Corrosion Forms II

Pitting and Crevice Corrosion Dr. Zuhair M. Gasem ME, KFUPM

Dr. Z. Gasem ME472-062 KFUPM

Forms of Electrochemical Corrosion

Four categories of corrosion forms:

General corrosion (uniform corrosion over the whole anode) Localized Corrosion (corrosion at isolated areas in the anode) Galvanic corrosion pitting corrosion Crevice corrosion Metallurgically Influenced Corrosion (corrosion is related to microstructure) intergranular corrosion of stainless steel Mechanically Assisted Corrosion (corrosion is accelerated due to mechanical factors) Erosion corrosion Corrosion Fatigue Environmentally Assisted Cracking (corrosion results in cracking) Stress corrosion cracking Hydrogen damage

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Forms of Corrosion

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Pitting Corrosion

Metals and alloys can be active (no protective passive film) or passive (passive film 10-30 nm in thickness) Pits Pitting corrosion : rapid corrosion penetration at small discrete areas where passive passive film breaks down andfilm appears as small diameter holes (0.1-5 mm). The remaining surface is not attacked. Pitting corrosion is common in passive metals above pitting potential (Ep) Weight loss is negligible

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Pitting Corrosion
Pitting of stainless steel, Ni alloys, Al alloys in aerated seawater or acids containing Clions Steel buried in the soil corrodes with the formation of pits. Pitting of steels and aluminum in alkaline solutions containing ClPitting can occur in any alloy that form a protective film and exposed to stagnant solution containing ClExample: 316 SS centrifuge head exposed to CaCl2 solution showing deep pits

Examples:

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Pitting Corrosion

Right: pitting in carbon steel pipe carrying strong acid. Below: deep pits on a carbon steel in HCl.

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Pitting Corrosion

Top: pits in stainless steel valve plate (stagnant solution). Bottom: internal pits in steel pipeline carrying water with dissolved CO2

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Pitting Corrosion
Stagnant solutions

Conditions favoring pitting:

Acidic solutions Presence of Cl and Br ( halides) High temperature rough surface finish Commonly occur in passive metals (such as stainless steels) Presence of surface deposits (deposits form localized concentrated environments around them) Rupture of protective coatings Pits form in gravity direction

pitting occurs during shutdown period more than during normal operation During shutdowns, solutions in pipes, pumps, and tubes are stagnant and allow pits formation.

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Pitting Corrosion
pitting corrosion is dangerous?
Pitting corrosion is not easily detected and evaluated and thus more dangerous than general corrosion or galvanic corrosion. Pits can grow and become like cracks Can lead to failure by perforation with minimum weight loss Pits formation may take place after a long period of initiation (tricky) Aluminum parts in the space shuttle Apollo were rejected because they contained pits having a diameter of a human hair.

Why

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Pitting Corrosion
Different misleading pit (hole) shapes Small weight loss Cant use thickness measurement Small pits are hard to observe visually Corrosion products may mask pits

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Difficulty of detection

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Stages in Pitting Corrosion

Pits initiation at film break downs due to

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Two stages in pitting: initiation and propagation

Pits initiation at surface deposits or scratches of paints

Mechanical scratch Localized High Cl- concentration Localized failure of coatings or paints At metal microstructural inhomogenity (inclusions in SS)

Most initiated pits become unstable and do not grow if the passive film reforms or the highly concentrated environments are washed off If passive film reformation is not possible (high concentration of Cl-), then a pit will grow at faster rate due to autocatalytic effect.

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Autocatalytic Nature of Pitting

O2 + 2H2O + 4e- 4 OH-

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In the propagation stage of pits in SS in aerated salt water (seawater):

Oxygen is depleted inside the pit and oxygen reduction takes place around the pit Anodic dissolution of the metal produces M+ ions inside the pit Cl ions diffuse toward the pit to neutralize cations charge. Cl and M+ inside the pit combine and produce more H+ by hydrolysis (M++Cl)+H2OMOH+H++Cl The electrolyte becomes more acidic inside the pit and more corrosive d (Pit depth) because higher H+ and Cl Reach autocatalytic stage where pit growth follows d = ktn.

