CORROSION

CORROSIONOVERVIEW
OVERVIEW
Corrosion : Spontaneous reaction occurring in the direction of lowering G
G1
<
G2
<
G3
> G1
Metal Ore Metal Extraction Forming & Shaping Rust
Oxide
Blast F'ce
Rolling, Forging
Metal oxide
Sulfide
Extrusion, etc.
(Chemical Energy)
(Mechanical Energy)
Aqueous Corrosion : Most low temperature corrosion
Electrochemical reaction in nature
High Temperature Corrosion : Most high temperature corrosion
Gas/Metal reaction in nature

CORROSION
CORROSIONSTUDY
STUDY
Corrosion Mechanism Study
- Liquid/Metal
- Gas/Metal
- Mechanical effect
- Irradiation effect
Corrosion Control
- Alloy design
- Coating : painting, plating
conversion coating
- Inhibitor
- Electrochemical protection

Design
- Process design
- Process development
- System design

Topics
Topicsfor
for Presentation
Presentation
- Principle of High Temperature Corrosion
- Experimental Methods for High Temperature
Corrosion
- Corrosion of Heat Exchanger Materials
- Case Study on Heat Exchanger Materials

Requirement
Requirement for
for High
High Temperature
Temperature Materials
Materials

- High mechanical strength

- Dense and protective oxide formation by reaction
between the substrate material and environment
- Good stability of oxide under thermal and mechanical
stresses
- Cost effective

TYPES
TYPES OF
OFHIGH
HIGH TEMPERATURE
TEMPERATURE CORROSION
CORROSION
Oxidation

: Pure metal oxidation

Alloy oxidation

Corrosion in Mixed Environment:

Sulphidation
Carburization
Hot Corrosion
Coal ash deposit corrosion
5

HIGH
HIGH TEMPERATURE
TEMPERATURE OXIDATION
OXIDATION
Simplified Mode for High Temperature Oxidation
METAL

SCALE

GAS

Cation
M = M2+ + 2eM + O2- = MO + 2e-

Cation vacancies
Electrons

M 2+ + 2e- +1/2O2 = MO
1/2O2 + 2e- = O2-

Anion

FUNDAMENTALS
FUNDAMENTALSOF
OFHIGH
HIGHTEMPERATURE
TEMPERATURECORROSION
CORROSION
Thermodynamic
Fundamentals

Elligham diagram
plots of the standard free energy of
formation versus temperature for the
compounds of type, e.g. oxides,
M + O2 = MO2
sulphides, carbides, etc.
M/MO2

O2

= exp

RT

M/MO2

O2

DG

MO2

aM

exp

DG

RT

(alloy)

Stability Diagram
: useful in interpreting the condensed
phases which form in the environment
containing more than one oxidants

Vapor Species Diagram

: most suited for presentation of vapor
pressure data in oxide systems are
log pMxOy, for a fixed T, versus log pO2

log (p SO2/pSO3)

log( p H2/pH2O)

22 20

18

16 14

12

10

14 12

10

-2

-4

-6

4
0

-15
-20

Ni(s)

Cr2O3(s)

-4
-8

Cr(g)

-12
-16
-20

(g
CrO

-35
-44 -40 -36 -32 -28 -24 -20 -16 -12 -8

log pO2 (atm)

Ni-O-S system at 1250 K

-4

O
Cr

)
(g

-24

-30

rO

-25

NiO(s)

Cr(s)

(g
)

(s)

-10

log pCrxOy (atm)

-5

NiSy(l)

O
NiS

log pS2 (atm)

-44 -40 -36 -32 -28 -24 -20 -16 -12 -8

-4

log pO2 (atm)

Cr-O system at 1250 K

Reaction Rate Fundamentals

2. Parabolic Rate Law

W2 = kt + A
Ex) Diffusion controlled oxidation
through fairly thick oxide

Weight (W)

