Corrosion

Corrosion
Corrosion: a chemical or electrochemical reaction between a material and its
environment that produces a deterioration of the material and its properties
Electrochemical reaction: chemical reactions in which elements are added or removed
from a chemical species and at least one of the species undergoes a change in the
number of valance electrons
Electrochemical Corrosion:
Wet (aqueous) - systems that corrode at low T with a liquid electrolyte
Dry (oxidation) - corrosion that occurs at high T (generally over 500C)
Aqueous:
Uniform or General
Galvanic or Two-metal
Crevice
Pitting
Intergranular
Velocity-assisted
Environment-assisted cracking

Oxidation:
High Temperature
No moisture nor dissolved electrolytes
Low Temperature
surfaces where T< 135C
condensation of the acidic sulphur and
chlorine-containing gases
2

Chemical Corrosion
Liquid Metal Embrittlement:
- The dissolution-diffusion model
adsorption of the liquid metal on the solid metal induces dissolution and inward
diffusion
under stress these processes lead to crack nucleation and propagation
- brittle fracture theory
adsorption of the liquid metal atoms at the crack tip weakens inter-atomic bonds and
propagates the crack
- diffusion penetration
penetration of liquid metal atoms to nucleate cracks which under stress
- ductile failure model
adsorption of the liquid metal leads to weakening of atomic bonds and nucleation of
dislocations which move under stress, pile-up and work harden the solid.
dissolution helps in the nucleation of voids which grow under stress and cause ductile
failure
Examples: Hg and aluminum alloys, Bi and copper alloys

Electrochemical Corrosion - Oxidation

Low Temperature
surfaces where T< 135C
condensation
acidic sulfur
chlorine-containing gases
High Temperature:
no moisture nor dissolved electrolytes
e.g. direct reaction with oxygen
Y2O3
Y2O3-X
Fe
Fe2O3

Oxidation Ellingham Diagram

Low Temperature
surfaces where T< 135C
condensation
acidic sulfur
chlorine-containing gases
High Temperature:
no moisture nor dissolved electrolytes
e.g. direct reaction with oxygen
Y2O3
Y2O3-X
Fe
Fe2O3
4Fe + 3O2

2Fe2O3

G = G0 + RT ln k
K = [C]c [D]d
[A]a [B]b
K= Po

Used for oxidation and reduction of ore

Galvanic Corrosion
Galvanic Cell
Two half cells
Half cell
charge balance
metal
solution of metal salt
One cell oxidizes the other
direction depends on driving force

Daniell Cell
Zn(s)

Zn2+ + 2e- Anodic

Cu2+ + 2eZn (s) + Cu2+

Cu(s) Cathodic
Zn2+ + Cu (s)

General Reaction
An+ + ne-

Bm+ + me-

mA + nBm+

nB + mAn+

Standard Hydrogen EMF Test 25C

Used to develop EMF Series
Two outcomes:
Metal sample mass decreases
(iron is the anode, -)

Metal sample mass increases

(gold is the cathode, +)

0
e- e

e-

ee-

H2

H+

Iron

H+
Fe2+

Fe2+
(1M Fe2+)

H+

ePlatinum

Fe2+

H+

(1M H+)

Vmetal < 0 (relative to Pt)

+
H+

Ag2+

Ag2+

ee-

H+
H+

Ag2+
(1M Ag2+)

Platinum

Gold

H+
(1M H+)

Vmetal > 0 (relative to Pt)

7

Standard EMF Series

EMF series
o
Vmetal
metal
Au
+1.420 V
Cu
+0.340
Pb
- 0.126
Sn
- 0.136
Ni
- 0.250
o
V =
Co
- 0.277
0.153V
Cd
- 0.403
Fe
- 0.440
Cr
- 0.744
Zn
- 0.763
Al
- 1.662
Mg
- 2.262
Na
- 2.714
K
- 2.924

more anodic

more cathodic

Metal with smaller

o
Vmetal
corrodes.

Ex: Cd-Ni cell

Cd

25C

Ni

1.0 M
1.0 M
Cd2+ solution Ni2+ solution

Data based on Table 17.1, Callister 6e.

8

Aqueous Types
Standard Calomel Electrode (SCE):
antiquated
contains mercury!
reaction between:
Hg
Hg2Cl2 (calomel)
aqueous phase: saturated KCl in H2O
referenced as 0V
redox potential is +0.2444 V vs. SHE at 25 C
Standard Hydrogen Electrode (SHE):
modern method

Aqueous Types
Galvanic Corrosion:
Two metals in contact act similar to a model corrosion cell
electrically conduction path
driving force (EMF)
electrolyte (aqueous solution, air)

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10

Aqueous Types
Galvanic Corrosion:
Can be detrimental, or beneficial, the difference is up to the engineer!

