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Theoretical Background

Corrosion of mild steel


Rust is a general term for a series of iron oxides. Colloquially, the term is applied to red
oxides, formed by the reaction of iron and oxygen in the presence of water or air
moisture. There are also other forms of rust, such as the result of the reaction of iron
and chlorine in an environment deprived of oxygen, such as rebar used in
underwater concrete pillars, which generates green rust. Several forms of rust are
distinguishable visually and by spectroscopy, and form under different circumstances.
[1]
Rust consists of hydrated iron(III) oxides Fe2O3·nH2O andiron(III) oxide-
hydroxide (FeO(OH), Fe(OH)3). Given sufficient time, oxygen, and water, any iron mass
will eventually convert entirely to rust and disintegrate. Surface rust provides no
protection to the underlying iron unlike the formation ofpatina on copper surfaces.

Rusting is the common term for corrosion of iron and its alloys, such as steel. Many other
metals undergo equivalent corrosion, but the resulting oxides are not commonly called
rust.
Oxidation of iron metal:
When iron is in contact with water and oxygen, or other strong oxidants and/or acids, it
rusts. If salt is present as, for example, in salt water, it tends to rust more quickly, as a
result of the electro-chemical reactions. Iron metal is relatively unaffected by pure water
or by dry oxygen. As with other metals, like aluminium, a tightly adhering oxide coating,
a passivation layer, protects the bulk iron from further oxidation. Thus, the conversion of
the passivating iron oxide layer to rust results from the combined action of two agents,
usually oxygen and water. Other degrading solutions are sulfur dioxide in water
and carbon dioxide in water. Under these corrosive conditions, iron hydroxide species are
formed. Unlike iron oxides, the hydroxides do not adhere to the bulk metal. As they form
and flake off from the surface, fresh iron is exposed, and the corrosion process continues
until all of the iron is either consumed or all of the oxygen, water, carbon dioxide, or
sulfur dioxide in the system are removed or consumed.
Associated reactions:
A rusted (and dirt-encrusted) bolt; note the surface pitting and gradual shape-
deformation, caused by severe oxidation
Rust in pipes can result in brown and black water.
The rusting of iron is an electrochemical process that begins with the transfer
of electrons from iron to oxygen.[3] The rate of corrosion is affected by water and
accelerated by electrolytes, as illustrated by the effects of road salt on the corrosion of
automobiles. The key reaction is the reduction of oxygen:

O2 + 4 e- + 2 H2O → 4 OH-
Because it forms hydroxide ions, this process is strongly affected by the presence of
acid. Indeed, the corrosion of most metals by oxygen is accelerated at low pH.
Providing the electrons for the above reaction is the oxidation of iron that may be
described as follows:

Fe → Fe2+ + 2 e−
The following redox reaction also occurs in the presence of water and is crucial
to the formation of rust:

4 Fe2+ + O2 → 4 Fe3+ + 2 O2−


Additionally, the following multistep acid-base reactions affect the course
of rust formation:
Fe2+ + 2 H2O ⇌ Fe(OH)2 + 2 H+
Fe3+ + 3 H2O ⇌ Fe(OH)3 + 3 H+
as do the following dehydration equilibria:
Fe(OH)2 ⇌ FeO + H2O
Fe(OH)3 ⇌ FeO(OH) + H2O
2 FeO(OH) ⇌ Fe2O3 + H2O

From the above equations, it is also seen that the corrosion products are dictated
by the availability of water and oxygen. With limited dissolved oxygen, iron(II)-
containing materials are favoured, including FeOand black lodestone (Fe3O4).
High oxygen concentrations favour ferric materials with the nominal formulae
Fe(OH)3-xOx/2. The nature of rust changes with time, reflecting the slow rates of
the reactions of solids.Furthermore, these complex processes are affected by the
presence of other ions, such as Ca2+, which both serve as an electrolyte, and thus
accelerate rust formation, or combine with the hydroxides and oxides of iron to
precipitate a variety of Ca-Fe-O-OH species.
Experiment No. 1
Objective: To calculate the corrosion rate of mild steel in mud.