1. Linear Rate Law

W = kt
Ex) Heat treatment in partial vacuum

a
e
n
Li

ate
r
r

cr
i
l
o
b
ara

ate

Time (t)

10

4. Inverse Logarithmic Rate Law

1/W = B - k log(t)
Ex) Electric field induced transport
of ions through thin oxide films

Weight (W)

3. Logarithmic Rate Law

W = k log(t + to) + A
Ex) Oxidation occurring typically
at low temp. up to 400C

5. Paralinear Rate Law

W = (kp/kl) ln(1/1-(klx/kp)) + kl(f - 1)- t
Ex) Hot corrosion through the inner
compact and outer porous layers

rate
c
i
m
h
t
Logari

er
v
n
I

g
o
l
e

ate
r
ic
m
th
ar i

Time (t)

11

OXIDATION
OXIDATION OF
OFPURE
PURE METALS
METALS
1. Systems forming single layer scales
Ni/NiO Zn/ ZnO
2. Systems forming multiple scale layers
Fe/FeO/Fe3O4/Fe2O3
Co/CoO/Co3O4
3. Systems forming volatile species
Cr/Cr2O3/CrO3 Mo/MoO2/MoO3
W/WO2/WO2.7/WO3
Si/SiO/SiO2
Pt/PtO2
Rh/RhO2
4. Systems with significant oxygen solubilities in the metal
Ti-O system
5. Systems with significant scale cracking
Nb-O system
Ta-O system

12

Oxidation of Iron
Formation of multi-layer scale
Wustite
1200

Magnetite

FeO

Temperature (oC)

+ FeO

Fe2O3
+
Fe3O4

FeO
+
Fe3O4

1000

800

Haematite

O2
+
Fe2O3

+ FeO

600
+ Fe3O4
22

24

26

28

30

Oxygen wt%
FeO

Fe3O4

Fe2O3

13

Oxidation
OxidationMechanism
Mechanismof
ofIron
Iron

Fe

FeO

Fe3O4

Fe2O3

O2

Fe2+
Fe

2Fe3+ + 6e- +

Fe3+

2+

3
O
2 2

= Fe2O3

Fe3+
e-

ee-

O21
2

O2 + 2e- = O2-

2Fe3+ + 3O2- = Fe2O3

Fe = Fe2+ + 2eFen+ + ne- + 4Fe2O3 = 3Fe3O4
Fe2+ + 2e- +Fe3O4 = 4FeO

14

Oxidation of Chromium
Scale thinning by CrO3 evaporation
Cr2O3

O2

Cr2O3

O2

CrO3
O2-

Cr
eCr3+

Cr2O3 + 32 O2(g) = 2CrO3(g)

Oxide thickness

Cr

Scale buckling as a result of

compressive stress development

00
14

C
o

0
20

Time

15

Vapor Species Diagram

most suited for presentation of vapor pressure data in oxide
systems are log pMxOy, for a fixed T, versus log pO2
log( p H2/pH2O)
14

12

10

-2

-4

-6

Cr(s)

Cr2O3(s)

-4

Cr(g)

-8
-12

(g)
O
r
C

-16

O
Cr

rO

(g
)

-20
-24

-44

)
(g

log pCrxOy (atm)

00

-40

-36

-32

-28

-24

-20

-16

-12

-8

-4

log pO2 (atm)

Cr-O system at 1250 K

16

Mechanism of High Temperature Oxidation

Growth here

Electrons
Metal
ions

Electron

Growth here

Gas

Gas

Gas
Electron

Oxide

Metal

Oxygen
ions
Metal

Metal
ions
Metal

Oxide

Oxide

Oxygen
ions

Growth here

17

Degradation of Oxide Film

Stress Development in the Oxide

1. Growth Stress
2. Thermal Stress
Growth stress : volume difference between the oxide and the metal
PBR =

V (per metal ion in oxide)

V (per metal atom in metal)