Stainless steel bolts in zinc plated steel.

Zinc anodes on painted LAS.

in both cases, the zinc is less noble. Its use determines the success of the system

11

Aqueous Types
Uniform Corrosion:
most common corrosion type
corrosion rate is often expressed as a distance per year
usually mils (1 mil = .001 inches = .0254 mm)
Mils penetration per year (MPY) = 534 x W / (At)
W = weight loss in milligrams
= density (g/cm3)
A = area (in2)
t = time (hrs)
< 1 MPY is outstanding, 5-20 good, 50-200 poor

12

Simple Aqueous Corrosion (uniform)

Require four components: anode, cathode, conduction path (contact), and electrolyte
Anaerobic
Fe2+ + 2e-

Fe

2H+ + 2e-

H2

Fe2+ + 2Cl-

Aerobic (Dissolved Oxygen)

3+ + 3e
2eFe2+

Anodic

Fe

Cathodic

O2 + 6e
4e- + 3H
2H2O

FeCl2(aq)

3+ + 4OH
2Fe2+
6OH-

2Fe(OH)3

Anodic
6OH
4OH-

Cathodic

2Fe(OH)32
Fe2O3 + 3H2O
Rust

H+

H+

H2

Cl-

H2

Cl-

H+ H+ H+

Fe2+

H+ H+ H+

O2

Fe2+

OH-

Fe
e(active corrosion)

OH-

O2

Fe
e-

e-

e-

(partially passivates)
13

Controlling Uniform Corrosion

Uniform Corrosion:
The earliest attempts at slowing corrosion involved additions of copper to steel
Still used today
High Strength Low Alloy Steel
not made to specific chemical composition
specific mechanical properties.
carbon content between 0.050.25%
retain formability and weldability
<2.0% Mn
Cu, Ni, Nb, N, V, Cr, Mo, Ti, Ca, Zr, or rare earth elements (Y, Hf)
Cu, Ti, V, and Nb are added for strengthening purposes
Cu, Si, Ni, Cr, P increase corrosion resistance
Zr, Ca, and REs control inclusion shape
Control-rolled, pearlite-reduced, microalloyed, acicular ferrite, dual-phase, and Weathering

14

Controlling Uniform Corrosion

Weathering Steel:
HSLA steel with ~0.3 wt. % Cu additions
forms adherent, solid oxide layer
dont need to be painted
use of uncoated weathering steel
initial cost savings of >10% (dont need to be painted)
life cycle cost savings >30% (durability)
The first bridge using this material was built over the New Jersey Turnpike in 1964.

15

Simple Aqueous Corrosion (uniform)

Require four components: anode, cathode, conduction path (contact), and electrolyte
Anaerobic
Fe2+ + 2e-

Fe

2H+ + 2e-

H2

Fe2+ + 2Cl-

Aerobic (Dissolved Oxygen)

3+ + 3e
2eFe2+

Anodic

Fe

Cathodic

O2 + 6e
4e- + 3H
2H2O

FeCl2(aq)

3+ + 4OH
2Fe2+
6OH-

2Fe(OH)3

Anodic
6OH
4OH-

Cathodic

2Fe(OH)32
Fe2O3 + 3H2O
Rust

H+

H+

H2

Cl-

H2

Cl-

H+ H+ H+

Fe2+

H+ H+ H+

O2

Fe2+

OH-

Fe
e(active corrosion)

OH-

O2

Fe
e-

e-

e-

(partially passivates)
16

Stainless Steels
What is stainless steel?
- an iron alloy containing >12% chromium
Applications
- endless applications
chemical handling, marine applications, aesthetics
- one purpose: corrosion resistance

Petrochemical

nuclear

architecture

consumer
17

Introduction
Stainless Steel
- rustless, stainless, inox (inoxydable)
- originally a miracle material
Stain-less Steel
- each SS type has its weakness
Austenitics
- pH value < 1.0
- chlorides
acidic chlorides (MgCl2 and BaCl2)
seawater
- galvanic
self, more noble alloys
Sensitization
- improper heat treatment
intergranular corrosion
New York Times: Jan 31, 1915

New York Times: Jan 22, 1922

18

How do Stainless Steels Work? Passivation

Oxidation
Begins with Cr and Fe oxidation
forms passivating layer
very rapid (ms)
HCP Cr2O3 layer
kinetic inhibitor
tenacious
allows cold work, welding, etc

