Environmental Effects on Materials p. 16.

Corrosion …
• … is dissolution (or other breakdown via chemical
reaction) of a solid, in which a fluid supplies one or
more of the reactants
• … involves…
• … thermodynamic stability of the solid in the fluid
environment
• … kinetics of any breakdown reaction that might
occur

Examples:
• Electrochemical corrosion of metals
• Oxidation or sulfidation of…
• Metals • Non-oxide ceramics
• Dissolution of refractories * by molten metals or glass

In contrast, erosion…
• … is the physical removal of solid material by the
mechanical action of a flowing fluid
• … involves…
• … fluid dynamics • … abrasion/wear resistance of
the solid
In real situations, corrosion and erosion often occur
simultaneously
* Refractories: structural materials used to contain and withstand high-
temperature processes such as steelmaking and glass melting.

EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
Environmental Effects on Materials p. 16.2

THERMODYNAMIC CONSIDERATIONS (start)

• Most metals are unstable in the presence of oxygen:

y
xM + 2 O 2 → Mx O y ∆Gox
• G ox > 0 ⇒ oxidation won’t occur without energy input
• G ox < 0 ⇒ oxidation can occur spontaneously
“Ellingham diagram” — Fig. 10.13, D.
R. Gaskell, “Introduction to
Metallurgical Thermodynamics,” 2nd
ed. McGraw-Hill, 1981. (2y/x)+
M
2–
O

e–

metal oxide gas

(M) (M x Oy ) (w/O2 )

… but rate of oxidation depends on diffusion of reactants

through oxide layer
⇒ “Corrosion” might just be a faster route
for approaching equilibrium (oxidation)

EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
Environmental Effects on Materials p. 16.3

THERMODYNAMIC CONSIDERATIONS (end)

• Phase diagrams as an indicator of solid dissolution

Application: contain molten A in solid B

(e.g. A = metal or glass, B = refractory)
Goal: minimize how much B is dissolved in liquid

Which gives lowest CB,L?

L L
CB,L CB,L
T +L T +L

A CB B A CB B

L L
CB,L CB,L
T T +L
+L

A CB B A CB B

Look for…
• Shallow eutectic T • A-rich eutectic compos’n
• High Tm,B

EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
Environmental Effects on Materials p. 16.4

AQUEOUS CORROSION (start)

• Neutral metal atoms become cations in sol’n, e.g.:

Zn(s) → Zn2+(aq) + 2e– (1)
“oxidation occurs at the anode”

• Electrons released in (1) reduce something else,

e.g. in an acidic solution:
2H+(aq) + 2e– → H2(g)↑ (2)
“reduction occurs at the cathode”

• Net reaction:
Zn(s) + 2H+ → Zn2+(aq) + H2(g)↑ (3)

• Other reactions are possible, depending on environment.

E.g., in aerated water:
2Fe(s) + O2(sol’n) + 2H2O → 2Fe 2+(aq) + 4OH–
2Fe 2+(aq) + 4OH– → 2Fe(OH) 2
1
2Fe(OH) 2 + 2 O 2(sol’n) + H2O → 2Fe(OH) 3(s)↓
“rust”

EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
Environmental Effects on Materials p. 16.5

AQUEOUS CORROSION (cont’d)

Note: an electrochemical reaction (e.g. reaction (3)) requires:

• Oxidation of one species at an anode
• Reduction of one species at a cathode
• Transport of ions through an electrolyte
• Transport of electrons from anode to cathode —
e.g. through an external circuit

Free energy considerations: If G < 0 for rxn. (3) on p. 4 …

• … the energy released can drive an electrical load —

a battery

• … the reverse reaction can be made to happen

with electrical energy input

Plating

• Consists of cations in sol’n being reduced to metal

atoms & depositing on an electrically conductive surface

• Is the reverse of reactions like (1) on p. 4:

Mn+(aq) + ne– → M(s) (4)

EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
Environmental Effects on Materials p. 16.6

THE STANDARD EMF SERIES (start)

