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01 Corrosion

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Environmental Effects on Materials p. 16.

1
EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
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.
Environmental Effects on Materials p. 16.2
EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
THERMODYNAMIC CONSIDERATIONS (start)
• Most metals are unstable in the presence of oxygen:
xM +
y
2
O
2
→ M
x
O
y
∆G
ox
• 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.
metal
(M)
oxide
(M O )
x y
M
(2y/x)+
O
2–
e

gas
(w/O )
2
… but rate of oxidation depends on diffusion of reactants
through oxide layer
⇒ “Corrosion” might just be a faster route
for approaching equilibrium (oxidation)
Environmental Effects on Materials p. 16.3
EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
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 C
B,L
?
A B
L
L
A B
T
T
L
A B
T
L
A B
T + L
+ L
+ L
+ L
C
B,L
C
B,L
C
B,L
C
B,L
C
B
C
B
C
B
C
B
Look for…
• Shallow eutectic T • A-rich eutectic compos’n
• High T
m,B
Environmental Effects on Materials p. 16.4
EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
AQUEOUS CORROSION (start)
• Neutral metal atoms become cations in sol’n, e.g.:
Zn(s) → Zn
2+
(aq) + 2e

(1)
“oxidation occurs at the anode”
• Electrons released in (1) reduce something else,
e.g. in an acidic solution:
2H
+
(aq) + 2e

→ H
2
(g)↑ (2)
“reduction occurs at the cathode”
• Net reaction:
Zn(s) + 2H
+
→ Zn
2+
(aq) + H
2
(g)↑
(3)
• Other reactions are possible, depending on environment.
E.g., in aerated water:
2Fe(s) + O
2
(sol’n) + 2H
2
O → 2Fe
2+
(aq) + 4OH

2Fe
2+
(aq) + 4OH

→ 2Fe(OH)
2
2Fe(OH)
2
+
1
2
O
2
(sol’n) + H
2
O → 2Fe(OH)
3
(s)↓
“rust”
Environmental Effects on Materials p. 16.5
EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
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:
M
n+
(aq) + ne

→ M(s) (4)
Environmental Effects on Materials p. 16.6
EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
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
1M [Zn ]
2+
1M [Fe ]
2+
Zn
Fe
e-
e-
V
membrane
– +
0.323 V
• Fe
2+
(aq) reduces to Fe(s) • Zn oxidizes to Zn
2+
(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
Environmental Effects on Materials p. 16.7
EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
THE STANDARD EMF SERIES (end)
Net electrochemical reaction (from p. 6):
Fe
2+
(aq) + Zn(s) → Fe(s) + Zn
2+
But replace Zn & Zn(II) sol’n with Cu & Cu(II) sol’n ⇒
• Fe corrodes into solution as Fe
2+
(aq)
• Cu
2+
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
Increasing
1
3
Au
3+
+ e


1
3
Au
+1.420
inertness Fe
3+
+ e

→ Fe
2+
+0.771
1
2
Cu
2+
+ e


1
2
Cu
+0.340
(arbitrary reference →)
H
+
+ e


1
2
H
2
0.000
1
2
Fe
2+
+ e


1
2
Fe
–0.440
Increasing
1
3
Cr
3+
+ e


1
3
Cr –0.744
reactivity
1
2
Zn
2+
+ e


1
2
Zn
–0.763
Environmental Effects on Materials p. 16.8
EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
• For alloys in seawater, the galvanic series provides a
qualitative listing (Table 17.2)
Environmental Effects on Materials p. 16.9
EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
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
2
Fe
2+
+ e


1
2
Fe V°
1
= –0.440 V
1
3
Cr → e

+
1
3
Cr
3+

2
= –(–0.744) V
1
2
Fe
2+
+
1
3
Cr →
1
2
Fe+
1
3
Cr
3+
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)
Cr, Al, Y, Mg → ¹
'
¹
oxidation-resistant
“superalloys”

