Fatigue Mechanism

• Crack grows incrementally

da typ. 1 to 6
  K 
m

dN
~    a
increase in crack length per loading cycle
crack origin
• Failed rotating shaft
--crack grew even though
Kmax < Kc
--crack grows faster as
•  increases
• crack gets longer
• loading freq. increases.
 Fatigue Design Parameters
S = stress amplitude
• Fatigue limit, Sfat: case for
unsafe steel (typ.)
--no fatigue if S < Sfat
Sfat
safe
Adapted from Fig.
8.19(a), Callister 7e.

10 3 10 5 10 7 10 9
N = Cycles to failure
• Sometimes, the
fatigue limit is zero! S = stress amplitude
case for
unsafe Al (typ.)

safe Adapted from Fig.

8.19(b), Callister 7e.

10 3 10 5 10 7 10 9
N = Cycles to failure
 Improving Fatigue Life
1. Impose a compressive S = stress amplitude
Adapted from
surface stress Fig. 8.24, Callister 7e.

(to suppress surface Increasing

near zero or compressive m
cracks from growing) m moderate tensile m
Larger tensile m

N = Cycles to failure

--Method 1: shot peening --Method 2: carburizing

shot
C-rich gas
put
surface
into
compression

2. Remove stress bad better

concentrators. Adapted from
Fig. 8.25, Callister 7e.
bad better
 THE COST OF CORROSION
• Corrosion:
-- the destructive electrochemical attack of a material.
-- Al Capone's
ship, Sapona,
off the coast
of Bimini.

Photos courtesy L.M. Maestas, Sandia

National Labs. Used with permission.

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

* H.H. Uhlig and W.R. Revie, Corrosion and Corrosion Control: An Introduction to
Corrosion Science and Engineering, 3rd ed., John Wiley and Sons, Inc., 1985.
**Economic Report of the President (1998).
 What is CORROSION?
Corrosion is a natural event
It represents a return of metals to their
more natural state as minerals (oxides)
Metal “Wants” to be Dirt
ENERGY

ORE
METAL
 Basics of Corrosion
Corrosion is essentially the oxidation of metal

Source: Moore, J.J. Chemical Metallurgy

Need:
1. An Anode (where oxidation is taking place)
2. A Cathode (where reduction is taking place)
3. Conductive electrolyte
4. Electrical contact between the Anode and Cathode
 Electrochemistry
 Corrosion is an electrochemical reaction
– ½ reaction at the anode: M Mn+ + ne-
– Possible ½ reactions at the cathode:
2H+ + 2e- H2
Acid Solutions: H2O + e- ½ H2 + OH-
½ O2 + 2H+ + 2e- 2OH-
 Important thing to note is the flow of electrons
 Thermodynamic Driving Force
 Like all chemical reactions – Thermodynamics
 What is the driving force for the reaction?
(otherwise stated as what is the electrochemical
potential for the reaction)
– Dissimilar metals
– Different cold work states
– Different grain sizes
– Difference in local chemistry
– Difference in the availability of species for a reaction
(concentration cells)
– Differential aeration cells
 Derivation of Nernst Equation
 a products 
G  G  RT ln(Q)  G  RT ln
o o

 areac tan ts 

For:
2 
Fe  Fe  2e
2 H   2e   H 2 ( g )
Fe  2 H   Fe 2  H 2( g )
1
 a ( Fe 2
)  f ( H )   [ Fe 2
]
G  G  ln
o  2 
 G  ln  2 
o

  
 a ( Fe)  a ( H  ) 2 
  [H ] 

1
 Derivation of Nernst Equation…

 Introduce: The total electropotential is
 G = -nFE
Where:
F = Faraday’s constant (total charge on Avogadro’s number of electrons)
n = the number of electrons transferred
E = The electrode potential

 nFE  nFE  RT ln(Q)o

or
nFE  nFE  RT ln(Q)
o
 Thermodynamics Continued
Nernst Equation:

RT
EE  o
ln(Q)
nF
THE Basic equation which describes ALL corrosion reactions

For Our Example:

RT  [ Fe ] 
2 Note: pH = -log10[H+]
EE 
o
ln  2 
nF  [ H ] 
 Pourbaix Diagram
 Potential vs pH
 pH is the measure
of [H+] ions in
solution
 Map regions of
thermodynamic
stability for metal’s
aqueous chemical
species
Source: www.corrosionsource.com
 STANDARD EMF SERIES
• EMF series o
• Metal with smaller
metal Vmetal Vometal corrodes.
Au +1.420 V • Ex: Cd-Ni cell
more cathodic

Cu +0.340
Pb - 0.126 - +
Sn - 0.136
Ni - 0.250
Co - 0.277 V o =
Cd - 0.403 0.153V
Cd 25°C Ni
Fe - 0.440
more anodic

Cr - 0.744
Zn - 0.763 1.0 M 1.0 M
Al - 1.662 Cd 2+ solution Ni 2+ solution
Mg - 2.363
Na - 2.714
K - 2.924
 Galvanic Series
HUNTINGTON CITY WATER, 25C
Volts: Saturated Calomel Half-Cell Reference Electrode

