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Corrosion

Corrosion

Why study corrosion ?

Corrosion is a worldwide problem

Constructions, chemical companies, marine industries, petroleum companies, food companies, automobiles, aircraft/aerospace, etc.

What is corrosion? Deterioration of a material (or its properties) because of reaction with its environment

The result? Rust !

Study in the US on cost of corrosion per year 1975: $70 billion 1982: $126 billion 1998: $275 billion USD (in US alone) = $370 billion NZD

References

1. Engineering Materials: Properties and Selection by Kenneth G.

Budinski and Michael K. Budinski, Pearson Prentice Hall, 8th edition,

2004

2. Corrosion Engineering by Mars G. Fontana, McGraw-Hill Book Company, 3rd edition, 1987

3. Corrosion Basics: An Introduction, National Association of Corrosion Engineers (NACE), Houston – Texas, 1984

Effects of Corrosion which can result in ……

• Loss of load-bearing cross-section

• or penetration

• Loss of load-bearing cross-section • or penetration • Crack Initiation (due to pits) & Growth

• Crack Initiation (due to pits) & Growth (due to H)

• Blockage

cross-section • or penetration • Crack Initiation (due to pits) & Growth (due to H) •
H H
H
H

Effects of Corrosion which can result in …

• Loss of Electrical Contact

• Decrease in Heat Transfer

• Debonding of Coatings, Spalling of Concrete

• Contamination of products

• Degradation of appearance

H 2 O Pb External Rust Spots
H 2 O
Pb
External
Rust Spots

• Maintenance and operating Cost

• Plant Shutdowns

• Lost valuable products

• Effects on Safety and Reliability

• Product Liability ….$100 billion per year (in the US)…to cover legal cost

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Nature of corrosion Corrosion Reactions Why corrosion occurs? Most metals want to return to their
Nature of corrosion
Corrosion Reactions
Why corrosion occurs?
Most metals want to return to their natural and stable form, i.e. ore.
Fe + H 2 O + 1/2O 2
Fe(OH) 2
Iron ores contain oxide of iron. A few metals, e.g. gold, is in metallic form
Iron
Water
Oxygen
Ferrous Hydroxide
The process allowing the metals to return to ore (oxide or sulfide) is
called corrosion.
Fe + 2HCl
FeCl 2
+
H 2
Practically, all environments are corrosive to some degree
Iron
Acid
Ferrous
Gas
Acids, e.g. hydrochloric, sulfuric, nitric
Air and moisture
Bases, e.g. fresh water, distilled water
Salt, e.g. seawater
Industrial atmosphere
Steam and other gases, e.g. chlorine, hydrogen sulfide
Chloride
General or Uniform corrosion
Forms of Corrosion
The most common form of corrosion
Coating
Metal or
non-
Normally occurs on the entire exposed surface or over a large area
metal
Represents the greatest destruction of metal on a tonnage basis
Filiform
Crevice
‘Uniform’
Pitting
Least damaging from technical point of view because the life of component
can be predicted from comparatively simple tests
More
noble
metal
Intergranular
Exfoliation
Selective
Galvanic
Flowing
Load
Corrodent
Fretting -
High Temperature
Erosion-Corrosion
Corrosion
‘Dry’ Corrosion
& Impingement

Control of General Corrosion

• Use protective coatings

• Use cathodic or anodic protection

protective coatings • Use cathodic or anodic protection Use both for underground steel structures • Treat

Use both for underground

steel structures

• Treat environment, e.g. remove O 2 , add inhibitors

• Select more resistant materials, (Consider non-metals)

• Ensure overheating of liquids cannot occur

“General” Corrosion

• Positions of Anodes & Cathodes change with time

• — occurs due to use of wrong material

general breakdown of coatings

unanticipated change of environment

• — testing should simulate all relevant details

e.g. welds, anode/cathode areas, degree of aeration, etc.

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Pitting Corrosion

Localized attack that results in holes, mainly small holes

Serious form of corrosion (one of the most destructive)

Often difficult to predict because their small size and are often covered with corrosion products

Stainless steels are prone to pitting corrosion especially in salt water. Brasses (Cu-Zn), bronzes (Cu-Sn) have better pitting resistance than stainless steels

corrosion especially in salt water. Brasses (Cu-Zn), bronzes (Cu-Sn) have better pitting resistance than stainless steels
corrosion especially in salt water. Brasses (Cu-Zn), bronzes (Cu-Sn) have better pitting resistance than stainless steels
corrosion especially in salt water. Brasses (Cu-Zn), bronzes (Cu-Sn) have better pitting resistance than stainless steels

Crevice corrosion

Usually associated with stagnant solution caused by gasket surfaces, lap joints.

