22.

Corrosion of Metals

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 Questions
• Why does rust form on the surface of steel
but not necessarily on aluminum?

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 Learning Objectives
• Describe in words the type of reactions occurring in
different parts of a corrosion reaction (electrodes
and electrolyte)
• Identify the conditions which lead to corrosion and
common methods of corrosion protection.

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 Environmental Degradation
• Environmental degradation is the degradation of one or more of a material
properties as results from exposure to its surrounding environment. E.g:

• degradation of steel due to exposure to water or salt water.

• degradation of an Ni-based superalloy due to exposure to a hot, post
combustion, gas
• degradation of a plastic due to exposure to UV light
• degradation of a metal due to exposure to radiation (nuclear reactor)

• Corrosion refers to the continued (unchecked) electrochemical attack of a

material normally resulting in oxidation of that metal. Corrosion typically
converts a refined metal to a more chemically-stable form found in the
environment.

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 Cost of Corrosion
Estimates to the cost of
corrosion in a developed
economy place it in the
range of 3 to 5% of
GDP.
Data is from a NACE
(National Association of
Corrosion Engineers)
study on the cost to the
US Economy (2002)

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Notes from MTRL 456 (Corrosion) - Rebecca Schaller, UBC Materials Engineering

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Notes from MTRL 456 (Corrosion) - Rebecca Schaller, UBC Materials Engineering

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 Corrosion of Metals
• It is not destroyed rather is converted to a different form.
• The driving force is a reduction in energy – e.g.

2Fe +3/2 O2  Fe2O3 DG0298 = -997,860 joules/mole

2Al +3/2 O2  Al2O3 DG0298 = -1,580,640 joules/mole

Huge thermodynamic driving force (-DG0 ) for oxidation to

occur – in essence a return to the mineral state.

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 Corrosion of Metals - Fe

During corrosion an active electro-chemical cell forms in which one part

of the metal surface serves as the Anode and the other as the Cathode

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 Corrosion of Metals - Fe

Anode Fe  Fe2+(aq) + 2e-

Cathode ½ O2 + H2O + 2e-  2OH-

Rust Precipitate Fe2+ + 2OH-  Fe(OH)2

Fe(OH)2+ + OH-  Fe(OH)3 Oxidation from Fe2+ to Fe3+
2Fe(OH)3 +3/2O2  Fe2O3+6H2O Partial Dehydration
to form Rust

Yikes Complicated – Often corrosion processes are very complex…

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 Key elements required for corrosion

1. Reduction in energy – thermodynamic driving force

2. Water/moisture present to act as a medium for ion
conduction and ionic transport (electrolyte)
3. Source of oxidant (normally O2, sometimes sulfur)
4. Mass transport of oxidant to the metal surface

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 Forms of Corrosion
• Uniform Attack - Oxidation
& reduction occur uniformly
over surface. Volume
change in the oxide can
mechanically displace the
oxide layer from the rest of
the material, exposing more
metal underneath for further
corrosion.

• Crevice Corrosion – Occurs

between two pieces of the
same metal, where access to
oxygen is restricted (example
shows a stainless steel
washer pushing on a
stainless steel plate)

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 Forms of Corrosion, cont
• Intergranular Corrosion - g.b.
occurs along grain boundaries, prec.
often where special phases
exist which are more
susceptible to corrosion. attacked
zones

• Galvanic Corrosion - two

different metals or alloys are
electrically coupled while
exposed to an electrolyte. The
more reactive metal acts as the
anode and corrodes, the less
reactive metal acts as the
cathode and is protected.
• Figure shown is from aluminum
foil in contact with stainless steel
container and an electrolyte
(ketchup + salt) overnight.
(Galvanic series and reactivity
discussed later in this lecture)

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 Forms of Corrosion, cont 2
• Pitting Corrosion - Downward
propagation of small pits & holes
occurs in the metal. Stainless steels
and Aluminum alloys in some
environments (high salt)

• Stress Corrosion - Stress & corrosion

work together at crack tips to
accelerate crack propagation and
failure. Figure shows a bar of steel
bent into a horseshoe shape While
immersed in seawater, stress
corrosion cracks formed along the
bend where the tensile stresses are
the greatest.