PBR>1 : compression
PBR<1 : tension

Oxide

PBR

Oxide

PBR

Oxide

PBR

K2 O

0.45

NiO

1.65

Fe2O3

2.14

MgO

0.81

FeO

1.68

Ta2O5

2.50

Na2O

0.97

TiO2

1.70-1.78

Nb2O5

2.68

Al2O3

1.28

CoO

1.86

V2O5

3.19

Zr2O

1.56

Cr2O3

2.07

WO3

3.30

Cu2O

1.64

Fe3O4

2.10

18

Oxidation of Molybdenum
Volatilization of oxides at high temperatures and high oxygen pressure
Unlike Cr, which develops a limiting scale thickness, complete oxide volatilization
log( p H2/pH2O)
14

12

10

-2

-4

-6

4
MoO2(s)

Mo(s)

MoO3(l)

)3 (
3

-4

(M
oO

log pCrxOy (atm)

g)

g)
O 3(
Mo

-8
-12

MoO2(g)

-16

Mo
O(
g)

-20

g)
o(
M

-24

-44

-40

-36

-32

-28

-24

-20

log pO2 (atm)

-16

-12

-8

-4

19

Thermal stress : difference in thermal expansion coefficient

of the oxide and the metal

ox =

EoxT(ox- m)
1 + 2(Eox/Emtox/tm)
System

Oxide coefficient

E : elastic modulus
a : coefficient of thermal
expansion
t : thickness
Metal coefficient

Ratio

Fe/FeO

12.2 X 10-6

15.3 X 10-6

1.25

Fe/Fe2O3

14.9 X 10-6

15.3 X 10-6

1.03

Ni/NiO

17.1 X 10-6

17.6 X 10-6

1.03

Co/CoO

15.0 X 10-6

14.0 X 10-6

0.93

Cr/Cr2O3

7.3 X 10-6

9.5 X 10-6

1.30

Cu/Cu2O

4.3 X 10-6

18.6 X 10-6

4.32

Cu/CuO

9.3 X 10-6

18.6 X 10-6

2.00

20

OXIDATION
OXIDATION OF
OFALLOYS
ALLOYS

1. The metals in the alloy have different affinities for oxygen

2. Ternary and higher oxides may form
3. A degree of solid solubility between the oxides may exist
4. Various metal ions have different mobilities in the oxide phases
5. Various metals have different diffusivities in the alloy
6. Dissolution of oxygen into the alloy may result in
internal oxidation of one or more alloying elements
21

Classification of Reaction Types

1. Noble parent with base alloying element
(A) Noble parent: Au, Ag, Pt
(B) Base metal: Cu, Ni, Fe, Co, Cr, Al, Ti
NB

A
+
BO

A- B

NB

Low conc. of B

A- B

BO

High conc. of B

2. Base parent with base alloying element

(A) Parent: Ni, Co
(B) Alloying element: Cr, Al, Ti
NB

A- B

A
+
BO

AO

Low conc. of B

NB
A- B

BO

High conc. of B

22

Internal Oxidation
Oxygen diffusion into an alloy causes sub-surface precipitation
of the oxide of one or more alloy elements
The necessary condition for the occurrence of the internal oxidation
1. DGo of formation for the solute metal oxide, BOn, must be more negative than
DGo of formation for the base metal oxide.
2. Base metal must have a solubility and diffusivity for oxygen which is sufficient
to establish the required activity of dissolved oxygen at the reaction front.
3. The solubility concentration of the alloy must be lower than that require for
the transition from internal to external oxidation
4. No surface layer must prevent the dissolution of oxygen into the alloy at the
start of oxidation

23

Fe-Cr alloys Oxidation

FeCr2O4
Fe2O3

Fe3O4

FeO

Fe-Cr

O2

Fe(FeCr)2O4

Fe2O3

Fe-Cr

O2
FeCr2O4

Fe-5Cr
Fe2O3

Fe3O4

FeO

Fe-15Cr
Fe-Cr

Cr2O3

Fe-Cr

O2

O2

Fe-10Cr

Fe-20Cr

Schematic Diagram of the Scale Morphologies on Fe-Cr alloys

24

Gettering Effect
In multi-component system, one alloy element aid another
to be selectively oxidized to form a stable external oxide