Environmental Effects on Materials p. 16.10
EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
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.:
acidic or
oxygenated water
will oxidize iron
Fe
O
2
Fe
2+
zinc oxidizes
& supplies electrons
to keep Fe reduced
Fe
Zn
2+
2
O
e–
H
+ H
+
Large ratio of
Zn surface area
Fe surface area
⇒ Zn won’t get depleted
• Other examples of cathodic protection — (Fig. 17.13)
underground
steel pipe
Mg
anode
e–
Mg
2+
earth
(damp)
spontaneous oxidation of Mg
supplies electrons
to keep iron reduced
inert
anode
e–
DC
power
ionic
current
external power supply
consumes energy
to provide electrons to iron
Environmental Effects on Materials p. 16.11
EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
CONCENTRATION EFFECTS — THE NERNST EQUATION
If the solution concentrations in a galvanic couple are ≠ 1 M,
corrosion tends to equalize the concentrations:
low [Fe ]
2+
high [Fe ]
2+
Fe
Fe
e-
e-
V
membrane
– +
High-Fe side: Fe
2+
+ 2e

→ Fe
(cathodic plating)
Low-Fe side: Fe → Fe
2+
+ 2e

(anodic
corrosion)
— in an ionic concentration cell,
corrosion occurs even
between the same metal (!)
• The Nernst equation:
V = (V°
2
– V°
1
) –
RT
nF
ln
¸

¸
[M
1
n+
]
[M
2
n+
]
R = 8.314 J mol
-1
F = 9.648 × 10
4
C mol
-1
n = # of e

’s in half-cell reaction
• Oxygen concentration cell:
high [O ]
2
Fe
Fe
e-
e-
V
membrane
– +
low [O ]
2
Low-[O
2
] side:
2Fe → 2Fe
2+
+ 4e

— anodic corrosion of a
particularly troublesome sort
High-[O
2
] side:
O
2
+ 2H
2
O + 4e

→ 4OH

— no plating (if no metal salts are
on the high-[O
2
] side of cell)
Environmental Effects on Materials p. 16.12
EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
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
¹
;
¹
3) Crevice corrosion
4) Pitting
⇐ oxygen concentration cell
• Mechanism
• Stagnant water in crevice or pit becomes
deoxygenated

¹
'
¹
¹
;
¹ 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
Environmental Effects on Materials p. 16.13
EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
EIGHT FORMS OF CORROSION (cont.) — Crevice
Corrosion
(Callister, Fig. 17.7)
Environmental Effects on Materials p. 16.14
EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
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
Environmental Effects on Materials p. 16.15
EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
OXIDATION
xM → xM
(2y/x)
+
+ (2y)e


y
2
O
2
+ (2y)e

→yO
2–
xM
(2y/x)+
+ yO
2–
→ M
x
O
y
xM(s) +
y
2
O
2
(g)→ M
x
O
y
(s)
• Will the oxide layer be…
• …porous? or • …protective?
⇒ Pilling-Bedworth ratio (PBR)
PBR ≡
oxide volume produced
metal volume consumed
=
MW
oxide
d
metal
xMW
metal
d
oxide

• PBR < 1 ⇒ porous oxide
• 1 < PBR < 2 ⇒ protective oxide
• 2 < PBR ⇒ oxide is heavily compressed ⇒ spalling
Environmental Effects on Materials p. 16.16
EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 04/14/03
OXIDATION KINETICS
• A porous oxide allows penetration of molecular oxygen
metal oxide
O
O
2
2
z
⇒ Rate of film formation is constant:
dz
dt
= c
1
⇒ Linear growth:
z = c
1
t + c
2
• A protective film requires diffusion through oxide layer for
further oxidation:
metal oxide
M
(2y/x)+
(2y)e–
metal oxide
(2y)e–
yO
2–
D >> D
M,oxide O,oxide
D >> D
M,oxide O,oxide
z z Recall Fick’s first law:
J
OorM
= –D
OorM

∆c
OorM
z

dz
dt
∝ J ⇒
dz
dt

1
z

z
2
= c
3
t + c
4
— parabolic growth
• Unlike linear growth, as z increases, growth slows:
or
∆m
t
linear
parabolic
z

13. McGraw-Hill. Gaskell. 10. De Guire rev. 1981. 04/14/03 .2 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.” 2nd ed. “Introduction to Metallurgical Thermodynamics. R. 16.Environmental Effects on Materials THERMODYNAMIC CONSIDERATIONS (start) • p. M (2y/x)+ 2– O e– metal oxide (M) (M x Oy ) gas (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. D.

g.L +L T L CB.L? L T CB.B • A-rich eutectic compos’n EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R.L +L A L T CB B CB. De Guire rev.Environmental Effects on Materials p.L +L B A CB B A CB B Look for… • • Shallow eutectic T High Tm. A = metal or glass. 04/14/03 . 16. B = refractory) Goal: minimize how much B is dissolved in liquid Which gives lowest CB.L +L T A L CB CB.3 THERMODYNAMIC CONSIDERATIONS (end) • Phase diagrams as an indicator of solid dissolution Application: contain molten A in solid B (e.