Parabolic growth

k is a constant and n ranges from 0.3 to 0.8

initiation

Propagation
time

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Effect of Temperature

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Pitting is strongly influenced by the service Temperature In stainless steels

there is a critical pitting temperature below which pitting will not initiate for each stainless steel alloy 304SS (critical pitting temperature = -2.5 C) 317SS (critical pitting temperature = -0 C) Pitting resistance is improved by increasing Cr (>18%) and Mo (2-4%).

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Temperature effect

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Three alloys are tested for pitting resistance by immersion for 24 hr in very aggressive solution.

All alloys have high resistance to pitting at 25 C Alloy G: Ni-20Fe-22Cr-6Mo

Shows pitting at 70 C Shows pitting at 102 C

Alloy 625: Ni-22Cr-9Mo

Alloy C-276: Ni-16Cr-16Mo4W

No pitting until 102 C

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Pitting Evaluation and Control

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Use of standard charts to estimate pitting density (number of pits per cm2 of metal surface) Pitting evaluation is given according to standard charts

A-4 pit density=100,000/m2 B-3 pit surface size = 8 mm C-2 Pit depth = 0.8 mm

Use pit opening diameter Average pit depth

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Control and Prevention of Pitting Corrosion Reduce Cl- content in the electrolyte Lower acidity of solution, lower O2 Shot peen the surface. Passivate stainless steels (SS) by washing with 20% HNO3 to give it a strong passive film. Replace 304 SS with 316 which contains higher Mo Avoid stagnant solutions in tanks, tubes, and pipes Redesign to ensure proper drainage

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Concentration Cells

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Variation in the electrolyte in: dissolved ion concentration dissolved O2 pH temperature create a concentration cell in the electrolyte where some region of the electrolyte will favor cathodic reactions and others favor anodic reactions. Corrosion of storage tanks: corrosion will be localized at the boundary between two electrolytes having different ion or O2 concentrations.

The electrode potential becomes more +ve as the metal ions concentration increases (see Nernsts equation)

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Oxygen Concentration Cell

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In oxygen concentration cell, for example, cathodic reactions are favored in region having high concentration of Oxygen. Example 1 : a drop of water on a metal surface. The cathodic reaction is:

In neutral solution (pH=7)

O2 + 2H2O + 4e- 4 OHe=0.82+0.059/4*log PO2 e is more +ve PO2

The drop surface dissolves O2 from the air and will have high concentration of O2. At the center of the drop, the O2 concentration is low. The metal at the periphery of the drop (high O2) will act as the cathode (more +ve e). The metal at the center of the drop (low O2) will act as the anode. This creates an oxygen concentration cell or air differential cell which localizes corrosion. Oxygen concentration cell is responsible for many corrosion problems. Example 2: oxygen concentration cells on the legs of offshore steel structure

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Differential aeration cell

Cathodic reaction: O2 + 2H2O + 4e- 4 OHCathode: at high conc of O2 near the top surface of tank or sea surface Anode at low conc of O2 below the surface

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Corrosion is frequently caused by concentration difference in O2 from air. Oxygen solubility in water at RT is very small (8 ppm) and decreases with temp.

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Differential aeration cell

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corrosion in stainless steel thermometer pocket in sea water cooled steam condenser. A stagnant layer of sea water formed along the stem on the downstream side Differential aeration cell

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Crevice Corrosion

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Crevice: narrow opening or small gap between two contacting surfaces. (0.025-0.1 mm) Crevice corrosion: localized corrosion resulting from a concentration difference b/w the electrolyte within the crevice and the electrolyte outside the crevice due to stagnation of electrolyte. Possible concentration difference in:

O2 H+ (acidity) Cl-

High PO2 ,low [Cl-] and H+

Low PO2 , high [Cl-] and H+

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Crevice Corrosion

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Inside the crevice: low concentration of O2, and high concentration of H+, and ions such as Cl(more ve Ecorr anode) Outside the crevice: high concentration of O2, and low concentration of H+, and ions such as Cl(more +ve Ecorr cathode) A concentration or differential cell develops between the electrolyte inside and outside the crevice. Accelerated corrosion occurs inside the crevice while the outside is protected.

