Types of Corrosion

Dr. Hamdy A. Kandil

Metallic corrosion

Forms of corrosion
Uniform corrosion Pitting Crevice corrosion Galvanic corrosion Erosion corrosion Cavitation Fretting corrosion

Forms of corrosion
Intergranular corrosion Exfoliation Dealloying (selective leaching) Environmental cracking Stress Corrosion Cracking (SCC) Corrosion fatigue Hydrogen embrittlement

Uniform corrosion

Uniform corrosion is characterized by corrosive attack proceeding evenly over the entire surface area, or a large fraction of the total area. On the basis of tonnage wasted, this is the most important form of corrosion.

Pitting

Pitting corrosion is a localized form of corrosion by which cavities or "holes" are produced in the material. Pitting is considered to be more dangerous than uniform corrosion damage because it is more difficult to detect, predict and design against.

A Pit

deep pit (anode) (small pits)

general attack

An aluminum A92519 specimen exposed to a 3,5% NaCl solution for seven days. The width of the picture is approximately 1 mm.
intact (cathode)

Causes of pitting

Localized chemical or mechanical damage to the protective oxide film. Low dissolved oxygen concentrations and high concentrations of chloride (as in seawater) Localized damage to, or poor application of, a protective coating The presence of non-uniformities in the metal structure of the component, e.g. inclusions.

Passive metals pit

Pitting corrosion on a stainless steel bar exposed to an alkaline solution loaded with chlorides.

Morphology of pitting
narrow/deep pits elliptical pits shallow pits

mesa attack

Morphology of pitting
Subsurface pits
Undercutting pits vertical grain attack

Horizontal grain attack

A pitting-related accident
The sewer explosion that killed 215 people in Guadalajara, Mexico, in 1992. Besides the fatalities, the series of blasts damaged 1,600 buildings and injured 1,500 people. Damage costs were estimated at 75 million U.S. dollars.

Crevice corrosion
Crevice corrosion is a localized form of corrosion usually associated with stagnant solutions in shielded areas such as those formed under gaskets, washers, insulation material, fastener heads, surface deposits, disbonded coatings, threads, lap joints, clamps, etc.

Example of crevice corrosion

Crevices corrosion of a S30400 stainless steel washer after 30 days in 0.5 FeCl3 + 0.05 M NaCl solution

Another example of crevice corrosion

Stainless steel bolt used in seawater after 5 years of exposure.

Initiation of crevice corrosion

Crevice corrosion is initiated by changes in local chemistry within the crevice:
Depletion of inhibitor in the crevice Depletion of oxygen in the crevice A shift to acid conditions in the crevice Build-up of aggressive ion species (e.g. chloride) in the crevice

Popped rivets found on an external section of a maritime patrol aircraft fuselage.

Analysis of a crevice-corrosion related problem (popped rivets)

Subsequent inspection revealed corrosion in the bonded area of the skin plates. The cause was believed to be water ingress from a global positioning system (GPS) antenna. It was believed that water penetrated through cracks in the seal surrounding the GPS antenna. Once the water was in, crevice corrosion began and it ultimately led to the loss of the bond between the two portions of the structure. The loss of this bond allowed more water to seep in the structure and generalized the corrosion problem.

Analysis of a crevice-corrosion related problem (continued)

Underside of panel where severe corrosion was found

Analysis of a crevice-corrosion related problem (continued)

Close-up picture showing the severity of corrosion

Advanced crevice corrosion pillowing

Notice how the rivet heads appear to be lower than the surrounding skin surface.

Stage 0 of crevice corrosion

Consider the case of a passive metal corroding Assume that the main cathodic species is dissolved oxygen Crevice shown is not drawn to scale (it is much narrower and longer in reality)

Initially,

the dissolved oxygen content in the crevice is equal to the one outside. The corrosion rate is uniform.

Stage 1 of crevice corrosion

Due to the difficult access caused by the crevice geometry, oxygen is rapidly depleted in the crevice by uniform corrosion. The corrosion reactions now separate, i.e. metal dissolves more in the crevice (anode) and oxygen is reduced more on the outside metal surface (cathode).
The large cathodic surface (Sc) vs. anodic surface (Sa) ratio (Sc/Sa)

leads to an acceleration of the anodic (corrosion) reaction in the crevice.

Stage 2 of crevice corrosion

The metal ions produced by the anodic corrosion reaction form corrosion products (hydrolyze) giving off protons (acid) and. The pH in a crevice can reach very acidic values, sometimes equivalent to pure acids.
The acidification of the local environment produces a serious increase in the corrosion rate of most metals. The corrosion products seal even further the crevice environment and the problem gets worse.

Galvanic corrosion

The driving force for corrosion is a potential difference between the different materials. In a bimetallic couple, the less noble material will become the anode of this corrosion cell and tend to corrode more compared with the uncoupled condition. The more noble material will act as the cathode in the corrosion cell and corrode less.

Example of galvanic corrosion

Stainless screw in contact with a cadmium plated steel washer

Nobility and galvanic corrosion

The relative nobility of a material can be predicted by measuring its corrosion potential. The well known galvanic series lists the relative nobility of certain materials in a given environment (e.g. seawater). A small anode/cathode area ratio is highly undesirable. In this case, the galvanic current is concentrated onto a small anodic area leading to a very high corrosion rate.