Occurs especially under bolt & rivet heads, gaskets, seals and within small holes and cracks

Different oxygen content in the stagnant area vs. open surface

Stainless steels and aluminium are susceptible to crevice corrosion

oxygen content in the stagnant area vs. open surface Stainless steels and aluminium are susceptible to
oxygen content in the stagnant area vs. open surface Stainless steels and aluminium are susceptible to

Size, Shape & Density of Pits can vary enormously

Size, Shape & Density of Pits can vary enormously Pitting often leads to initiation of fatigue,
Size, Shape & Density of Pits can vary enormously Pitting often leads to initiation of fatigue,

Pitting often leads to initiation of fatigue, SCC, etc.

Galvanic Corrosion

Occurs when two dissimilar metals are in contact (or electrically connected)

Metal with less corrosion resistant become anodic, and the more resistant

metal become cathodic (see galvanic series)

The farther apart two metals are in the galvanic series, the greater potential galvanic corrosion to occur. Magnesium to steel is a very bad combination; Monel (Ni-Cu) to stainless steel will show negligible activity.

to occur. Magnesium to steel is a very bad combination; Monel (Ni-Cu) to stainless steel will
to occur. Magnesium to steel is a very bad combination; Monel (Ni-Cu) to stainless steel will
to occur. Magnesium to steel is a very bad combination; Monel (Ni-Cu) to stainless steel will

Galvanic Series

Platinum

Gold

Titanium Silver 18-8 austenitic stainless steels (passive cond.) Iron-chromium alloys (passive cond.) Inconel (passive) Nickel Monel Bronzes Copper

Brasses Inconel (active) Nickel (active) Tin Lead 18-8 Austenitic stainless steels (active) Cast iron Mild steel and iron Aluminum alloys Zinc Magnesium and magnesium alloys

MostMostMostMost cathodiccathodiccathodiccathodic orororor resistantresistantresistantresistant totototo corrosioncorrosioncorrosioncorrosion (noble)(noble)(noble)(noble)

MostMostMostMost anodicanodicanodicanodic orororor easyeasyeasyeasy totototo corrodecorrodecorrodecorrode (active)(active)(active)(active)

Filiform Corrosion

Occurs under protective films, e.g. lacquered (transparent surface films)

Commonly observed on food or beverage cans

Observed on steel, magnesium and aluminium surfaces covered by tin, silver, gold, phosphate

Does not weaken or destroy metallic components but affects surface appearance

Appears as network with an active head and red-brown corrosion product tail

components but affects surface appearance Appears as network with an active head and red-brown corrosion product
components but affects surface appearance Appears as network with an active head and red-brown corrosion product

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Exfoliation Corrosion

Specifically attack on flattened and elongated grains

Appears as layers below metal surface (flakes, layer and peel off)

Typically found in aluminium alloys on aircraft components (skins, spar, etc.)

metal surface (flakes, layer and peel off) Typically found in aluminium alloys on aircraft components (skins,
metal surface (flakes, layer and peel off) Typically found in aluminium alloys on aircraft components (skins,

Intergranular Corrosion

Occurs preferentially along grain boundaries

Usually caused by segregation along grain boundaries

Segregation leads to dissimilar composition between grain boundaries (anodic) and the grains (cathodic)

The most common case: sensitization and welding of stainless steels

When stainless steels are heated in the temperature range of 400 to 850 o C, chromium carbides (CrC) tend to form along grain boundaries

Also observed in high-strength aluminium alloys and copper alloys

carbides (CrC) tend to form along grain boundaries Also observed in high-strength aluminium alloys and copper
carbides (CrC) tend to form along grain boundaries Also observed in high-strength aluminium alloys and copper

Stress Corrosion Cracking (SCC)

Material deterioration (cracking) due to combination of corrosive environment and tensile stress

Found in aluminium alloys, stainless steels, copper alloys, titanium alloys, etc

Stainless steels and aluminium are prone to chloride-containing solutions; brasses crack in ammonia-containing solutions

Strongly influenced by materials treatment (heat treatment and stresses)

Normally intergranular

solutions Strongly influenced by materials treatment (heat treatment and stresses) Normally intergranular
solutions Strongly influenced by materials treatment (heat treatment and stresses) Normally intergranular
solutions Strongly influenced by materials treatment (heat treatment and stresses) Normally intergranular

Intergranular Corrosion of Stainless Steel (“Weld Decay”)

Intergranular Corrosion of Stainless Steel (“Weld Decay”) Holding or slow cooling in the range 500-800°C is

Holding or slow cooling in the range 500-800°C is responsible

Dealloying (selective leaching)

Occurs on metal where one constituent of metal alloy is removed from the alloy

There are two forms:

Dezincification: removal of zinc from brass (Cu-Zn) Graphitization: dissolution of iron from gray cast irons leaving only the graphite