Aerobic (Dissolved Oxygen)

Fe

Fe2+ + 2e-

O2 + 4e- + 2H2O
2Fe2+ + 4OH-

O2

Anodic
4OH-

Cathodic

2Fe(OH)2

Fe-Cr(OH)2-3
O2

OH-

Cr2O3
Cr-rich
base metal

Fe2+
Fe-Cr

e-

OH-

e-

(fully passivates)
19

Transpassive Corrosion
Breakdown
increased potential (e.g. very low pH)
attacks passivating layer
accelerated in pitted area
pitting

Low pH Corrosion
Fe

Fe2+ + 2e-

2H+ + 2eFe2+ + 2Cl-

H2

H2

H2

Anodic
Cathodic

FeCl2(aq)

Fe-Cr(OH)2-3

H+ H+ H+
Cr2+
Fe-Cr

Cr2O3
Cr-rich
base metal

Fe2+

Fe2+
e-

e-

(partially passivates)
20

Breakdown of the Passivating Layer

Crevice Corrosion
1) Oxygen is consumed in crevice by slow passive corrosion
2) Passive corrosion continues, and pH falls by Cr3+ hydrolysis
O2 + 4e- + 2H2O
4OH- (Cathodic)
Cr
Cr3+ + 3e- (Anodic)
Cr3+ + 3H2O
Cr(OH)3 + H+
H+ + ClHCl(aq)
localized decrease in pH (<2)
3) Passive film breaks down in acid and rapid active corrosion starts
4) Active corrosion causes even stronger acidification and stabilizes the crevice corrosion

O2
OH-

ClM+

H+

e-

21

Breakdown of the Passivating Layer

Breakdown
Surface Roughness

Electrolyte
Flow

Local environment
pH

Cl- ClCl-

H+ H+ H+

Film disruption
chloride ions

Underlying microstructure
inclusions
slip bands
surface roughness
phase interfaces
grain boundaries

Steel

Stress gradients

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson

Learning is a trademark used herein under license.

22

Carbide Formation
Chromium Additions to Steel
- Beginning in 18201
- added to medium steel (0.10-0.30% C)
improved hardenability
- 1913, stainless steel invented
Harry Brearley
Brown Firth Laboratories
Fe-12.8% Cr-0.24% C
(martensitic)
Carbide Formation
- too brittle for practical use
1000C
- solubility limit (<0.02%C)
- Cr23C6 precipitates
800C

Fe-Cr
Fe-Cr-0.1C
Phase Diagram
Phase Diagram
(Calphad)
Air cool

Cr23C6

600C
400C
0.1 hr

1 hr

10 hr 100 hr 1000hr
23

Chromium Additions - Carbide

Temper-Brittleness
brittle carbide on grain boundary
limitation with early Fe-Cr alloys
Carbon Content
Lower C, less propensity to carbide formation
move the nose
stainless iron c. 1920

1000C

Air cool

800C

Cr23C6

600C
400C

0.05%
0.15%
0.30%

Quench
0.1 hr

1 hr

10 hr 100 hr 1000hr

Sourmail,
Aitchison,T.L.Stainless
Engineering
Steel.Steels:
University
An exposition
of Cambridge.
of the2010.
properties. D. Van Nostrand Company. New York. 1921.
24

Nickel and Chromium Additions

Fe-Ni
Austenite stabilizer
demotes martensite formation
tough, solid solution
1889 first nickel additions (for strength)1

Austenitic Stainless Steel

Fe-Ni Phase diagram (Calphad)

1914 austenitic stainless steel invented

<1% C, <20% Ni and 15-40% Cr
Friedrich Krupp AG
Eduard Maurer and Benno Strauss
Provide ductility, toughness, workability

1Riley

25

Not so Fast
Austenitic Stainless Steel
- invented in 1914
Friedrich Krupp AG
Eduard Maurer and Benno Strauss
- limited use throughout the war effort
high temperature applications (e.g. valves)
Krupp Krankheit (Krupps Disease)
that peculiar property of nickel chromium steels known as temper-brittleness
- intergranular disintegration
without apparent external cause
- decay is always observed from the surface
corrosion process
- only in isolated cases
traced to faulty heat treatment
Aitchison, L. Engineering Steels: An exposition of the properties. D. Van Nostrand Company. New York. 1921.
26

Sensitization Corrosion Theories

Microcell Theory1
local galvanic couple
(Cr-Fe)23C6 cathode (noble)
matrix anode
weakness: self healing, >12% Cr
Stress Theory2
local stresses around carbide
imperfect passivation
weakness: magnitude