-1.2
-1.1

-1.6
-1.3
-1.4

-1.7
-1.8
-1.5
-0.3

-0.7

-1.0
-0.1
-0.2

-0.4

-0.6
-0.5

-0.9
-0.8
+0.3
+0.4

+0.2
+0.1
0
Magnesium
Manganese
Cast Iron
Zinc
Aluminum
Aluminum Alloy 5052
Mild Steel
Tin
Lead
Nickel - Silver
Copper
Alloy 20Cb3
Alloy 18-18-2
Brass Alloys
Alloy 3RE60
70 - 30 Copper-Nickel
90 - 10 Copper-Nickel
Alloy EFE62
Bronze Alloys
Alloy 6X
Alloy 17-4PH
Alloy 255 (ferrallium)
Alloy 230 (Coronel)
Alloy 26-1, 26-1 - 1/4
Alloys C276, G, X
Alloy 254 SLX
MONEL alloys 400, R405, K500
Alloy B, P, PD (Illium)
INCOLOY alloy 800, 825, 840
Nickel 200, 270
Stainless Steel 304, 316, 317, 403
INCONEL alloys 600, 617, 618, 625, 671, 690, 702, X750
Titanium
Alloy 700 (Jessop)
+0.64 - 0.76V Platinum

Source: Crum and Scarberry, Corrosion of Nickel Base Alloys Conference Proceedings - ASM 1985
Kinetics Describes Rate of Reaction
Evan’s Diagram
-
+ +2e
0.1 2H
iofor H2 IC
0 H2
NOD
E A
on Fe A
0.0 2H
+
POTENTIAL VOLTS (SHE)

+2
e- A

C
-0.1

A
TH
H

O
D
2
E CORR

IC
-0.2

-
-0.3 +2 +2e
Fe
IC
0 io Fe F
e OD
-0.4 E B
AN

B i CORR
Fe

+2

-0.5
C

+2
A

-
TH

e
O
D

-0.6
IC

Fe

-0.7
10 -10 10 -9 10 -8 10 -7 10 -6 10 -5 10 -4 10 -3 10 -2
CURRENT DENSITY, A/cm²
 Area Effects
Aa = Area Inside Crevice (Anodic)
Ac = Area Outside Crevice (Cathodic)
Aa << Ac

-
+ +e
io H+ Aa io H+ A c M
M

E io O Aa
EO /OH +
2
ia O Ac
2 2

½O
2 +H
2 O+
2e -
2O
H-
E M/M +

icorr in very
Crevice
Effect aggresive environment

No Crevice PLUS Crevice

Effect Effect

Log i
Effect of Oxidizer Concentration (e.g., Oxygen) on the
Electrochemical Behavior of an Active - Passive Metal

Increasing Oxidant
Concentration

M+
M

Log i
[Fontanna and Greene, Corrosion Engineering, McGraw-Hill, 1967]
Effect of Temperature and Dissolved O2
35

30

25
CORROSION RATE (MPY))

20

15

10 Volts: Sature dCalom elHaf- CelRf renc Electrod

+0.432 .1
0-.1 .2
0.3-4 .5
-0.67 .8
-0.91 .1
-1.23 .4
-1.56 .7
-1.8
Galvnic Seris- Concet ratedH ydrochli Acida t25°C

0
0 1 2 3 4 5 6 7 8 9 10 11
DISSOLVED O2 (PPM)
0 0.7 1.4 2.1 2.8 3.5 4.2 4.9 5.6 6.3 7.0 7.7
DISSOLVED O2 (Mg / H2O)
LEGEND
FRESH WATER @ 50°F
FRESH WATER @ 90°F
FRESH WATER @ 120°F
VELOCITY = 2.5 FPS
pH=7, R=100M-0HM
pH=7, R=2500M-0HM
Types of Aqueous Corrosion Cells

– General Corrosion
– Localized Corrosion
Pitting

Crevice Corrosion

Under-deposit Corrosion

MIC

– Tuberculation
– Galvanic Corrosion
General Corrosion
 General Corrosion
O  Random Creation and
O e- Destruction of Anodes and
e- M+
e- Cathodes
M +
e- O  Movement of Anodes and
O Cathodes
OH-  Near Uniform Thinning
-
OH e-
e- M+  Weight Loss is a Useful
M + e- Measure
e- O
O e-
M+

Source: Corrosion, ASM Handbook, Volume 13, 1987

General Corrosion

Original Surface

Penetration due to Corrosion

Localized Corrosion
Carbon Steel
Localized Corrosion
Carbon Steel
 Localized Corrosion
 Stationary Electrodes
M(OH)n M(OH)n
OH- OH-  All of the dissolution occurs
CI- in one location
Mn+  Weight loss measurement –
not useful
e e-
 Local Penetration
– Sometimes local weakening
Source: Corrosion, ASM Handbook, Volume 13, 1987
– May or may not jeopardize
structural integrity
– Determines “failure”
Potential and Current Fields in Electrolyte in
the Vicinity of a Localized Corrosion Site

Potential

Volts: Sature dCalom elHaf- CelRf renc Electrod

+0.432 .1
0-.1 .2
0.3-4 .5
-0.67 .8
-0.91 .1
-1.23 .4
-1.56 .7
-1.8
Galvnic Seris- Concet ratedH ydrochli Acida t25°C

+
Anodic
Current
Density

- Localized Anodic Site Cathodic

Metal