Galvanic series in seawater

Platinum Gold Graphite Titanium Silver Chlorimet 3 Hastelloy C 18-8 Mo stainless steel (passive) 18-8 stainless steel (passive) Chromium steel >11 % Cr (passive) Inconel (passive) Nickel (passive)

Galvanic series in seawater (continued)

Silver solder Monel Bronzes Copper Brasses Chlorimet 2 Hastelloy B Inconel (active) Nickel (active) Tin Lead

Galvanic series in seawater (continued)

Lead-tin solders 18-8 Mo stainless steel (active) 18-8 stainless steel (active) Ni-resist Chromium steel >11 % Cr (active) Cast iron Steel or iron 2024 aluminum Cadmium Commercially pure aluminium Zinc Magnesium and its alloys

Erosion corrosion
Erosion corrosion is an acceleration in the rate of corrosion attack in metal due to the relative motion of a corrosive fluid and a metal surface.

Example of erosion corrosion

pump rotor destroyed by erosion corrosion Aggravating factors: high flow velocity flow disturbances presence of solids multiphase flow

Example of erosion corrosion

Inside of the stainless steel pump column spools pumping seawater serving in the Arabian gulf.

Cavitation
Cavitation occurs when a fluid's operational pressure drops below the vapor pressure causing bubbles to form and then increases causing them to violently collapse.

Cavitation usually happens

At the suction side of a pump, especially if operating near the net positive suction head At the discharge of a valve or regulator, especially when operating in a nearclosed position At flow expansions in other processes incurring sudden pressure drops and increases

Fretting

Fretting corrosion is damage at contact surfaces rubbing against each other (under load and in repeated relative surface motion, as induced for example by vibration).

Intergranular corrosion
Intergranular corrosion is localized attack along the grain boundaries, or immediately adjacent to grain boundaries, while the bulk of the grains remain largely unaffected.

Causes of intergranular corrosion

This form of corrosion is usually associated with chemical segregation effects (impurities have a tendency to be enriched at grain boundaries) or specific phases precipitated on the grain boundaries. Such precipitation can produce zones of reduced corrosion resistance in the immediate vicinity.

Example of intergranular corrosion

Sensitization of stainless steels: Chromium-rich grain boundary precipitates lead to a local depletion of Cr immediately adjacent to these precipitates, leaving these areas vulnerable to corrosive attack in certain electrolytes. Reheating a welded component during multi-pass welding is a common cause of this problem.

Exfoliation

Exfoliation is a form of intergranular corrosion associated with high strength aluminum alloys that have been extruded or otherwise worked heavily, with a microstructure of elongated, flattened grains.

failed aircraft component made of 7075-T6 aluminum (picture width = 400 m)

Anisotropic grain structure

in wrought aluminum alloys

Example of exfoliation
exfoliation of an aircraft component

Dealloying (selective leaching)

Dealloying or selective leaching is a selective removal of one or more elements from an alloy by the corrosion processes. Examples: dezincification of unstabilized brass graphitization of gray cast iron

Environmental cracking

Stresses that cause environmental cracking arise from: Residual cold work Welding Grinding Thermal treatment Service conditions To be effective the stresses must be tensile.

Types of environmental cracking

Stress Corrosion Cracking (SCC)

Sulfide stress cracking Chloride induced SCC Caustic induced SCC

Hydrogen embrittlement Corrosion fatigue

Cracks

The cracks form and propagate approximately at right angles to the direction of the tensile stresses at stress levels much lower than those required to fracture the material in the absence of the corrosive environment. As cracking penetrates further into the material, it eventually reduces the supporting cross section of the material to the point of structural failure from overload.

Stress Corrosion Cracking

Stress corrosion cracking (SCC) is the cracking induced from the combined influence of tensile stress and a corrosive environment.

intergranular SCC of an Inconel heat exchanger tube

Stress Corrosion Cracking

Usually, most of the surface remains unattacked, with fine cracks penetrating into the metal. In the microstructure, these cracks can have an intergranular or a transgranular morphology. Macroscopically, SCC fractures have a brittle appearance. SCC is classified as a catastrophic form of corrosion, as the detection of such fine cracks can be very difficult and the failure not easily predicted.

Example of SCC
SCC in a 316 stainless steel chemical processing piping system containing chlorides. Chloride stress corrosion cracking in austenitic stainless steel is characterized by the multi-branched "lightning bolt transgranular crack pattern.

A catastrophic case history

On October 4, 1992 an EL AL Boeing 747 freighter crashed in Amsterdam, killing all four people on board and over 50 people on the ground. The cause of the crash was the number 3 and 4 engines separated from the wing, causing a loss of control. The reason for the number 3 engine separation was a breakage of the fuse pin weakened by a crack. The pin was designed to break when an engine seizes in flight, producing a large amount of torque.

Hydrogen embrittlement
Also called: hydrogen induced cracking Involves the ingress of hydrogen into the metal causing:

Reduced ductility and load-bearing capacity, Subsequent cracking and Catastrophic brittle failures at stresses below the yield stress of susceptible materials

Most vulnerable are high-strength steels, titanium alloys and aluminum alloys

Sources of hydrogen
In the metal making process In meatl processing (phosphating, pickling) From welding In storage or containment of hydrogen gas As a by-product of general corrosion From cathodic protection In electroplating

Hydrogen embrittlement of stainless steel

Hydrogen (atoms) present at the surface enters the steel Hydrogen diffuses along the grain boundaries and combines with the carbon, which is alloyed with the iron, to form methane gas Methane gas is not mobile and collects in small voids along the grain boundaries and reduces ductility The gas can build up enormous pressures that can initiate cracks

Corrosion Fatigue

Corrosion-fatigue is the result of the combined action of an alternating stress and a corrosive environment. The fatigue process is thought to cause rupture of the protective passive film, upon which corrosion is accelerated. The introduction of a corrosive environment often eliminates the normal fatigue limit of a ferrous alloy, thereby creating a finite life regardless of stress level.