(Cr-Fe)23C6
<12Cr

18Cr-8Ni

Carbide Corrosion Theory3

carbides preferentially corrode
18%
weakness: noble
Cr
4,5,6,7
Chromium Depletion Theory
12%
Cr below passivating
generally applicable
8%
1Stickler,

1963

2Lula,

1954

3Shvartz, 1959

4Strauss

et al, 1930

5Bain,1933

6Hillert,

1969

7Tedmon,

1971
27

Chromium Depletion Theory

~70% Cr

18% Cr
12% Cr
18%
5.68% C
0.3% C
0.1% C
0.08% C
20nm

Cr 12%
0nm

20nm

8%
28

Chromium Depletion Theory II

Microcell Theory1
local galvanic couple
(Cr-Fe)23C6 cathode (noble)
matrix anode
weakness
self healing
resistance above 12% Cr

Vacancy Theory3,4,5,6
sintering
preferential diffusion
weaknesses
rate
<12Cr

(Cr-Fe)23C6
18Cr-8Ni

Stress Theory2
local stresses around carbide
imperfect passivation
weakness
magnitude
18%
Chromium Depletion Theory3,4,5,6
Cr below passivating Cr
12%
generally applicable
8%

1Stickler

and Vinckier, 1963

2Lula

et al, 1954.

3Strauss

et al, 1930

4Bain

et al,1933

5Hillert

et al, 1969

6Tedmon

29
et al, 1971

1930 Strauss, Schottky, and Hinnber

Goal/Hypothesis
Provide explanation for Krupp Krankheit
Method
Relate problem to heat treatment
carbide formation
Increasing Carbon Content
0.04% C, 9.30% Ni, 18.3% Cr
0.06% C, 9.22% Ni, 18.0% Cr
0.12% C, 8.40% Ni, 18.6% Cr

strain

UTS

Summary
1) > potential w/> C = carbides
2) > carbide precip at > T, but < corrosion
3) depletion in immediate region, at higher t the C had more time to diffuse
4) > hardness - martensite being formed? (magnetism detected)
5) corrosion still seen in austenitic nickel-containing alloys (no magnetism)
7) 25%Cr, 20% Ni, 0.15% C has only weak tendency to intergranular corrosion
Strauss, B., H. Schottky, and J. Hinnber. Zeitschrift fr anorganische und allgemeine Chemie. Vol 188. No. 1. pp 309-324. 1930.
30

Modeling efforts
Shvartz and Kristal
C control for sensitization
Cr control for self-healing
Baumel
GB diffusion for sensitization
volume diffusion for self-healing
Strawstrm and Hillert
sensitization and self-healing
uniform grain boundary film
alloy-carbon-M23C6 local equilibrium
Tedmon, Vermilyea, and Rosolowski
sensitization only
non uniform carbide film
free energy of carbide formation

20nm

0nm

20nm

Strawstrom, C., and M. Hillert. An Improved Depleted-Zone Theory of Intergranular Corrosion of 18-8 Stainless Steel. Journal of the Iron and
Steel Institute. Vol 207. pp 77-85. 1969.
31

Analytical Techniques
Early Studies
Corrosion Testing
(Moneypenny-)Strauss Test: H2SO4-CuSO41
Huey Test: boiling HNO3
optical microscopy
showed pits/trenches
low resolution
no chemical information

Aitchinson, 1921

Models
all proposed before proof of depletion
Strauss, Schottky, and Hinnber, 1930
Bain , Aborn and Rutherford,1933
Strawstrm and Hillert, 1969
Tedmon, Vermilyea, and Rosolowski, 1971
Bain, 1933
1Strauss et

al, 1930

2Mahl,

1940

2Schaefer

and Harker, 1942

32

Proof of Chromium Depletion

First Confirmation
Joshi and Stein, 1972
Auger electron spectroscopy
fracture surfaces
sulfur, silicon, nitrogen, and phosphorus at GB
confirmed Cr-depletion
Subsequent Study
AES1,2
Atom Probe13
STEM/EDS3,4,5,6,7,8,9,10,11,12
increasing resolution
1977
>50nm
1983-1984 50nm
1983-1986 25nm
1989
5nm
Model Validation
main chromium depletion effect

Ortner,
Hall, 1984
1989 50nm
5nm probe
probesize
size

Hopkinson, B.E. and K.G. Carroll. Metallurgy: Chromium Distribution around Grain Boundary
33