FORMS OF CORROSION

Forms of Corrosion

Uniform Corrosion
Most common Corrosive environment evenly distributed over entire metal surface Metal: metallurgically and compositionally uniform On the basis of tonnage waste, the most important forms of corrosion Most readily detectable (visual) and preventable (alloying)
Atmospheric corrosion (rusting) Corrosion in acid solutions

Localized Corrosion (Attack)

Sources of localized corrosion Environment
Oxygen concentration Chloride ion concentration pH Fl Flow rate t

Material

Segregation g g Inclusions Different phases Grain boundaries

Mechanical

Static stress Fluctuating stress

Galvanic Corrosion (Dissimilar Metal Corrosion) ( )

A potential difference exists between two dissimilar metals connected electrically a current will flow between them corrosion rate of less resistance metal (anodic) .
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Galvanic Corrosion

Galvanic Corrosion (cont.)

The driving force for galvanic corrosion is a potential difference between the difference metals. metals. In a bimetallic couple, the less noble (active) metal will become the anode of this corrosion cell and tend to corrode more compared with the uncoupled condition. The more noble metal will act as the cathode in the corrosion cell and corrode less. Important factors in galvanic corrosion
Relative areas of anode and cathode Difference in potential between anode and cathode Effect of anodic polarization on anode

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., (e g seawater). seawater seawater) ) ).
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Galvanic Corrosion (cont.)

The galvanic series Ordered by observed behavior in service Allows for corrosion products Can be defined for alloys Different for every environment N t th Note that t some alloys ll can appear twice according to whether they are active or passive.

TABLE. Galvanic Series in Seawater (or Fig. 6.1)

A more detailed galvanic g series in water

Example Corrosion of a Soldered Brass Fitting

QUESTION A brass fitting used in a marine application is joined by soldering with leadlead-tin solder. Will the brass or the solder corrode? SOLUTION From the galvanic series, we find that all of the coppercopper-based alloys are more cathodic than a 50% Pb - 50 50% % Sn solder. Therefore, the solder is the anode and corrodes corrodes.

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Galvanic Corrosion (cont.)

Galvanic corrosion can occur between different phases in an alloy. This is especially important when one of the phases is much more active as a cathode, e.g.,
CuCu-containing precipitates in aluminum alloys initiate pitting corrosion Fe and Cu impurities in commercial Zn cause a large increase in corrosion rate compared to pure zinc

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Local electrode cell

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Avoiding Galvanic Corrosion

Insulation

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Beneficial Application of Galvanic Corrosion

Cathodic protection (CP), sacrificial anode protection Galvanized steels; Zn coating is anodic to steel, act as a sacrificial metal

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Differential Aeration (cont.)

cathode

cathode

anode

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Differential Aeration (cont.)

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Differential Aeration (cont.)

water-line corrosion

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Crevice Corrosion ()
A localized form of corrosion usually associated with a stagnant solution on the micro micro-environmental level. S h stagnant Such t t microenvironments i i t t tend dt to occur i in crevices i ( (shielded hi ld d areas) ) such as those formed under gaskets, washers, insulation material, fastener heads, surface deposits, disbonded coatings, threads, lap joints and clamps (usually ( y mismatch of components p at interface). )

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Initiation of Crevice Corrosion

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

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n+

Chronology of Crevice Corrosion

M O2 OH-

anodic

Cathodic

O2

OHM

n+

O2

OHM

n+

1 anodic and cathodic reactions occur over the entire surface

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n+

Chronology of Crevice Corrosion

M O2 OH-

anodic

Cathodic

O2

OH- O2

OHM

n+

n+

n+

2 Depletion of oxygen inside the crevice 3 - Metal dissolution takes place inside the crevice

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Chronology of Crevice Corrosion

M n + + nCl + nH2O M(OH )n + nHCl

ClO2 OH- O2 OHM M M M n+ M n+ M n+

4 Attraction of Cl- inside the crevice (charge balance) 5 pH decreases inside the crevice (more acid) enhance dissolution
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Chronology of Crevice Corrosion

ClClO2 OH- O2 OHM M M M
n+

n+

n+

H+

6 The crevice formation is an auto-catalytic process

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Crevice Corrosion - Summary

AutoAuto-catalytic process A small area anodic inside the crevice a large cathodic aereated area outside. Dangerous !!!

