Lunit-V Corrosion
Lunit-V Corrosion
Lunit-V Corrosion
CORROSION
Definition
“Corrosion is defined as the gradual destruction (or) deterioration of metals (or) alloys by
the chemical (or) electrochemical reaction with its environment.
Basic reason for metallic corrosion.
Metals are exposed to environment, such as moisture, gases, liquids etc the
exposed metal surfaces begin to decay due to formation of their oxides, carbonates, sulphides,
chlorides and silicates.
1. Noble state
Metals those occurring in nature in native (or) free (or) uncombined state are non-reactive
with the environment. They are noble metals they do not undergo corrosion.
Ex: Au, Pt, Ag
2. Combined state
Expect noble metals ,all other metals are reactive & react with environment and form stable
compounds as oxides, sulphides ,chlorides and carbonates. They exist in the form of stable
compounds called ores& minerals.
Ex: Fe2O3, ZnO, PbS, CaCo3 etc.
CONSEQUENCES OF CORROSION
1. Due to the formation of corrosion product over the machinery, the efficiency of the
machine get lost.
2. The products gets contaminated due to corrosion.
3. The corroded equipments must be replaced frequently.
4. Plant get failure due to corrosion.
5. It is necessary for over design to compensate for the corrosion.
6. Corrosion releases toxic products, health hazard, etc
Reason for corrosion
The metals are extracted from their ores by
reduction. During extraction of metals, energy is
supplied.
Pure metals in excited state (higher energy
content) are unstable, reverse to combined state
(lower energy state) by oxidation process, resulting
corrosion takes place. Due to corrosion, some of the
useful properties of metals such as electrical.
Classification [Theories of corrosion]
Corrosion is classified into two types
(i) Chemical (or) Dry corrosion
(ii) Electro chemical (or) wet corrosion
Chemical (or) dry corrosion
This type of corrosion is due to the direct chemical attack of metal surfaces by atmospheric
gases such as 02, H2S, S02, N02. There are 3 main types of dry corrosion.
1. Oxidation corrosion
2. Corrosion by hydrogen
3. Liquid – metal corrosion
1. Oxidation corrosion :
Oxidation corrosion is brought by the direct attack of oxygen at low (or) high
temps on metal surfaces in the absence of moisture alkali metal and alkaline earth (Mg, Ca, Sn)
metals are rapidly oxidized at low temp – At high temp almost all metals except Ag, Au, and Pl are
oxidized.
M – M n+ + ne-
n/2 02 + 2 ne- → N0 2−
M n+ + NO 2− → M2 On
metal oxide
(iv) Protective (or) non-protective oxide film (Pilling bed worth rule)
a) According to pilling bed worth rule, if the volume of the oxide layer formed is less than the
volume of the metal, the oxide layer is porous and non-protective.
Ex: The volume of oxides of alkali and alkaline earth metals such as Na, Mg, Ca etc is less
than the volume of the metal consumed.
Hence the oxide layer formed is porous and non-protective
b) On the other hand, if the volume of the oxide layer formed is greater than the volume of the
metal, the oxide layer is non-porous and protective.
Ex: The volume of oxides of heavy metals such as Pb, Sn, etc is greater than the volume of
the metal. Hence the oxide layer formed is non-porous and protective.
T
he
rate
corrosion will be more, when the area of cathode is larger and the area of anode is smaller.
Therefore more materials removed from the spot as results of small pit is formed on the surface of
the metal.
2. Crevice corrosion
If a crevice between different metallic objects in
contact with liquids, the crevice becomes anodic and
suffers corrosion, due to less oxygen in this area. The
exposed area acts as cathode. The space between the two
metals is stagnant and higher concentration of metal ions
allowing corrosion occurs at the edge of the joint due to
dirt deposits.
3. Pipeline corrosion
Buried pipelines passing from one type of soil to the other(i.e.,clay -less aerated to sand-
more aerated) will get corroded due to differential aeration.
i) Nature of metal
(a) Position in emf series
Corrosion depends on the position of the metal in the emf service. Metals above the
hydrogen in emf series get corroded vigorously.
Lower the reduction potential greater is fine rate of corrosion, when two metals are in
contact the more active metal undergoes corrosion.
The rate and severity of corrosion depends on the difference in their positions in the emf
series. Greater the difference faster is the corrosion rate.
b) Relative areas of the anode and cathode
The rate of corrosion will be more, when the cathodic area is larger when the cathodic area
is larger, the demand for electrons will be more and this results in an increased rate of corrosion of
metals at anodic area.
c) Purity of the metal
The 100% pure metal will not undergo any type of corrosion. But the presence of
impurities in a metal create heterogeneity and thus galvanic calls are set up with distinct anodic
and cathodic area in the metal.
Higher the % of impurity, faster the rate of corrosion of the anodic metal.
d) Over voltage (or) over potential
The over voltage of a metal in the corrosive environment is inversely proportional to
corrosion rate over voltage & corrosion rate.
Over voltage α 1/ corrosion rate
e) Nature of the surface film
The nature of the oxide film formed on the metal surface decides the extent of corrosion
which can be decided by pilling bed worth rule.
(i) In the case of alkali and alkaline earth metals such as Mg, Ca, etc form oxide, whose
volume is less than the volume of the metal.
(ii)Hence the oxide film will be porous and further corrosion form oxide, whose volume is
greater than that of the metal.
(iii) Hence the oxide film will be non-porous and protective and prevents further corrosion.
f) Nature of the corrosion product
If the corrosion product is soluble in the corroding medium, the corrosion rate will be faster
similarly if the corrosion product is volatile (like MoO3 & MO surface) the corrosion rate will be
faster.
ii) Nature of the environment
a) Temperature
The rate of corrosion is directly proportional to temp. this is because, the rate of chemical
reaction and the rate of diffusion of the ions increases with rise in temp.
