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
• Fatigue limit, Sfat: S = stress amplitude
case for
--no fatigue if S < Sfat unsafe steel (typ.)
Sfat
safe Adapted from Fig.
8.19(a), Callister 7e.
3 5 7 9
10 10 10 10
N = Cycles to failure
• Sometimes, the
fatigue limit is zero! S = stress amplitude
case for
unsafe Al (typ.)
N = Cycles to failure
bad better
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**
* 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
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
2H 2e H 2 ( g )
Fe 2H Fe2 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
or
nFE nFE RT ln( Q)
o
Thermodynamics Continued
Nernst Equation:
RT
EE o
ln( Q)
nF
THE Basic equation which describes ALL corrosion reactions
RT [ Fe ]
2 Note: pH = -log10[H+]
EE
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, 25C
Volts: Saturated Calomel Half-Cell Reference Electrode
-1.2
-1.1
-1.6
-1.3
-1.4
-1.5
-1.7
-1.8
-1.0
-0.3
-0.1
-0.2
-0.4
-0.6
-0.7
-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
0.1
0
iofor H2
on Fe
0.0
E A
POTENTIAL VOLTS (SHE)
A
-0.1
-0.2 E CORR
-0.3
0 io Fe
-0.4 E B
B i CORR
-0.5
-0.6
-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
io H+ Aa io H + A c
E io O Aa
EO
2
ia O Ac
2 /OH + 2
EM/M+
icorr in very
Crevice aggresive environment
Effect
Log i
Effect of Oxidizer Concentration (e.g., Oxygen) on the
Electrochemical Behavior of an Active - Passive Metal
Increasing Oxidant
Concentration
Log i
[Fontanna and Greene, Corrosion Engineering, McGraw-Hill, 1967]
Effect of Temperature and Dissolved O2
35
30
CORROSION RATE (MPY))
25
20
15
+ 0.4
+ 0.3
+ 0.2
+ 0.1
0
-0.1
-0.2
-0.3
-0.4
-0.5
-0.6
-0.7
-0.8
-0.9
-1.0
-1.1
-1.2
-1.3
-1.4
-1.5
-1.6
-1.7
-1.8
Magnesium
Manganese
Alum inum
Cadm ium
Zinc
Lead
Copper
Alloy PE 62
Alloy 26-1, 26-1 1/4
Carbon Steel
Tin
MONEL alloy 451
Alloy 18-18-2
Alloy 70Cb3
Alloy 20
Stainless Steel 304, 316, 316L, 317
Cast Iron
Ni-Resist 2
Alloy 254 SLX
Alloy 904L
INCONEL alloys 600, 601, 690, 702, 748, X750
INCOLOY alloy 825
Alloy G
Alloy B, P
, PD (Illium )
Alloy 6X (HA)
Silver
Alloy 6X
Alloy G
INCOLOY alloy 800
Alum inum
INCONEL alloys 617, 618E, 625
Alloy 5052
Stainless Steel 430
Titanium
+ 0.4-0.48V Platinum
92345r1
Ga lva nic Series - Conc entra ted Hyd roc hloric Ac id a t 25°C
[Crum and Sc a rb erry, Corrosion of Nic kel Base Alloys Conferenc e Proc eed ing s - ASM 1985]
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
M+
e-
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+
Original Surface
+ 0.3
+ 0.2
+ 0.1
0
-0.1
-0.2
-0.3
-0.4
-0.5
-0.6
-0.7
-0.8
-0.9
-1.0
-1.1
-1.2
-1.3
-1.4
-1.5
-1.6
-1.7
-1.8
Magnesium
Alum inum
Manganese
Cadm ium
Zinc
Alloy PE 62
Copper
Alloy 255 (Ferralium )
Lead
Alloy 18-18-2
Tin
MONEL alloy 451
Carbon Steel
Alloy 70Cb3
Alloy 230 (Corronel)
Cast Iron
Alloy 20
Stainless Steel 304, 316, 316L, 317
Ni-Resist 2
Alloy 254 SLX
Alloy 904L
Alloy G
Alloy 6X (HA)
Alloy B, P
, PD (Illium )
Alloy G
Silver
Alloy 6X
Alum inum
INCONEL alloys 617, 618E, 625
INCOLOY alloy 800
+ 0.4-0.48V Platinum
Titanium
Ga lva nic Series - Conc entra ted Hyd roc hloric Ac id a t 25°C
92345r1
[Crum and Sc a rb erry, Corrosion of Nic kel Base Alloys Conferenc e Proc eed ing s - ASM 1985]
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
+ 0.4
+ 0.3
+ 0.2
+ 0.1
0
-0.1
-0.2
-0.3
-0.4
-0.5
-0.6
-0.7
-0.8
-0.9
-1.0
-1.1
-1.2
-1.3
-1.4
-1.5
-1.6
-1.7
-1.8
Magnesium
Manganese
Alum inum
Cadm ium
Zinc
Lead
Copper
Alloy PE 62
Alloy 26-1, 26-1 1/4
Carbon Steel
Tin
MONEL alloy 451
Alloy 18-18-2
Alloy 70Cb3
Alloy 20
Stainless Steel 304, 316, 316L, 317
Cast Iron
Ni-Resist 2
Alloy 254 SLX
Alloy 904L
INCONEL alloys 600, 601, 690, 702, 748, X750
INCOLOY alloy 825
Alloy G
Alloy B, P
, PD (Illium )
Alloy 6X (HA)
Silver
Alloy 6X
Alloy G
Alum inum
INCONEL alloys 617, 618E, 625
INCOLOY alloy 800
Alloy 5052
Stainless Steel 430
Titanium
+ 0.4-0.48V Platinum
92345r1
Ga lva nic Series - Conc entra ted Hyd roc hloric Ac id a t 25°C
[Crum and Sc a rb erry, Corrosion of Nic kel Base Alloys Conferenc e Proc eed ing s - ASM 1985]
+
Anodic
Current
Density