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Corrosion
Definition Causes of Corrosion Formation of Corrosive Films Electrochemical Mechanisms for Corrosion Corrosion Prevention Methods Application
Definition of Corrosion
Corrosion
Corrosion is also defined as the oxidation of a metal to
an alloy because of chemical or electrochemical reaction with its surrounding environment or medium
It is an inconvenient, costly and sometimes unavoidable
1Sheir,
Environments in Corrosion1
L.L., R.A. Jarman, and G.T. Burstein, eds. Corrosion. 3rd ed. Vol. 1. 2000, Butterworth-Heinemann: Oxford.
2Fontana,
Corrosion Basics
Occurs mostly in ionic, aqueous environments Primarily a concern for metals Oxidation Reduction Reaction:
Corrosion Basics
Only Cu and precious metals such as gold, silver and
Corrosion Basics
Iron, a common construction metal often used in forming
acids, because these materials make electrically conductive solutions that make electron transfer easy
Causes of Corrosion
Multifactorial (many factors) problem-depends on geometry, metallurgy, stresses,
solution chemistry
Driven by two primary factors: thermodynamic driving forces (Oxidation/Reduction) and kinetic barriers An electro-chemical attack resulting in material degradation Exacerbated by mechanical and biological attack Compromises Material Properties Mechanical Integrity Biocompatibility Aesthetics
Causes of Corrosion
Metals corrode because we use them in environments where they
water and oxygen, though other substances in the earth and in the atmosphere can also cause corrosion.
Effects of Corrosion
The consequences of corrosion are many and varied and the
effects of these on the safe, reliable and efficient operation of equipment or structures are often more serious than the simple loss of a mass of metal.
General corrosion, also referred to as uniform corrosion, is one of the most common types of corrosion
It damages the entire surface of the material at about the same rate, causing the metal to thin.
It is a chemical attack, easily detected by its appearance. Controlling general corrosion is relatively easy. However, if not controlled, the metal surface continues to thin until nothing is left.
General Corrosion
Crevice corrosion, also called concentration cell corrosion This type of corrosion forms when a liquid corrosive is trapped in narrow gaps of space between metals, or between nonmetals and metals. such as chlorides must be present in the
Aggressive ions,
electrolyte.
Once
the liquid has settled in the gap, a corrosion reaction begins to take place.
The reaction consumes the oxygen in the bottom of the gap, and an anodic area develops adjacent to the oxygen-depleted zone. The material on the exterior acts as the cathode. Crevice corrosion develops quite similar to pitting corrosion after the initiation stage with a gradual decrease of the pH and an increase of the chloride concentration within the crevice.
Can arise from localized oxygen depletion and metal ion concentration gradients
OHOH-
O2 O2 O2 OHOH-
between components results in fretting corrosion that can lead to initiation of crevice corrosion
Metallic implants rely on passive oxide film for protection from corrosion.
Repetitive motion leads to continuous breakdown and repassivation. Repeated breakdown consumes oxygen in crevice and results in drop in pH--crevice corrosion.
materials, such as gaskets, fasteners, surface deposits, washers, threads, clamps, and any close-fitting surfaces often initiates crevice corrosion.
Crevice Corrosion
Crevice corrosion can be
Unpassivated metal is exposed to initially oxygen rich fluid. Oxidation occurs--depleting oxygen in crevice fluid--increases free metal
Metal chlorides react with water to form metal hydroxide and HCl--lowers
Galvanic corrosion occurs in the presence of an electrolyte such as seawater when dissimilar types of metals join together. Most metals have different electrical potentials. When connected electrically and placed in an electrolyte, the more active metal becomes the anode because it has more negative potential and corrodes faster than if it were alone in the environment.
The more noble (less active) metal becomes the cathode because it has more positive potential and corrodes at a slower rate than if it were alone in the environment. Electrical current flows between the metals until their potentials are equal. Galvanic corrosion typically appears in joints where the two dissimilar metals meet.
electrolytic environment
M+
M+
nM =
nM+ +ne-
eM
N+ N+
M+ M+
nN+ + ne- = N
N+ N+
N+
Metal 1
Metal 2
Galvanic Corrosion
Pitting corrosion causes damage by randomly attacking a limited section of the metal's surface, leaving behind holes that are larger in depth than width.
The "pit" that forms functions as the anode and the metal that is left undamaged functions as the cathode.
The corrosion process starts with a chemical breakdown in a small spot such as a scratch or a nick, usually occurring under a surface coating that has experienced wear or damage.