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Crevice Corrosion

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Crevice corrosion commonly occurs in three different ways:

Geometric crevices: metal-to-metal tight contact where the solution can get between the two contacting metals

Threaded parts Bolted and lap joints

Metal-to-nonmetal absorbent: the nonmetal absorbs the solution and continually moisten the metal

Wood/metals Paper gasket/metals Sponge rubber gaskets in metallic pipe joints

Deposit corrosion: deposits that are porous and absorbent of the solution such as sediment, lime, and rust on metal surfaces

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1. Geometric crevices

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Example of a crevice corrosion of a bolted joint. The threads in the nut and bolt will experience crevice corrosion. Examples of crevices created in pipe connections:
a. b. c. d.

Incomplete penetration of a butt weld A threaded joint A socket connection A flange connection with foamed rubber gasket

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2. Metal-to-nonmetal absorbent

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Crevices are created by design such as gaskets in flanges, Orings, washers, and insulations.

Crevice corrosion at the flange/gasket contact

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3. Deposit corrosion

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Thick calcium carbonate (CaCO3) deposits on a condenser tubes

Thick greasy deposits on steel tank. Corrosion attack is due to crevice effect.

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Alloys susceptible to crevice corrosion

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Crevice corrosion can attack active and active-passive metals and alloys but active-passive metals are more susceptible as stainless steels and aluminum. Example:

stainless steel universal joint showing crevice corrosion beneath the rubber grommet Crevice corrosion at the washer-bolt contact in SS fastener in seawater

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Crevice Corrosion

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Materials resistance to crevice corrosion is tested using Teflon blocks in very corrosive electrolyte:

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Alloys susceptible to crevice corrosion

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316 SS is more resistant to crevice and pitting corrosion than 304 SS.

304 SS is pitted badly in very corrosive electrolyte (acid condensate) which prevented crevice corrosion (figure a) 316 SS is not pitted in the same environment but crevice corrosion is evident (figure b) 304 SS in mild aggressive environment showing Crevice corrosion (figure c)

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Alloys susceptible to crevice corrosion

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Cast iron and steel show excessive crevice corrosion beneath rubber orings Often times crevice corrosion is masked by uniform corrosion in carbon steels

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Development of Crevice Corrosion

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Initiation and Propagation in C.C.

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Propagation of crevice corrosion (SS in neutral aerated NaCl solution): Anodic (MMn++ne-) and cathodic reactions (O2 + 2H2O + 4e- 4 OH-)occur inside and outside the crevice. Oxygen is consumed inside the crevice Oxygen can be supplied at the outside of crevice. A differential aeration cell develops. Oxygen reduction occurs only outside the crevice Anodic reaction inside the crevice produces more +ve ions by (MMn++ne-) Cl- migrate to the crevice for charge neutrality Mn+ and Cl- react and produce high concentration of H+ inside the crevice by hydrolysis (M++Cl)+H2OMOH+H++Cl The pH inside the crevice 2 (acidic) The pH outside the crevice 7 More anodic reaction inside the crevice

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Pitting and Crevice Corrosion

and crevice corrosion are

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Pitting

Different in initiation Similar in propagation (autocatalytic or self sustained corrosion)

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Crevice Corrosion Control

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Crevice corrosion is controlled by the same methods used for pitting and

Reduce crevices in design Use welding if possible instead of bolting two surfaces in contact. Use continuous welds instead of skip welds. Avoid electrolyte stagnation Use none-absorbent gaskets such as Teflon instead of absorbent gaskets such as fiber and wood gaskets. Cleaning to reduce local concentrations of acids, chlorides, ext

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Condensate corrosion

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Hot gases containing H2O vapor and other vapors such as SO2, CO2, or H2S may condensate in droplets on cooler metal surfaces producing localized corrosion which appear as severe pitting. Prevention

maintain the metal temp above the dew point of the hot gasses to prevent condensation. Apply insulation on pipes carrying hot gases Avoid attaching bare metal to hot pipes which may act as cooling fin.

Insulated hot pipe

Flow of hot gases

Connection pipe (no insulation)

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Filiform corrosion

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A crevice can be created due to breach in protective paints. This type of crevice corrosion is very common and called filiform corrosion.