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CHAPTER 16:

CORROSION AND DEGRADATION

ISSUES TO ADDRESS...
• Why does corrosion occur?
• What metals are most likely to corrode?
• How do temperature and environment affect
corrosion rate?
• How do we suppress corrosion?

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THE COST OF CORROSION
• Corrosion:
--the destructive electrochemical attack of a material.
--Al Capone's
ship, Sapona,
off the coast
of Bimini.

• Cost:
--4 to 5% of the Gross National Product (GNP)*
--this amounts to just over $400 billion/yr**

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CORROSION OF ZINC IN ACID
• Two reactions are necessary:
-- oxidation reaction: Zn  Zn2  2e
-- reduction reaction: 2H  2e  H2 (gas )

• Other reduction reactions:


-- in an acid solution -- in a neutral or base solution
O2  4H  4e   2H2O O2  2H2O  4e  4(OH) 
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STANDARD HYDROGEN (EMF)
• Two outcomes:
TEST
--Metal sample mass --Metal sample mass

--Metal is the anode (-) --Metal is the cathode (+)


o o
Vmetal  0 (relative to Pt) Vmetal  0 (relative to Pt)

Standard Electrode Potential


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STANDARD EMF SERIES
• EMF series o
• Metal with smaller
metal Vmetal o
Vmetal corrodes.
Au +1.420 V • Ex: Cd-Ni cell
Cu +0.340
Pb - 0.126
Sn - 0.136
Ni - 0.250 o
Co - 0.277 DV =
Cd - 0.403 0.153V
Fe - 0.440
Cr - 0.744
Zn - 0.763
Al - 1.662
Mg - 2.262
Na - 2.714
K - 2.924
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CORROSION IN A GRAPEFRUIT
Cathode Anode
Cu +
-
H+ Zn
H+ Zn2+

reduction 2e - oxidation
2H  2e  H2 (gas )
H+
O2  4H  4e   2H2O H+
Acid H+
H+ H+

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EFFECT OF SOLUTION
CONCENTRATION
• Ex: Cd-Ni cell with • Ex: Cd-Ni cell with
standard 1M solutions non-standard solutions
o o RT X
VNi  VCd  0.153 o o
VNi  VCd  VNi  VCd  ln
- nF Y
+
n = #e-
per unit
oxid/red
Cd T Ni reaction
(=2 here)
F=
XM YM Faraday's
Cd2+ solution Ni2+ solution constant
• Reduce VNi - VCd by =96,500
C/mol.
--increasing X
--decreasing Y
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GALVANIC SERIES
• Ranks the reactivity of metals/alloys in seawater
Platinum
Gold
Graphite
Titanium
Silver
316 Stainless Steel
Nickel (passive)
Copper
Nickel (active)
Tin
Lead
316 Stainless Steel
Iron/Steel
Aluminum Alloys
Cadmium
Zinc
Magnesium
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FORMS OF CORROSION
• Stress corrosion
Stress & corrosion
• Uniform Attack work together • Erosion-corrosion
Oxidation & reduction at crack tips. Break down of passivating
occur uniformly over layer by erosion (pipe
surface. elbows).
• Selective Leaching • Pitting
Preferred corrosion of Downward propagation
one element/constituent of small pits & holes.
(e.g., Zn from brass (Cu-Zn)).
• Intergranular
Corrosion along
grain boundaries, • Galvanic
often where special Dissimilar metals are
• Crevice Between two
phases exist. pieces of the same metal.
physically joined. The
Rivet holes
more anodic one
corrodes.(see Table
17.2) Zn & Mg
very anodic.
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DETERIORATIVE
• Stress & Saltwater... • Heat treatment: slows
--causes cracks! crack speed in salt water!

4mm
--material:
7150-T651 Al "alloy"
(Zn,Cu,Mg,Zr)

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Uniform Corrosion: Rust!

Prevention:
• Paint
• Plate
• Sacrificial anode
Galvanic Corrosion

Causes:
Dissimilar metals
Electrolyte
Current Path

Described by Galvanic Series

Solutions:
Choose metals close in galvanic
series
Have large anode/cathode ratios
Insulate dissimilar metals
Use “Cathodic protection”
Pitting and Creviced
Corrosion

Causes: concentration gradients in


electrolyte cause some areas high in ion Prevention:
concentrations that accelerate oxidation
Weld – don’t rivet
Use non-absorbing gaskets
Polish surfaces
Add drains – avoid stagnant water
Adjust composition; e.g., add Mo to SS
Intergranular Corrosion
Occurs in specific alloys – precipitation of corrosive
specimens along grain boundaries and in particular
environments
e.g. : Chromium carbide forming in SS, leaving adjacent areas depleted in Cr

Solutions: High temp heat treat to redissolve carbides


Lower carbon content (in SS) to minimize carbide
formation
Alloy with a material that has stronger carbide
formation (e.g., Ti or Nb)
Erosion Corrosion

Causes: abrasive fluids impinging on


surfaces
Commonly found in piping, propellers,
turbine blades, valves and pumps

Solutions:
•Change design to minimize or eliminate fluid
turbulence and impingement effects.
•Use other materials that resist erosion
•Remove particulates from fluids
Selective Leaching
• Occurs in alloys in which one
element is preferentially removed –
e.g., in Brass, Zinc is electrically
active and is removed, leaving
behind porous Copper
• Occurs in other metals, such as Al,
Fe, Co, Cr

Solutions:
• Use protective coating to protect surfaces
• Use alternative materials
Stress Corrosion

Aka: stress corrosion cracking


Cracks grow along grain
boundaries as a result of residual or
applied stress or trapped gas or
solid corrosion products
e.g., brasses are sensitive to
ammonia
Stress levels may be very low

Solutions: Reduce stress levels


Heat treatment
Atmosphere control
Hydrogen Embrittlement

• Metals loose strength when Hydrogen is


absorbed through surface, especially along
grain boundaries and dislocations
• Often occurs as a result of decorative
plating
• High strength steels particularly susceptible
• Can be removed by “baking” the alloy
CONTROLLING CORROSION
• Self-protecting metals!
--Metal ions combine with O
to form a thin, adhering oxide layer that slows corrosion.
• Reduce T (slows kinetics of oxidation and reduction)
• Add inhibitors
--Slow oxidation/reduction reactions by removing reactants
(e.g., remove O2 gas by reacting it w/an inhibitor).
--Slow oxidation reaction by attaching species to
the surface (e.g., paint it!).
• Cathodic (or sacrificial) protection
--Attach a more anodic material to the one to be protected.

Adapted
from Fig.
17.14,
Callister
6e.
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Corrosion prevention
Sacrificial Anode Applied Voltage
Surface coatings & Passivation

Some materials, such as


Aluminum or Stainless
Steel, form oxide
barrier coatings that
prevent oxidation at
active surface – this is
called “passivation”

Surface can be coated with protective layers:


painted, anodized, plated (Caution!!! Cracks in
plating or paint can lead to crevice corrosion!)
SUMMARY
• Corrosion occurs due to:
--the natural tendency of metals to give up electrons.
--electrons are given up by an oxidation reaction.
--these electrons then are part of a reduction reaction.
• Metals with a more negative Standard Electrode
Potential are more likely to corrode relative to
other metals.
• The Galvanic Series ranks the reactivity of metals in
seawater.
• Increasing T speeds up oxidation/reduction reactions.
• Corrosion may be controlled by:
-- using metals which form -- adding inhibitors
a protective oxide layer -- painting
-- reducing T --using cathodic protection.

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