Environmental Effects on Materials AQUEOUS CORROSION (start) • p.g. 16. depending on environment. E.g. in an acidic solution: 2H+(aq) + 2e– → H2(g)↑ “reduction occurs at the cathode” (2) • Net reaction: Zn(s) + 2H+ → Zn2+(aq) + H2(g)↑ (3) • Other reactions are possible. e. De Guire rev.g.. in aerated water: 2Fe(s) + O2(sol’n) + 2H2O → 2Fe 2+(aq) + 4OH– 2Fe 2+(aq) + 4OH– → 2Fe(OH) 2 2Fe(OH) 2 + 2 O 2(sol’n) + H2O → 2Fe(OH) 3(s)↓ “rust” 1 EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R.4 Neutral metal atoms become cations in sol’n.: Zn(s) → Zn2+(aq) + 2e– “oxidation occurs at the anode” (1) • Electrons released in (1) reduce something else. 04/14/03 . e.

Environmental Effects on Materials AQUEOUS CORROSION (cont’d) p. 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.5 Note: an electrochemical reaction (e. through an external circuit Free energy considerations: If G < 0 for rxn. (3) on p.g. 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. De Guire rev. 16. 04/14/03 .g. 4: Mn+(aq) + ne– → M(s) (4) • • EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R.

6 When two species are present in an electrochemical couple.323 V EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev.t.r. 04/14/03 .t.r. Fe • Fe plates on the Fe electrode• Zn corrodes into the solution • voltmeter reads 0.0 M Fe(II) salt Metallic Zn in an aqueous sol’n of 1. 16. which gets oxidized and which gets reduced? Consider a cell: • • • • • Metallic Fe in an aqueous sol’n of 1.0.Environmental Effects on Materials THE STANDARD EMF SERIES (start) p. Zn • Zn oxidizes to Zn2+(aq) • Zn is anodic w.323 V e- 2+ 1M [Fe2+ ] 1M [Zn ] membrane • Fe 2+(aq) reduces to Fe(s) • Fe is cathodic w.0 M Zn(II) salt Separated by a slightly permeable membrane Electrodes connected to a voltmeter 25°C + Fe V – Zn e.

420 +0.771 +0. 04/14/03 . De Guire rev. V Increasing inertness 1 3 Au 3+ + e– → Au Cu2+ + e– → Cu 1 2 1 3 +1.Environmental Effects on Materials THE STANDARD EMF SERIES (end) Net electrochemical reaction (from p.763 Fe 3+ + e– → Fe 2+ 1 2 1 2 (arbitrary reference →) H+ + e– → 1 2 H2 1 2 1 3 Cr 1 2 Fe 2+ + e– → Fe Cr3+ + e– → Zn2+ + e– → Zn Increasing reactivity 1 3 1 2 EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R.744 –0.7 Metals can be placed in a series indicating their relative tendencies to oxidize — the standard emf series Electrode reaction V°.000 –0.440 –0.340 0. 16. 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 p.

04/14/03 .Environmental Effects on Materials p. the galvanic series provides a qualitative listing (Table 17.2) EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. 16. De Guire rev.8 • For alloys in seawater.

Environmental Effects on Materials p. Mg → oxidation-resistant   “superalloys” EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev.440 V 1 3 Cr 1 1 Fe 2+ + 3 Cr 2 → e – + 3 Cr3+ → 1 2 V° 2 = –(–0.744) V V° = 0.: 1 2 1 2 Fe 2+ + e– → Fe 1 V° 1 = –0. 16.1) Cr.9 APPLICATIONS OF THE STANDARD EMF SERIES (start) Q. or Fe alloys might be expected to oxidize more readily than the host metal? A. Ni. but do not multiply V° by a constant to match the reaction V° > 0 ⇒ reaction occurs spontaneously • Q.304 V Fe+ 1 3 Cr3+ Note: • Balance e–’s when writing half-cell reactions.: Which alloying elements in Co.: What would be the voltage from a standard galvanic cell consisting of Cr/Cr(III) and Fe/Fe(II)? A.: (see Table 17. Y. Al. 04/14/03 .