When two species are present in an electrochemical couple,

which gets oxidized and which gets reduced?
Consider a cell:
• Metallic Fe in an aqueous sol’n of 1.0 M Fe(II) salt
• Metallic Zn in an aqueous sol’n of 1.0 M Zn(II) salt
• Separated by a slightly permeable membrane
• Electrodes connected to a voltmeter
• 25°C
V
+ –
e- 0.323 V e-

Fe Zn

2+
1M [Fe2+ ] 1M [Zn ]

membrane

• Fe 2+(aq) reduces to Fe(s) • Zn oxidizes to Zn2+(aq)

• Fe plates on the Fe electrode• Zn corrodes into the solution
• Fe is cathodic w.r.t. Zn • Zn is anodic w.r.t. Fe
• voltmeter reads 0.323 V

EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
Environmental Effects on Materials p. 16.7

THE STANDARD EMF SERIES (end)

Net electrochemical reaction (from p. 6):

Fe 2+(aq) + Zn(s) → Fe(s) + Zn2+

But replace Zn & Zn(II) sol’n with Cu & Cu(II) sol’n ⇒

• Fe corrodes into solution as Fe2+(aq)
• Cu2+ plates on the Cu electrode as Cu(s)
• Voltmeter reads 0.780 V in opposite direction

Metals can be placed in a series indicating their relative

tendencies to oxidize — the standard emf series
Electrode reaction V°, V
1 1
Increasing 3 Au 3+ + e– → 3 +1.420
Au
inertness Fe 3+ + e– → Fe 2+ +0.771
1 1
2 Cu2+ + e– → 2 +0.340
Cu
1
(arbitrary reference →) H+ + e– → 2 H2 0.000
1 1
2 Fe 2+ + e– → 2 –0.440
Fe
1 1
Increasing 3 Cr3+ + e– → 3 Cr –0.744
1 1
reactivity 2 Zn2+ + e– → 2 –0.763
Zn
EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
Environmental Effects on Materials p. 16.8
• For alloys in seawater, the galvanic series provides a
qualitative listing (Table 17.2)

EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
Environmental Effects on Materials p. 16.9

APPLICATIONS OF THE STANDARD EMF SERIES (start)

Q.: What would be the voltage from a standard galvanic cell

consisting of Cr/Cr(III) and Fe/Fe(II)?
A.:
1 1
2 Fe 2+ + e– → 2 Fe V° 1 = –0.440 V
1 1
3 Cr → e – + 3 Cr3+ V° 2 = –(–0.744) V
1 1 1 1
2 Fe 2+ + 3 Cr → 2 Fe+ 3 Cr3+ V° = 0.304 V

Note:
• Balance e–’s when writing half-cell reactions, but
do not multiply V° by a constant to match the
reaction
• V° > 0 ⇒ reaction occurs spontaneously

Q.: Which alloying elements in Co, Ni, or Fe alloys might be

expected to oxidize more readily than the host metal?
A.: (see Table 17.1)
oxidation-resistant

Cr, Al, Y, Mg →  “superalloys”

EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
Environmental Effects on Materials p. 16.10

APPLICATIONS OF THE STANDARD EMF SERIES (end)

Q.: How does a thin layer of Zn applied to plain carbon

steels (galvanized steel) provide corrosion protection?
A.:
+ H + O2 Zn2+
H O2
Fe2+
e–
Fe Fe
acidic or zinc oxidizes
oxygenated water & supplies electrons
will oxidize iron to keep Fe reduced

Zn surface area
Large ratio of Fe surface area ⇒ Zn won’t get depleted

• Other examples of cathodic protection — (Fig. 17.13)

DC
power
earth e–
(damp)
e– ionic
Mg 2+ current

Mg inert
underground anode anode
steel pipe
spontaneous oxidation of Mg external power supply
supplies electrons consumes energy
to keep iron reduced to provide electrons to iron

EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
Environmental Effects on Materials p. 16.11

CONCENTRATION EFFECTS — THE NERNST EQUATION

If the solution concentrations in a galvanic couple are ≠ 1 M,

corrosion tends to equalize the concentrations:

+ – High-Fe side: Fe2+ + 2e– → Fe

e- V e-
(cathodic plating)
Low-Fe side: Fe → Fe 2+ + 2e–
Fe Fe (anodic
corrosion)
— in an ionic concentration cell,
high [Fe2+ ] low [Fe2+ ] corrosion occurs even
between the same metal (!)
membrane

• The Nernst equation:

 [M n+] R = 8.314 J mol -1
RT  1
V = (V°2 – V°1) – nF ln  F = 9.648 × 10 4 C mol-1
 [M2n+]
n = # of e–’s in half-cell reaction

• Oxygen concentration cell:

V
+ – Low-[O2] side:
e- e- 2Fe → 2Fe 2+ + 4e–

Fe Fe
— anodic corrosion of a
particularly troublesome sort

High-[O2] side:
high [O2 ] low [O2 ] O 2 + 2H2O + 4e– → 4OH–
membrane — no plating (if no metal salts are
on the high-[O2] side of cell)
EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
Environmental Effects on Materials p. 16.12

EIGHT FORMS OF CORROSION (start)

1) Uniform attack — tarnishing; widespread rust

2) Galvanic corrosion between dissimilar metals

• Steel corrodes in electrochemical contact
with copper, brass
• Mitigated by…
• …large anode area
• …open circuit
• …third metal anodic to both

3) Crevice corrosion
4) Pitting  ⇐ oxygen concentration cell

• Mechanism
• Stagnant water in crevice or pit becomes
deoxygenated
 Oxygen reduction at 
•  
large aerated surface ⇒ oxidation of crevice metal
• Mitigated by…
• …welding (vs. rivets or bolts)
• …eliminating moisture (nonabsorbing gaskets)
• …removing accumulating deposits
• …design to ensure complete drainage

EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
Environmental Effects on Materials p. 16.13
EIGHT FORMS OF CORROSION (cont.) — Crevice
Corrosion
(Callister, Fig. 17.7)

EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
Environmental Effects on Materials p. 16.14

EIGHT FORMS OF CORROSION (end)

5) Intergranular corrosion
• Grain boundaries are areas of local high reactivity
• Specific mechanisms involve segregation of
particular elements into precipitates

6) Selective leaching
• Dezincification of brass
• Lead from glassware & ceramic glazes

7) Erosion-corrosion
• Passive coating may be abraded away
• Alleviated by reducing…
• …fluid turbulence
• …bubbles & particulates

8) Stress corrosion
• Local stresses (residual or external) increase
corrosion
• High strain energy
• High dislocation density
• Alleviated by reducing stress:
• Larger area • Lower loads • Annealing
EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
Environmental Effects on Materials p. 16.15

OXIDATION

xM → xM(2y/x) + + (2y)e–
y
2 O 2 + (2y)e → yO
– 2–

xM(2y/x)+ + yO2– → Mx O y
y
xM(s) + 2 O 2(g)→ Mx O y(s)

• Will the oxide layer be…

• …porous? or • …protective?

⇒ Pilling-Bedworth ratio (PBR)

oxide volume produced MWoxidedmetal
PBR ≡ metal volume consumed = xMW metaldoxide

• PBR < 1 ⇒ porous oxide

• 1 < PBR < 2 ⇒ protective oxide

• 2 < PBR ⇒ oxide is heavily compressed ⇒ spalling

EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
Environmental Effects on Materials p. 16.16
OXIDATION KINETICS

• A porous oxide allows penetration of molecular oxygen

z ⇒ Rate of film formation is constant:

dz
O2 dt = c1
O2
⇒ Linear growth:
oxide metal z = c1t + c2

• A protective film requires diffusion through oxide layer for

further oxidation:
z z Recall Fick’s first law:
M
(2y/x)+
yO2– ∆cOorM
JOorM = –DOorM z
(2y)e– (2y)e–
dz dz 1
dt ∝ J ⇒ dt ∝ z
oxide metal oxide metal
DM,oxide >> D O,oxide DO,oxide >> DM,oxide z 2 = c3t + c4
— parabolic growth

• Unlike linear growth, as z increases, growth slows:

linear
z
or parabolic
∆m

EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03