Ni-Cr-Al system
1/3 Go(Al2O3) < 1/3 Go(Cr2O3) < G one)
Ni-9%Cr-6%Al produces continuous
protective Al2O3 scales
Cu-Zn-Al system

25

Synergistic effect of
Cr on the producing
of Al2O3 scales;
gettering during
transient oxidation of
Ni-15Cr-6Al at 1000
C

26

Fig.
Comparison of
the oxidation of
various alloys in
1 atm O2 at
1200 C

27

CORROSION
CORROSION IN
IN MIXED
MIXED ENVIRONMENT
ENVIRONMENT
Fe-O-S System

FeS

Fe3O4
Fe

FeO

28

HOT
HOT CORROSION
CORROSION
Definition: Accelerated form of high temperature oxidation
by fluxing action of the salt deposit
Types of Hot Corrosion
1. High Temperature Hot Corrosion (HTHC)
Main mechanism: Basic fluxing
2. Low Temperature Hot Corrosion (LTHC)
Main mechanism: Acidic fluxing
29

High Temperature Hot Corrosion

HTHC by Na2SO4 Deposit
Temperature: above melting point of Na2SO4 (884C)
Atmosphere: SO2 containing environment
Degradation mechanism: basic fluxing
Basic Fluxing
MO + O2- = MO22ex) 2NiO + O2- + 1/2 O2 = 2 NiO2(At constant basicity the solubility of NiO increases
with increasing oxygen pressure.)
Cr2O3 + O2- = 2 CrO2- (at low oxygen pressure)
Cr2O3 + 2 O2- + 3/2 O2 = 2 CrO42- (at high oxygen pressure)
Al2O3 + O2- = 2 AlO2- (at low oxygen pressure)
30

Stability Diagram
for Ni-O-S System

31

Schematic Diagram illustrating the Na2SO4 induced Hot Corrosion

32

Basic Mechanism of Hot Corrosion

Degradation of alloys caused by presence of liquid salt deposit

4
NiO

Fe2O3

Salt

Oxide

Al2O3

2
Co3O4

2CrO22- = Cr2O3 + O 2-

Cr2O3

Cr + 3/2O2 = Cr2O3

Metal

Log Concentration (ppm)

Dissolution and reprecipitation of oxide

5 6 7 8 9 10 11 12 13 14 15 16 17
Cr2O3 + O2- = 2CrO22-

-Log a Na2O

33

Low Temperature Hot Corrosion

LTHC by Na2SO4 Deposit
Temperature: below melting point of Na2SO4 (884C)
Atmosphere: oxygen and SO3 containing environment
Degradation mechanism: acidic fluxing
Acidic Fluxing
MO = M2+ + O2ex) NiO + SO3 = Ni2+ + SO42Cr2O3 + 3 SO3 = 2 Cr3+ + 3 SO42Al2O3 + 3 SO3 = 2 Al3+ + 3 SO42SO3 + SO42- = S2O722-

34

Comparison of
theoretically estimated
values of the critical SO3
pressures
needed to form molten
Na2SO4+NiSO4 and the
lowest SO3 pressures at
which formation of molten
sulphate was observed

35

Schematic diagram of the reaction mechanism of low temperature

hot corrosion of Ni in O2+SO2 and/or SO3 atmospheres.
36

Schematic illustration of the reaction mechanism of low temperature

hot corrosion of Ni-Cr alloy in SO3-containing gases
37

The temperature dependence of the corrosion rate of Ni-30%Cr coated with Na 2SO4
in 1 atm of O2+1%(SO2+SO3) and of Ni-20%Cr (no salt deposit) in 1 atm of
38
SO2:O2=1:1.