As the pitting progresses, the metal becomes thinner, and fatigue and stress corrosion cracking begins at the base of the corrosion pits. The failure can be catastrophic. For example, a gas line that was positioned over a sewer line killed 215 people in Guadalajara, Mexico, because of a single pit that had formed in the gas line.
M+
M+ H+ Cl-
M+
H+ Cl-
M+
M+
Pitting Corrosion
boundaries
Corrosive Films
Corrosive film is a formation on the surface of a material
due to acidic substances and environments such as, Seawater, carbon steel rust and Iron Chloride (FeCl3).
Corrosive films will deteriorate the material on a molecular
level, spreading through the material homogenously at a fast or slow rate depending on the type of material.
Eg. Stainless steel isnt easily corroded, even in a coastal
atmosphere. But when it is contaminated by alien pollutants such as carbon steel rust or Iron Chloride (FeCl3) in combination with seawater, corrosive films begin to develop quicker.
surface film formation on stainless steel contaminated by alien pollutants (a) clean bare surface after 60 days exposure; (b) carbon steel rust + seawater; (c) FeCl3 + seawater
Electrochemical Corrosion
Electrochemical corrosion is a process through which a
such as gold, and therefore are already stable in metallic form, which is why gold doesnt corrode.
Unstable metals become stable throughout the years by
Electrochemical Corrosion
In order for electrochemical corrosion to take place a
anode, a cathode, an electrolyte and a metallic pathway connecting the anode and cathode.
Without any of these four elements corrosion will not take
Electrochemical Corrosion
The anode is where metal loss takes place. By ionizing into the electrolyte the ions release electrons
through an elaborate series of chemical reactions producing ferric oxide (Fe2O3) and oxygen.
Ferric oxide is Rust. The cathode is an important element of the corrosion cell
Electrochemical Corrosion
Electrons from the anode travel to the cathode and are accommodated there.
The more electrons a cathode can accommodate the faster the anode will corrode.
This is the primary relationship between the anode and the cathode in a corrosion cell.
The Electrolyte is also an important element of the corrosion cell as it is the solution that surrounds the anode and the cathode.
Electrochemical Corrosion
The electrolyte also has an effect over corrosion rate
since the conductivity of the electrolyte will either allow electrons to freely move from the anode to the cathode or restrict their flow, thus reducing corrosion rate.
The metallic pathway is referred to as the internal
circuit as it is provided by the metal where the anode and cathode reside.
The metallic pathway closes the corrosion circuit.
Electrochemical Corrosion
Oxygen is considered to be an important factor to
corrosion since without oxygen corrosion slows down and eventually stops. ions that are released at the cathode due to the electron accommodation.
the cathode and prevent electron accommodation, thus stopping the corrosion process. This phenomenon is called polarization
Preventing Corrosion
Corrosion of metals can be prevented if the contact between the
something which does not allow moisture and oxygen to react with it.
Coating of metals with paint, oil, grease or varnish prevents the
corrosion of metals.
The coating of corrosive metals with non-corrosive metals also
prevents corrosion.
Corrosion prevention
Preventing Corrosion
Coating to keep out air and water.
oxidized. Alloying with metals that form oxide coats. Cathodic Protection - Attaching large pieces of an active metal like magnesium that get oxidized instead.
Iron is galvanized by dipping it in molten zinc. It is then taken out and allowed to cool. Galvanizing is an effective methods of protecting steel because even if the surface is scratched, the zinc still protects the underlying layer.
molten tin.
Cooking vessels, made of copper and brass get a greenish coating due to corrosion.
We have seen that the oxide layer on the surface of aluminium metal
connecting the metal to the anode in an electrolytic cell with sulfuric acid as the electrolyte.
The thick oxide film that forms is easily dyed to give an attractive
appearance.
The resultant metals, called alloys, do not corrode easily, e.g. stainless steel.
In cathodic protection, a second, more reactive metal is placed in electrical contact with the metal object being protected from corrosion. The more reactive metal behaves as the anode in the electrochemical cell, thus forcing the other metal to function as the cathode
bridges and pipelines, but instead rusting can be minimized by cathodic protection.
A large block of an active metal, such as zinc or magnesium, is
reduce oxygen.
The active metal therefore corrodes, but is cheaper to replace
is intentionally oxidized under carefully controlled conditions to form a thin, adhering layer of oxide on the surface of the metal.
Treating iron with aqueous sodium chromate forms
a layer of Fe(III) and Cr(III) oxides that protects the iron from contact with oxygen and water:
2Fe(s) + 2Na2CrO4(aq) + 2H2O Fe2O3(s) + Cr2O3(s) + 4NaOH(aq)
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
Rainwater Guttering
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.
Aluminium Rim
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.
Bicycle
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.
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.