Apparatus:
• Weight balance
• Vernier calipers
• Cutter to cut samples

Procedure:
• First of all cut the samples of appropriate size by using a
cutter then weight these samples by using an electric
weight balance and also calculate the dimensions of sample
by using vernier calipers.
• Then area of sample is calculated.
• After that samples are buried in the earth
• Samples are took out from the earth with a period of one,
two and three weeks for sample one, two and three
respectively.
• Then again weight the samples and calculate weight loss
• In last by using corrosion rate expression find the corrosion
rate of mild steel and plot a graph

Precautions:
• Dimensions of samples should be accurately measured to calculate the
accurate surface area.
• Appropriate grinding of samples should be done before it got buried.
• Time of experiment is also noted.
Experiment No. 2
Objective: To calculate the corrosion rate of mild steel in tap water.

Apparatus:
• Weight balance
• Vernier calipers
• Wires of copper
• Cutter to cut samples
• Beaker having tap water

Procedure:
• First of all cut the samples of appropriate size by using a
cutter then weight these samples by using an electric
weight balance and also calculate the dimensions of sample
by using vernier calipers.
• Then area of sample is calculated.
• After that samples are hanged in tap water beaker by using
copper wires.
• Samples are took out from the beaker with a period of one,
two and three weeks for sample one, two and three
respectively.
• Then again weight the samples and calculate weight loss
• In last by using corrosion rate expression find the corrosion
rate of mild steel and plot a graph

Precautions:
• Dimensions of samples should be accurately measured to calculate the
accurate surface area.
• Appropriate grinding of samples should be done before it got buried.
• Time of experiment is also noted.
Experiment No. 3
Objective: To calculate the corrosion rate of mild steel in 5% HCl solution.

Apparatus:
• Weight balance
• Vernier calipers
• Wires of copper
• Cutter to cut samples
• Beaker having 5% HCl solution

Procedure:
• First of all cut the samples of appropriate size by using a
cutter then weight these samples by using an electric
weight balance and also calculate the dimensions of sample
by using vernier calipers.
• Then area of sample is calculated.
• After that samples are hanged in 5% HCl solution beaker
by using copper wires.
• Samples are took out from the beaker with a period of one,
two and three weeks for sample one, two and three
respectively.
• Then again weight the samples and calculate weight loss
• In last by using corrosion rate expression find the corrosion
rate of mild steel and plot a graph

Precautions:
• Dimensions of samples should be accurately measured to calculate the
accurate surface area.
• Appropriate grinding of samples should be done before it got buried.
• Time of experiment is also noted.
Experiment No. 4
Objective: To calculate the corrosion rate of mild steel in 5% H2SO4 solution.

Apparatus:
• Weight balance
• Vernier calipers
• Wires of copper
• Cutter to cut samples
• Beaker having 5% H2SO4 solution

Procedure:
• First of all cut the samples of appropriate size by using a
cutter then weight these samples by using an electric
weight balance and also calculate the dimensions of sample
by using vernier calipers.
• Then area of sample is calculated.
• After that samples are hanged in 5% H2SO4 solution beaker
by using copper wires.
• Samples are took out from the beaker with a period of one,
two and three weeks for sample one, two and three
respectively.
• Then again weight the samples and calculate weight loss
• In last by using corrosion rate expression find the corrosion
rate of mild steel and plot a graph