The Ni-S Phase Diagram

39

The NiSO4-Na2SO4 Phase Diagram

40

Comparison of Na2SO4-induced hot corrosion of Ni-30%Cr and

Co-30%Cr in O2+1%(SO2+SO3) and O2+0.15%(SO2+SO3), respectively

41

Alloy Induced Acidic Fluxing

In high Mo containing alloys
Ex: B-1900 (Ni-8Cr-6Al-6Mo-10Co-1Ti-4.3Ta-0.11C-0.15B0.072Zr)
1. Initially attacked by basic fluxing, as the protective scale is
broken up,
then, the alloy is oxidized
Mo + 3/2 O2 = MoO3
2. MoO3 gradually dissolves in the melt as Na2 MoO4
MoO3 + SO42- = MoO42- + SO3
This reaction changes the acidity of the melt to acidic fluxing
3. MoO3 also dissolves the protective alumina scale
Al2O3 + 3 MoO3 = 2 Al3+ + 3 MoO4242

(590-620C)

Corrosion of
Heat Exchanger
Materials

(400-425C)

Schematic Illustration of a Utility Boiler

43

Boiler Operation
Peak Flame Temperature: 1550 - 1750 C
Metal Temperature of Steel Tube: 400 - 450 C
Superheater: The water-free steam is heated to 650C.
at 16.5MPa for subcritical boiler
at 24.0MPa for supercritical boiler
(Max. at 650C, 34.5MPa)
Economizer: The condensed water from steam is
preheated
before recycling to the boiler.
Gas temp in the region: 800C in, 300 C
out
44

Oxidation Limits

Material
Carbon Steel
Carbon + 0.5%Mo
1.25%Cr + 0.5%Mo
2.25%Cr-1%Mo
18%Cr-10%Ni

ASME Spec.
SA-178, SA-210, SA-192
SA-209-T1
SA-213-T11
SA-213-T22
SA-213-321H

Temp.(C)
454
482
552
579
816

45

Effect
Effect of
ofAlloying
Alloying Elements
Elements
Si: added to all steels as a deoxidizing element
mild ferrite strengthener
when added in amount up to 2.5%, the strength is increased
without any adverse effects on ductility
Mo: ferrite strengthener
increases the strength without any loss of ductility
mild carbide stabilizer
retards the formation of graphite upon prolonged heating
graphitizing temp.: carbon steel - 420C, carbon-Mo steel - 455C
Cr: greatly enhances the oxidation resistance
oxidation limit: T-11(1.5%Cr) - 550 C, T-22(2.25%Cr) - 580 C
improves the high-temp. strength and creep properties
carbide stabilizer: Cr-Mo steels do not form graphite under any condition

46

POSTECH
Metals
MetalsUsed
UsedininBoilers
Boilers
Product
Form
Tubes

Pipe
Plate
Tubes

Plate

ASAE
Number
SA-178A
SA-192
SA-210Al
SA-178C
SA-106B
SA-515-70
SA-516-70
SA-209-T1
SA-213-T11
SA-213-T22
SA-213-TP304H
SA-213-TP321H
SA-213-TP347H
SA-213-TP316H
SA-240-304
SA-240-321
SA-240-347
SA-240-316

0.06-0.18
0.06-0.18
0.27
0.35
0.3
0.35
0.31
0.10-0.20
0.15
0.15
0.04-0.10
0.04-0.10
0.04-0.10
0.04-0.10
0.08
0.08
0.08
0.08

Mn

0.27-0.63
0.27-0.63
0.93
0.80
0.29-1.06
0.90
0.85-1.20
0.30-0.80
0.30-0.60
0.30-0.60
2.00
2.00
2.00
2.00
2.00
2.00
2.00
2.00

Si

0.25
0.10
0.10
0.15-0.30
0.15-0.30
0.10-0.50
0.50-1.00
0.50
0.75
0.75
0.75
0.75
1.00
1.00
1.00
1.00