Hence the rate of corrosion increases with temp.
b) Humidity
The rate of corrosion will be more when the humidity in the environment is high. The
moisture act as a solvent for the oxygen in the air to produce the electrolyte which is essential for
setting up a corrosion cell.
c) Presence of corrosive gases
The acidic gases like CO2, SO2, H2S and fumes of HCl, H2S04 etc produce electrolytes
which are acidic and increases the electrochemical corrosion.
d) Presence of suspended particles
Particles like NaCl (NH4)2 SO4 along with moisture act as powerful electrolytes and thus
accelerate the electrochemical corrosion.
e) Effect of PH
The possibility of corrosion with respect to PH of the electrolytic solution and the
electrode. Potential of the metal is correlated with the
help of a pourbaix diagram.
Types Of Inhibitors
Inhibitors are classified into 3 types
1. Anodic inhibitors
2. Cathodic inhibitors
3. Vapour phase inhibitors
1. Anodic inhibitors
Ex: Chromates, nitrates, phosphates, tungstates (or) other ions of transistion elements with
a high oxygen content.
Anodic inhibitors are those that prevent the corrosion reaction, occurring at the anode,
by forming an insoluble compound with the newly produced metal ions. These precipitates are
adsorbed on the metal (anode) surface, forming a protective film and reducing the corrosion rate.
Though this type of control is effective of may be dangerous since severe local attack can
occur, if some areas are uncovered.
2. Cathodic inhibitors
In an electrochemical corrosion the cathodic reactions are of two types depending upon the
environment.
a) In an acidic solution
Ex: Organic inhibitors like amines, mercaptanes, heterocyclic nitrogen compounds,
thioureas, substituted ureas, heavy metal soaps.
In an acidic solution, the cathodic in evolution of H2 (i.e)
2H+ + 2e - → H2 ↑
The corrosion can be reduced into 2 ways,
(i) By slowing down the diffusion of H+ ions to the cathode. This can be done by adding
organic inhibitors like amines, pyridines etc. Which are absorbed at the metal
surfaces.
(ii) By increasing the over voltage of hydrogen evolution. This can be done by adding
antimony and arsenic oxides, which deposit adherent film of metallic arsenic (or)
antimony at the cathodic area.
b) In a neutral solution
Ex: Sodium sulphite (Na2 So3)
Hydrazine (N2 H4)
In a neutral solution the cathodic reaction is
H2o + ½ O2 + 2e –→ 2OH ─
The corrosion can be reduced in two ways.
(i) By eliminating the oxygen from the neutral solution thereby formation of OH─ ions are
inhibited. This can be done by adding reducing agents like Na2 So3, N2 H4 etc.
(ii) By eliminating the OH─ ions from the neutral solution. This can be done by adding Mg,
Zn, (or) Ni Salts. Those react with OH─ ions form insoluble hydroxides which are
deposited on the cathode forming more (or) less impermeable self-barriers.
3. Vapour phase inhibitors (VPI)
Ex: Dicyclo hexyl ammonium nitrate, benzotriazole etc..
Vapour phase inhibitors (VPI) are organic inhibitor which readily vapourize and form
protective layer on the metal surface. VPI are used in the protection of storage containers. Packing
materials, sophisticated equipment etc.
PITTING CORROSION
In pitting corrosion rapid penetration in some area of metal takes place due to the break down
of the oxide film is some part of the metals like Al,
Ti and alloys like stainless steel are prone to such
kind of attach.
Pitting corrosion is influenced by PH and
temperature of the medium as well as critical
pitting potential. Pitting diminishes (or) slows
down with increase in PH due to the increase of
OH- ions. Increase in temp can decreases the critical pitting potential and increases the pitting rate.
Critical pitting potential in the redox potential of the metal solution able which there is a
sharp increase in the pitting rate.
This kind of corrosion can happen in the presence of chloride ions (cl-) whereas pitting is
reduced by the oxcenions like S04 2─ , NO3─ , CrO4 2─, SiO3 2─ etc.
Pitting corrosion starts with the small cervices (pits). Once the pit formation is
established the metallic part below the pit becomes anode and further corrosion takes place at
anode area.
The other parts of the metal become cathode and absorbs the liberated e-s from the
anode.
Stress corrosion
Stress corrosion is caused by the conjoint action of a local corrosion attack and tensile stress
in the presence of specific corrosion environment.
Stress corrosion will be severe only when there is severe stress as well as the environment
favoring the stress corrosion.
Ex: Mild carbon steels in the presence of strong alkali solutions produce stress corrosion.
Mg & al alloys are affected by stress corrosion in the presence of chloride ions (cl -).
Stress corrosion starts with preexisting surface discontinuity (or) crack where the stress is
naturally more under favorable environment (or) medium for electrochemical type of corrosion
progress.
For example aluminum alloy (or) stainless steel in the presence of Hydrochloric acid
medicines undergoes stress corrosion.
At the end of the crack stress is concentrated as well as it acts as anode where the metal
deteriorates in to its ion (M 2+ ).
M → M 2+ + 2e- (anode)
The e-s produced at the anode are absorbed at the oxide film which, as cathode. In this type
of corrosion inside the cracks (or) discontinuities
of the metal hydrolysis of water produces acidic
solutions which will further increase stress
corrosion.
O2 + 4H+ + 4e- → 2H2O(cathode)
The stress propagates in 2 way in the
grains of the crystalline metals.
Inter granular stress corrosion propagates
along the grain boundary of the metal.
Usually the metal under stress will have grain boundaries with higher energy levels, which
acts an anode. The grain centres won’t be affected easily by stress and hence they will be in the
normal energy state and acts as cathode. At the anode the deterioration of metal takes place.