Precautions:
• Dimensions of samples should be accurately measured to calculate the
accurate surface area.
• Appropriate grinding of samples should be done before it got buried.
• Time of experiment is also noted.
Corrosion behavior of Aluminum and Aluminum Alloys
Aluminum owes its excellent corrosion resistance and its usage as one of the
primary metals of commerce to the barrier oxide film that is bonded strongly to its
surface and, that if damaged, re-forms immediately in most environments.
On a surface freshly abraded and then exposed to air, the barrier oxide film is only 1 nm
thick but is highly effective in protecting the aluminum from corrosion.
The natural film can be visualized as the result of a dynamic equilibrium between
opposing forces-those tending to form compact barrier layer and those tending to break it
down.
If the destructive forces are absent, as in dry air, the natural film will consist only of the
barrier layer and will form rapidly to the limiting thickness. If the destructive forces are
too strong, the oxide will be hydrated faster than it is formed, and little barrier will
remain.
Between these extremes, where the opposing forces reach a reasonable balance, relatively
thick (20 to 200 nm) natural films are formed.
Pitting corrosion:
Corrosion of aluminum in the passive range is localized, usually manifested by random
formation of pits. The pitting potential principle establishes the conditions under which
metals in the passive state are subject to corrosion by pitting.
For aluminum, pitting corrosion is most commonly produced by halide ions, of which
chloride (Cl -) is the most frequently encountered in service. Pitting of aluminum in
halide solutions open to the air occurs because, in the presence of oxygen, the metal is
readily polarized to its pitting potential.
Generally, aluminum does not develop pitting in aerated solutions of most nonhalide salts
because its pitting potential in these solutions is considerably more noble (cathodic) than
in halide solutions and it is not polarized to these potentials in normal service.
Solution Potentials:
Because of the electrochemical nature of most corrosion processes, relationships among
solution potentials of different aluminum alloys, as well as between potentials of
aluminum alloys and those of other metals, are of considerable importance.
Furthermore, the solution potential relationships among the microstructural constituents
of a particular alloy significantly affect its corrosion behavior. Compositions of solid
solutions and additional phases, as well as amounts and spatial distributions of the
additional phases may affect both the type and extent of corrosion.
The solution potential of an aluminum alloy is primarily determined by the composition
of the aluminum rich solid solution, which constitutes the predominant volume fraction
and area fraction of the alloy microstructure. Solution potential is not affected
significantly by second phase particles of microscopic size, but because these particles
frequently have solution potentials differing from that of the solid solution matrix in
which they occur, localized galvanic cells may be formed between them and the matrix.
Since most of the commercial aluminum alloys contain additions of more than one of
these elements; effects of multiple elements in solid solution on solution potential are
approximately additive. The amounts retained in solid solution, particularly for more
highly alloyed compositions, depend highly on fabrication and thermal processing so that
the heat treatment and other processing variables influence the final electrode potential of
the product.
Solution potential measurements are useful for the investigation of heat treating,
quenching, and aging practices, and they are applied principally to alloys containing
copper, magnesium, or zinc.
In aluminum-copper and aluminum-copper-magnesium (2xxx) alloys, potential
measurement can determine
the effectiveness of solution heat treatment by measuring the amount of copper in solid
solution. Also, by measuring
the potentials of grain boundaries and grain bodies separately, the difference in potential
responsible for intergranular corrosion, exfoliation, and stress corrosion cracking (SCC)
can be quantified. Solution-potential measurement of alloys containing copper also show
the progress of artificial aging as increased amounts of precipitates are formed and
the matrix is depleted of copper.
Potential measurement are valuable with zinc-containing (7xxx) alloys for evaluating the
effectiveness of the solution heat treatment, for following the aging process, and for
differentiating among the various artificially aged tempers.
These factors can affect corrosion behavior.
In the magnesium containing (5xxx) alloys, potential measurements can detect low-
temperature precipitation and are useful in qualitatively evaluating stress-corrosion
behavior. Potential measurement can also be used to follow the diffusion of zinc or
copper in alclad products, thus determining whether the sacrificial cladding can continue
to protect the core alloy.
Atmospheric Corrosion:
Most aluminum alloys have excellent resistance to atmospheric corrosion (often called
weathering), and in many outdoor applications, such alloys do not require shelter,
protective coatings or maintenance.
Corrosion in Waters:
Aluminum alloys of the 1xxx, 3xxx, 5xxx and 6xxx series are resistant to corrosion by
many natural waters. The more important factors controlling the corrosivity of natural
waters to aluminum include water temperature, pH, and conductivity, availability of
cathodic reactant, presence or absence of heavy metals, and the corrosion potentials
and pitting potentials of the specific alloys.

Experiment No. 5
Objective: To calculate the corrosion rate of aluminum in 5% H2SO4 solution.
Apparatus:
• Weight balance
• Vernier calipers
• Wires of copper
• Cutter to cut samples
• Beaker having 5% H2SO4 solution

Procedure:
• First of all cut the samples of appropriate size by using a
cutter then weight these samples by using an electric
weight balance and also calculate the dimensions of sample
by using vernier calipers.
• Then area of sample is calculated.
• After that samples are hanged in 5% H2SO4 solution beaker
by using copper wires.
• Samples are took out from the beaker with a period of one,
two and three weeks for sample one, two and three
respectively.
• Then again weight the samples and calculate weight loss
• In last by using corrosion rate expression find the corrosion
rate of mild steel and plot a graph

Precautions:
• Dimensions of samples should be accurately measured to calculate the
accurate surface area.
• Appropriate grinding of samples should be done before it got buried.
• Time of experiment is also noted.
• Samples should be properly dipped in solution.

