR drop through the electrolyte

Vcathode

Steady state current

Current (I)

Prevention of Corrosion

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Basic goal protect the metal avoid localized corrosion

When possible chose a noble metal
Avoid electrical / physical contact between metals with very different electrode
potentials (avoid formation of a galvanic couple)
If dissimilar metals are in contact make sure that the anodic metal has a larger
surface area / volume
In case of microstructural level galvanic couple, try to use a course
microstructure (where possible) to reduce number of galvanic cells formed
Modify the base metal by alloying
Protect the surface by various means
Modify the fluid in contact with the metal
Remove a cathodic reactant (e.g. water)
Add inhibitors which from a protective layer
Cathodic protection
Use a sacrificial anode (as a coating or in electrical contact)
Use an external DC source in connection with a inert/expendable electrode

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Galvanic
Concentration of electrolyte solution 1 Molar
Concentration of electrolyte solution is not 1 Molar

Different ion concentration cells

Different oxygen concentration cells

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Concentration of electrolyte solution 1 Molar

Zn ---> Zn2+ + 2eCu ---> Cu2+ + 2e-

E0 = -0.763 V
E0 = +0.337 V

Oxidation: Zn ---> Zn2+ + 2eReduction: Cu2+ + 2e- ---> Cu

Total:

E0 = -0.763 V
E0 = -0.337 V

Zn + Cu2+ ---> Zn2+ + Cu E0cell = -1.100 V

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Exercise 1 Galvanic consist of Zn in ZnSO4 [1M] and Ni in NiSO4

[1M] This Separated by porous wall
(a) Which is oxidation
(b) Which is anode
(c) Which is corrosion
(d) How much for galvanic emf
Sol-n

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Concentration of electrolyte solution is not 1 Molar

M ---> Mn+ + neEffect of ion concentration Cion (emf standard at 25oC) by
Nernst equation

E = New emf of half cell

E0 = Standard emf of half cell
n = Number of electron (M---->Mn+ + ne-)
Cion = Ion concentration (Molar)

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Exercise 2 Galvanic cell at 25oC consist of Zn in ZnSO4 [0.1M]

and Ni in NiSO4 [0.05M] This Separated by porous wall. How
much for galvanic emf
Sol-n

Different ion concentration cells

Low concentration is anode
High concentration is cathode
Calculate from Nernst equation

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Exercise 3 Steel immersed in electrolyte solution of Fe2+ [0.02M]

and Fe2+ [0.005M] This Separated by porous wall
(a) Which is corrosion
(b) How much for Ecell

Sol-n

Different oxygen concentration cells

Cathode reaction require oxygen and electron
Therefore, High concentration of O2 is cathode
Low concentration of O2 is anode

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Rate of Corrosion (Kinetics)

Electroplating in solution
From Faraday equation;

w = Weight of metal (g)

I = Current (A)
M = Atomic weight of Metal (g/mol)
n = Number of Electron/Atom
F = Faraday constant = 96,500 C/mol (A.s/mol)

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Corrosion of metal in term of current stream

i (A/cm2) ----> I = iA

i = Current density (A/cm2)

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Ex Coppor electroplating process used current 15 A in coppor

solution from anode (corrosion) and coppor electroplating on
cathod. How long it will take to make the coppor anode corrosion
8.5 g
Sol-n From eq,

or

In this case, w = 8.5 g

n = 2 for Cu ----> Cu2+ +2eF = 96,500 A.s/mol
M = 63.5 g/mol
I = 15 A, t = ? s

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Ex Steel Cylindrical tank with height 1 m and diameter 50 cm

containing air dissolved in water. Height of water 60 cm, weight
of tank loss from corrosion 304 g after 6 weeks. Calculate
(a) Current from corrosion
(b) Current density from corrosion

(a) Sol-n From eq,

In this case, w = 304 g
n = 2 for Fe ----> Fe2+ +2eF = 96,500 A.s/mol
M = 55.85 g/mol
t = 6 weeks, I = ? A

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(b) Sol-n From eq,

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Exercise 4 Wall of the tank is made of steel, which contains water

with dissolved air in corrosion rate with 54.7 mdd. How much it
would take to make the thickness of the wall of the tank, down 0.5
mm.
Sol-n

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Exercise 5 Zinc corrosion regularly with current density of 4.27 x

10-7 A / cm2 in a solution Calculate the rate of corrosion of zinc in
mdd. Oxidation reaction of zinc is Zn---->Zn2+ + 2e-

Sol-n

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Corrosion Control
Materials
Selection:
Metallic
Nonmetallic

Coatings:

Metallic
Inorganic
Organic

Design:

Avoid excessive
stresses
Avoid dissimilar
metal contact
Avoid crevices
Exclude air

Cathodic
and anodic
protection:

Environmental
control:
Temperature
Velocity
Oxygen
Concentration
Inhibitors
Cleaning