De Guire rev.13) DC power earth (damp) e– Mg 2+ e– ionic current Mg underground anode steel pipe spontaneous oxidation of Mg supplies electrons to keep iron reduced inert anode external power supply consumes energy to provide electrons to iron EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. 17. 04/14/03 .: How does a thin layer of Zn applied to plain carbon steels (galvanized steel) provide corrosion protection? A.10 APPLICATIONS OF THE STANDARD EMF SERIES (end) Q. 16.Environmental Effects on Materials p.: H O2 Fe acidic or oxygenated water will oxidize iron + Fe2+ H + O2 Zn2+ e– Fe zinc oxidizes & supplies electrons to keep Fe reduced Large ratio of Zn surface area Fe surface area ⇒ Zn won’t get depleted • Other examples of cathodic protection — (Fig.

corrosion occurs even between the same metal (!) high [Fe2+ ] low [Fe2+ ] membrane • The Nernst equation: RT V = (V°2 – V°1) – nF ln  [M n+]  1   [M2n+] R = 8. corrosion tends to equalize the concentrations: + eFe V – eFe High-Fe side: Fe2+ + 2e– → Fe (cathodic plating) Low-Fe side: Fe → Fe 2+ + 2e– (anodic corrosion) — in an ionic concentration cell. De Guire rev.11 CONCENTRATION EFFECTS — THE NERNST EQUATION If the solution concentrations in a galvanic couple are ≠ 1 M.648 × 10 4 C mol-1 n = # of e–’s in half-cell reaction • Oxygen concentration cell: + eV – eFe Low-[O2] side: 2Fe → 2Fe 2+ + 4e– — anodic corrosion of a particularly troublesome sort High-[O2] side: O 2 + 2H2O + 4e– → 4OH– — no plating (if no metal salts are on the high-[O2] side of cell) Fe high [O2 ] low [O2 ] membrane EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. 16.Environmental Effects on Materials p.314 J mol -1 F = 9. 04/14/03 .

Environmental Effects on Materials EIGHT FORMS OF CORROSION (start) 1) 2) Uniform attack — tarnishing. De Guire rev. 04/14/03 . 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.12 Crevice corrosion   ⇐ oxygen concentration cell Pitting • Mechanism • • • • • • • Stagnant water in crevice or pit becomes deoxygenated  Oxygen reduction at    large aerated surface ⇒ oxidation of crevice metal Mitigated by… …welding (vs. brass Mitigated by… • • • 3) 4) …large anode area …open circuit …third metal anodic to both p. 16. widespread rust Galvanic corrosion between dissimilar metals • • Steel corrodes in electrochemical contact with copper.

13 EIGHT FORMS OF CORROSION (cont.7) EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. 04/14/03 . Fig.Environmental Effects on Materials p. 17. De Guire rev.) — Crevice Corrosion (Callister. 16.

Environmental Effects on Materials EIGHT FORMS OF CORROSION (end) 5) Intergranular corrosion • • p. 04/14/03 .14 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 • Lower loads • Annealing Alleviated by reducing stress: • Larger area EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. De Guire rev. 16.

De Guire rev.Environmental Effects on Materials OXIDATION xM → xM(2y/x) + + (2y)e– p.15 y – 2– 2 O 2 + (2y)e → yO 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) MWoxidedmetal oxide volume produced 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. 16. 04/14/03 .

oxide • Unlike linear growth.oxide >> D O. 16.oxide DO.16 A porous oxide allows penetration of molecular oxygen z O 2 O2 oxide metal ⇒ Rate of film formation is constant: dz dt = c1 ⇒ Linear growth: z = c1t + c2 • A protective film requires diffusion through oxide layer for further oxidation: z M (2y/x)+ z yO2– (2y)e– metal oxide metal Recall Fick’s first law: JOorM = –DOorM ∆cOorM z (2y)e– oxide dz dz 1 ∝ J ⇒ dt ∝ z dt z 2 = c3t + c4 — parabolic growth DM. De Guire rev. growth slows: linear z or ∆m parabolic t EMSE 201 — Introduction to Materials Science & Engineering © 2003 Mark R. as z increases.oxide >> DM. 04/14/03 .Environmental Effects on Materials OXIDATION KINETICS • p.

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