Dezincification occurs when brass exposed/operates at a relatively high temperatures, e.g. 80 o C for several months

Graphitization occurs on gray cast irons pipes over a period of time

C for several months Graphitization occurs on gray cast irons pipes over a period of time

dezincification

C for several months Graphitization occurs on gray cast irons pipes over a period of time

graphitization

Erosion-Corrosion

Erosion-Corrosion Turbulent Flow (relative motion of fluid and metal surface) Mechanical Force of Liquid removes Corrosion

Turbulent Flow

(relative motion of fluid and metal surface)

Mechanical Force of Liquid removes Corrosion Products /Protective Films

Pits / Grooves with directional pattern produced

Occurs in • Pipes at changes of section, bends

• Propellers, etc. • Valves at seals that leak

Exacerbated by solid particles in liquid

at changes of section, bends • Propellers, etc. • Valves at seals that leak Exacerbated by

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Erosion - Corrosion of Steel Pipe

Section of Large diameter 0.2%C Steel Pipe

Weld

Pipe Section of Large diameter 0.2%C Steel Pipe W e l d water flow — Erosion

water flow

Erosion Corrosion

due to weld metal protruding into flow causing turbulence

0.2%C Steel Pipe W e l d water flow — Erosion Corrosion due to weld metal

Cavitation Corrosion

Formation & Collapse of Vapour Bubbles due to Hydrodynamic Pressure Changes

of Vapour Bubbles due to Hydrodynamic Pressure Changes Pressure of Shock Wave produces spalling of Oxide

Pressure of Shock Wave produces spalling of Oxide & localised plasticity

of Shock Wave produces spalling of Oxide & localised plasticity Oxide reforms—Bubble reforms in same place

Oxide reforms—Bubble reforms in same place

Erosion -Corrosion of Sensor Tube

- exposed to flowing sea water at 4m/s

Specified material : 70:30 Cu-Ni

flowing sea water at 4m/s Specified material : 70:30 Cu-Ni 12mm Erosion- corrosion due to use
12mm
12mm

Erosion- corrosion due to use of 90:10 Cu:Ni material (which is rated to 3m/s maximum flow rate)

Examples of Cavitation

Examples of Cavitation 316 Stainless Steel Pump Impeller (Vacuum Evaporation Unit) 70°C Skimmed Milk 1 yr.

316 Stainless Steel Pump Impeller (Vacuum Evaporation Unit) 70°C Skimmed Milk 1 yr. in service

Evaporation Unit) 70°C Skimmed Milk 1 yr. in service C Steel Pipe Condensate+Steam leaking from trap

C Steel Pipe Condensate+Steam leaking from trap Several yrs. service

Cavitation Corrosion of Pipe

Sectioned Mild Steel pipe

Cavitation Corrosion of Pipe Sectioned Mild Steel pipe Deep, Steep-sided Pits — caused by Cavitation due

Deep, Steep-sided Pits

— caused by Cavitation due to vibration of pipe filled with water

Remedy:

Secure pipe to wall with more brackets to reduce vibration — don’t just repair (by welding) without addressing cause

Corrosion Control

• Design & Fabrication Practice

• Material Selection / Surface Modification

• Environment Modification e.g. Inhibition, Oxygen Removal

(Impressed Current, Sacrificial Anodes)

Cathodic Protection

• Coatings

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Cathodic Protection

Cathodic Protection
Cathodic Protection
Cathodic Protection
Cathodic Protection

How to minimise or avoid corrosion

Material Selection

Remember to:

• Anticipate range of conditions (e.g. Commisioning, Shut Down, Cleaning)

• Consider Local Factors e.g. Cl - conc n of cooling water even if designs/materials used successfully elsewhere

• Consider effects of Fabrication / Heat-treatment

Remember that:

• Corrosion resistance of “minor” components e.g. screws, pins, etc. may be just as important as major ones

screws, pins, etc . may be just as important as major ones Examples of Design Features
screws, pins, etc . may be just as important as major ones Examples of Design Features
screws, pins, etc . may be just as important as major ones Examples of Design Features

Examples of Design Features to Avoid

• Avoid Dissimilar Metals …see Galvanic Series

• Avoid stagnant regions / deposits / crevices

Features to Avoid • Avoid Dissimilar Metals …see Galvanic Series • Avoid stagnant regions / deposits
Features to Avoid • Avoid Dissimilar Metals …see Galvanic Series • Avoid stagnant regions / deposits
Features to Avoid • Avoid Dissimilar Metals …see Galvanic Series • Avoid stagnant regions / deposits
Features to Avoid • Avoid Dissimilar Metals …see Galvanic Series • Avoid stagnant regions / deposits
Features to Avoid • Avoid Dissimilar Metals …see Galvanic Series • Avoid stagnant regions / deposits

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