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 Forms of Corrosion, cont. 3
• Erosion-Corrosion - Break down of
passivating layer by erosion with abrasive
two-phase fluids (e.g. pipe elbows carrying
air and water).
• Selective Leaching - Preferred
corrosion of one element/constituent
(e.g., Zn from brass (Cu-Zn)).
http://www.berkeleyrc.com/FAcasestudies.html
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 Corrosion Protection for Metals

General Methods of Protection:

1. Self formation of a protective oxide;
2. Physical barriers (paint, noble coating);
3. Sacrificial or cathodic protection.

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 1. Self Formation of a Protective Oxide Layer
For some metals and alloys, a protective oxide coating forms upon initial exposure to oxygen
(that is, some oxidation occurs, but the oxide layer acts as protection against further corrosion).
This occurs if the oxide adheres to the surface and is dense enough to limits oxygen transport to
the surface as a passive protective layer.
Examples include some Aluminum alloys, Stainless Steel (Cr added as an alloy addition), Titanium.

Flaking of oxide layer on Chromium oxide layer adhering to stainless steel,

plain steel – no good as the which provides good protection (stainless steel is
oxide expands and at least 10.5% chromium)
mechanically cannot adhere
to the surface Similar protection occurs for many aluminum
alloys. Al2O3 forms on the surface as a passive
protective layer.
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 2. Physical Barriers (film, paints, noble coatings)
Coating the surface with a nonreactive material to inhibit contact of
water and oxygen with the surface or the metal.

http://vancouversun.com/news/local-news/pattullo-bridge-history-built-
in-1937-the-span-was-expected-to-last-50-years

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 2. Physical Barriers (film, paints, noble coatings) vs.
3. Sacrificial or cathodic protection

Noble coating uses a less chemically
active metal layer than the main metal.
The noble coating acts as a physical
barrier until it is physically or chemically
damaged itself, just like paint or film.
Often nickel, tin or chromium.
Sacrificial coatings use a more chemically active metal
layer than the main metal. As the material is sacrificed.
The sacrificial coating acts as the anode, and corrodes
while the main metal stays intact. This is using Galvanic
Corrosion to protect the metal used as the cathode.
The above example material (Zinc on Steel) is known as
galvanized steel, with the steel dipped in molten zinc.
Called “galvanized” since zinc is highly active on the
galvanic series (discussed in 2 slides).
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 3. Sacrificial or cathodic protection (cont)
Metal to be protected is electrically coupled to a sacrificial anode. Anode can be
made from a more active metal on the galvanic scale for passive (unpowered)
protection, or can be driven by an applied external power source to electrically
bias the electrodes correctly for protection.

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 Galvanic Series EMF series
(Ranks the reactivity of (measured relative to standard
metals/alloys in seawater at 25oC) hydrogen reference half cell)

VoSHE

more cathodic
more cathodic
Platinum
Au +1.420 V
Gold
Cu +0.340

(inert)
(inert)

Graphite
Titanium Pb - 0.126
Silver Sn - 0.136
316 Stainless Steel (passive) Ni - 0.250
Nickel (passive) Co - 0.277
Copper
Cd - 0.403
Nickel (active)
Tin Fe - 0.440

more anodic
more anodic

Lead Cr - 0.744

(active)
(active)

316 Stainless Steel (active) Zn - 0.763

Iron/Steel Al - 1.662
Aluminum Alloys Mg - 2.363
Cadmium
Na - 2.714
Zinc
Magnesium K - 2.924

• Galvanic Series lists metals and alloys (EMF only metals)

• EMF calculated from thermodynamic principles (Galvanic measured experimentally)
• Galvanic includes effects of passive films, oxidation kinetics, and the environment

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Sacrificial zinc anode on hull of boat

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Sacrificial Anode in Hot Water Tanks
(aluminum or magnesium)

New

Depleted

Left – ecodaddyo.com
Right – RV anodes (youtube)

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 Additional Means of Reducing Corrosion

• Reduce Temperature (slows kinetics of oxidation and reduction)

• Removing reactants – e.g. remove O2 gas to create a more reducing

environment.

• Add inhibitors to fluids – e.g. coolant additives in automotive cooling

systems (radiators) provide corrosion prevention in addition to
protection against freezing.

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 Corrosion prevention video
• https://www.youtube.com/watch?v=M_a5
hG9sInY&t=8s (from min 4)

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 Learning Objectives
• Describe in words the type of reactions occurring in
different parts of a corrosion reaction (electrodes
and electrolyte)
• Identify the conditions which lead to corrosion and
common methods of corrosion protection.

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