Experiment No. 6
Objective: To calculate the corrosion rate of aluminum in 5% HCl solution.
Apparatus:
• Weight balance
• Vernier calipers
• Wires of copper
• Cutter to cut samples
• Beaker having 5% H2SO4 solution

Procedure:
• First of all cut the samples of appropriate size by using a
cutter then weight these samples by using an electric
weight balance and also calculate the dimensions of sample
by using vernier calipers.
• Then area of sample is calculated.
• After that samples are hanged in 5% HCl solution beaker
by using copper wires.
• Samples are took out from the beaker with a period of one,
two and three weeks for sample one, two and three
respectively.
• Then again weight the samples and calculate weight loss
• In last by using corrosion rate expression find the corrosion
rate of mild steel and plot a graph

Precautions:
• Dimensions of samples should be accurately measured to calculate the
accurate surface area.
• Appropriate grinding of samples should be done before it got buried.
• Time of experiment is also noted.
• Samples should be properly dipped in solution.

Experiment No. 7
Objective: To calculate the corrosion rate of aluminum in 5% HNO3 solution.
Apparatus:
• Weight balance
• Vernier calipers
• Wires of copper
• Cutter to cut samples
• Beaker having 5% H2SO4 solution

Procedure:
• First of all cut the samples of appropriate size by using a
cutter then weight these samples by using an electric
weight balance and also calculate the dimensions of sample
by using vernier calipers.
• Then area of sample is calculated.
• After that samples are hanged in 5% HNO3 solution beaker
by using copper wires.
• Samples are took out from the beaker with a period of one,
two and three weeks for sample one, two and three
respectively.
• Then again weight the samples and calculate weight loss
• In last by using corrosion rate expression find the corrosion
rate of mild steel and plot a graph

Precautions:
• Dimensions of samples should be accurately measured to calculate the
accurate surface area.
• Appropriate grinding of samples should be done before it got buried.
• Time of experiment is also noted.
• Samples should be properly dipped in solution.

Experiment No. 8
Objective: To calculate the corrosion rate of aluminum in tap water.
Apparatus:
• Weight balance
• Vernier calipers
• Wires of copper
• Cutter to cut samples
• Beaker having tape water

Procedure:
• First of all cut the samples of appropriate size by using a
cutter then weight these samples by using an electric
weight balance and also calculate the dimensions of sample
by using vernier calipers.
• Then area of sample is calculated.
• After that samples are hanged in tap water beaker by using
copper wires.
• Samples are took out from the beaker with a period of one,
two and three weeks for sample one, two and three
respectively.
• Then again weight the samples and calculate weight loss
• In last by using corrosion rate expression find the corrosion
rate of mild steel and plot a graph

Precautions:
• Dimensions of samples should be accurately measured to
calculate the accurate surface area.
o Appropriate grinding of samples should be done before it got
buried.
o Time of experiment is also noted.
o Samples should be properly dipped in solution.

Experiment No. 9
Objective: To color (Bluing) the mild steel sample to prevent it from
corrosion.

Apparatus:
• Wires of copper
• Cutter to cut samples
• Beaker having color solution
• Burner with tripod stand
Bath Composition:
• NaNO2 90 gm
• NaNO3 110 gm
Bath Temperature:
230-300 C

Procedure:
• First of all cut the samples of appropriate size by using a
cutter
• Then solution is prepared according to given bath
composition.
• After that samples are hanged in solution beaker by using
copper wires.
• Solution is heated by a gas burner to a temperature of 230-
300 C
• Samples are kept in heated solution for 30-40 minutes.
• Then samples are dipped in NaOH for 1-2 minutes.

Precautions:
o Bath composition should be accurate
o Appropriate grinding of samples should be done before dipped
in solution.
o Samples should be properly dipped in solution.
o Temperature of bath should be continuously monitored by a
thermometer.

Experiment No. 10
Objective: To color (Blackening) the mild steel sample to prevent it from
corrosion.

Apparatus:
• Wires of copper
• Cutter to cut samples
• Beaker having color solution
• Burner with tripod stand
Bath Composition:
• NaOH 80 gm
• KNO3 40 gm
• NaNO3 5 gm
• Distilled Water 200 ml
Bath Temperature:
120-130 C

Procedure:
• First of all cut the samples of appropriate size by using a
cutter
• Then solution is prepared according to given bath
composition.
• After that samples are hanged in solution beaker by using
copper wires.
• Solution is heated by a gas burner to a temperature of 120-
130 C
• Samples are kept in heated solution for 20-30 minutes.
• Then samples are dipped in NaOH for 1-2 minutes.

Precautions:
o Bath composition should be accurate
o Appropriate grinding of samples should be done before dipped
in solution.
o Samples should be properly dipped in solution.
o Temperature of bath should be continuously monitored by a
thermometer.