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Crevice Corrosion - Example

Crevice corrosion of Ti flange in hot seawater

C i corrosion Crevice i of f SS

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Crevice Corrosion at Pipe Socket Joint

Crevice corrosion of socket weld at gap formed between type 304L pipe And type 316L valve

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Pitting Corrosion ()
Pitting corrosion 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.

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

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Morphology of Pitting

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Undercutting of a Pit

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Underdeposit Corrosion

Underdeposit pitting of carbon steel sprinkler pipes

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Pitting on Stainless Steel in Cl- Environments

Inside the growing pit, the hydrolysis of Cr3+ lowers the pH and breaks down the passive film. The cathodic oxygen reduction reaction continues outside the pit. pit. The presence of chloride is important, as it allows a pH of about 1 to be achieved (HCl (HCl is a strong acid, and does not associate) and the metal chloride are very soluble. soluble.

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Pitting Corrosion: Examples

Pitting of exterior of lead cable sheath due to stray current

Chloride pitting of stainless steel due to soldering flux contamination

Carbon steel Pitting underground

Pitting of Aluminum air duct due to salt contamination

Pitting of Inconel in Brine

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Management of Pitting
Stainless steels
Pitting breakdown potential (that potential above which the anodic current starts to increase); lower pitting breakdown potential implies greater susceptibility to pitting. Critical pitting temperature (CPT, temperature at which pitting is observed in aggressive conditions); lower CPT implies greater susceptibility. tibilit Pitting resistance equivalent (formula based on composition (e.g., Cr+3Mo+30N) gives ranking of alloys

Pit growth tends to follow a law of the form

Depth = constant timen where n is between 0.3 and 0.5

Pitting is a statistical process, and can be modeled by extreme value statistics.

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Dealloying (Selective Leaching)

Alloy containing one noble element and one base element (e.g., brass, Cu + Zn) Base element can dissolve leaving a matrix of noble element
Dezincification of brass Graphitization of grey cast iron

Causes a loss of mechanical strength g without obvious change g in shape

Color change Drastic reduction in strength g Minimal volume change Special evaluation technique

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Dezincification of a Brass

Uniform annulus of De-zincification

Plug t Pl type of f De-zincification

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Dezincification of a Brass

Denickelification
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Dealuminification of a C95800 Ni-Al bonze pump impeller in service in a wastewater plant

Dezincification of a admiralty brass

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Intergranular Corrosion (IGC; )

IGC is a localized attack along the grain boundaries, or immediately adjacent to grain boundaries, while the bulk of the grains remain l largely l unaffected. ff t d

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Cause of Intergranular Corrosion

Grain boundaries are somewhat more reactive than the matrix of an alloy, but since the difference in reactivity is slight, grain boundary effects ff t are usually ll of f little littl consequence. Chemical segregation effects (Impurities have a tendency to be enriched at grain boundaries.) Specific phases precipitated on the grain boundaries. Such precipitation can produce zones of reduced corrosion resistance in the immediate vicinity.

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Example of IGC (Sensitization)

Sensitization of Stainless Steel or Weld Decay y
When grain boundary Cr carbide precipitation has occurred the stainless steel is occurred, said to be sensitized. Sensitization frequently occurs in the heat heat-affected zone ( (HAZ) ) during welding, and the resultant corrosion is called Weld decay.

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Solving Welding Decay

Use a low carbon grade of stainless steel (304L, 316L SS) Use a stabilized grade of steel, which includes a strong carbide carbideforming element (Ti or Nb) Nb) to lock up the carbon in the grain. For existing components that have been sensitized, heat treat to reredissolve the carbides. (but this is very difficult in practice)

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Flow Effects

Flow can
Increase the transport of oxygen to the metal surface (may help to passivate) passivate ) Increase the rate of dissolution of corrosion product films Mechanically y remove oxides

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Erosion Corrosion
Corrosion accelerated by impact by solid particles These may remove metal, or they may just remove oxide and allow metal to corrode more quickly. They are unexpected mostly because evaluation corrosion tests run under static conditions or because the erosion effects were not considered.

Schematic of erosion corrosion of heat exchanger handling water

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Erosion Corrosion (cont.)

Vulnerable equipment includes:
pipes (bends, elbows, tees); valves; pumps; blowers; propellers, impellers; stirrers; stirred vessels; HX tubing (heaters, (heaters condensers); flow-measuring orifices, venturies; turbine blades; nozzles; baffles; metal-working equipment (scrapers, cutters, grinders, mills); - spray impingement components; - etc. etc

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Example of Erosion Corrosion Seawater pump

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Cavitation Corrosion
Cavitation occurs when a fluids operational pressure drops below the vapor pressure causing gas pockets and bubbles to form and collapse.

C it ti corrosion Cavitation i of f a deaerator d t

HighHigh-speed pressure oscillations (pumps, etc.) can create shockwaves > 60 ksi. ksi. Surface attack resembles closelyclosely-spaced pitting Plastic deformation of metal: the presence of slip lines in equipments subject to cavitations
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Fretting Corrosion
Wear process due to relative motions in highly loaded devices exaggerated by corrosive environment
Roughness of contacting surfaces Device micromotions

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Fretting Corrosion

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Environmental Cracking
Corrosion cracking caused by a combination of conditions that can specifically result in one of the following form of corrosion damage. Tensile stresses that cause environmental cracking arise from
Residual cold work Welding Grinding Thermal treatment Service conditions

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Types of Environmental Cracking

Stress corrosion cracking (SCC)
Sulfide stress corrosion cracking Chloride induced SCC Caustic induced SCC

Corrosion fatigue (CF) Hydrogen embrittlement (HE) Liquid metal embrittlement (LME; )

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Stress Corrosion Cracking (SCC)

SCC is the cracking is the cracking induced from the combined influence of tensile strength and a corrosive environments Usually most of the surface remains unattacked, unattacked, with fine cracks penetrating into the metal These cracks can have an intergranular (IG) or transgranular (TG) morphology in the microstructure. 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 yp predicted.

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SCC - Examples

IGSCC of an Inconel heat exchanger tube (500X)

Chloride SCC of S31603 (316L) chemical processing piping system. It can be characterized by the multi-branched lightning bolt TG crack pattern (300X)

Caustic SCC in a 304L SS pipe in methanol reforming service oxalic acid etch (50X)
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Hydrogen Embrittlement
Also called: hydrogen induced corrosion (HIC) Involves the ingress of hydrogen into the metal causing
Reduced ductility and load load-bearing capacity Subsequent cracking and Catastrophic brittle failures at stresses below the yield stress of susceptible materials

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

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

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Corrosion Fatigue (Cracking)

The fatigue fracture of a metal aggravated by a corrosive environment or the SCC of a metal aggravated by cyclic stress to decrease the number of cycles to failure.

Stress Range

F Ferrous

N f Non ferrous

Ferrous with corrosion Non ferrous with corrosion log. number of cycles to failure (Nf) 10
7

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Corrosion Fatigue

Corrosion fatigue cracks on the ID of a Admiralty Brass exchanger tube

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References
Corrosion: Understanding the Basics, ASM International, 2000 Corrosion: L.L. Shreir Shreir, , Corrosion, 3rd ed., ButterworthButterworth-Heinemann, UK, 2000. Basic Corrosion Course, NACE International, 2003. D.R. Askeland Askeland, , The Science and Engineering of Materials, 4th ed., Ch.22: Corrosion and Wear. M.G. MG F Fontana, t C Corrosion i E Engineering, i i 3rd ed., d 1986 1986. Corrosion Doctors, www.corrosion www.corrosion-doctors.org. POSCO www.steelPOSCO, www.steel t l-n.com. Kennedy Space Center, NASA, corrosion.ksc.nasa.gov. Corrosion Testing Laboratories, Inc., www.corrosionlab.com Metallurgical M t ll i l Technologies, T h l i I Inc., www.met www.mett-tech.com t h

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