Ni

8.00-11.00
9.00-13.00
9.00-13.00
11.00-14.00
8.00-10.50
9.00-12.00
9.00-13.00
10.00-14.00

Cr

Mo

0.44-0.65
1.00-1.50 0.44-0.65
1.90-2.60 0.87-1.13
18.00-20.00
17.00-20.00
17.00-20.00
16.00-18.00 2.00-3.00
18.00-20.00
17.00-19.00
17.00-19.00
16.00-18.00 2.00-3.00

Other

UTS

47,000
60,000
60,000
60,000
80,000
80,000
55,000
60,000
60,000
75,000
Ti 0.6Max
75,000
Ta 1.0Max
75,000
75,000
75,000
Ti 0.7Max
75,000
Ta+Nb 1.10 75,000
75,000

26,000
37,000
37,000
35,000
38,000
38,000
30,000
30,000
30,000
30,000
30,000
30,000
30,000
30,000
30,000
30,000
30,000

(Alloy content:wt%, Stress:psi)

Surface and Coating Technology

47

Coal Ash Deposit Problem

1. Heat transfer to the working fluid either water or steam

is reduced due to low thermal conductivity of the deposit.
2. The designed lifetime of the boiler tubes is shortened by
the very corrosive environment created by the deposit.
3. Slag accumulation on upper furnace walls can lead to the
formation of large deposits of frozen material which may
impedes gas flow.

48

Melting Points of Complex Sulfates

Compound
K3Fe(SO4)3
K3Al(SO4)3
KFe(SO4)2
Na3Fe(SO4)3
Na3Al(SO4)3
NaFe(SO4)2
Na2S2O7
K S2O7SO atmosphere
(a) In2high

Temperature, C
618
654
694(a)
624
646
690(a)
401
300

49

Corrosion of Steel by Trisulfates

Mainly responsible for corrosion of superheaters and reheaters
in temperature range of 480 - 730C

- Deposition of alkalies on exposed metal surface

- Conversion of alkali oxides to alkali metal sulfates by SO3
(Na or K)2O + SO3 (Na or K)2SO4
- Formation of alkali trisulfates with adsorption of SO3 and
dissolution of transition metal oxides
3(Na or K)2SO4 + Fe2O3 + 3 SO3 2(Na or K)3Fe(SO4)3
- Reestablishment of transition oxides on metal surfaces
Fe + 1/2 O2 FeO
3FeO + 1/2 O2 Fe3O4
3 Fe3O4 + 1/2 O2 2Fe2O3

50

CORROSION OF STEEL BY PYROSULFATES

(Temperature Range: 400 - 500C)

- Deposition of alkalies on exposed metal surface

- Convection of alkalies to Na2SO4 and K2SO4
- Oxidation of SO2 in the bulk flue gas to SO3
SO2 + 1/2 O2 SO3 (on catalytically active surfaces)
- Formation of pyrosulfates
(Na or K)2SO4 + SO3 (Na or K)2S2O7
- Reaction of pyrosulfates with the scale on metal surfaces
3(Na or K)2S2O7 + Fe2O3 2(Na or K)3Fe(SO4)3
which then dissociate
2(Na or K)3Fe(SO4)3 3(Na or K)2SO4 + Fe2O3 + 3SO3
- Further oxidation of the metal to replace its scale
3Fe + 2O2 Fe3O4

51

Corrosion of Steel by Sulfides

Due to poor combustion,
the furnace wall tubes corrode by unoxidized sulfides

- Condensation of alkali sulfates on the oxidized tube surface

- Unburned coal and particles of pyrites (FeS2) adhere to the
tube
surface and form a thick deposit
- Pyrites gradually oxidize to FeS and Fe3O4
FeS2 FeS + 1/2S2
3FeS + 5 O2 Fe3O4 + 3 SO2
- These sulfides, SO2 and SO3, then form trisulfates, (Na or
K)3Fe(SO4)3
in small quantities leading to loss of metal

52

Effect
Effect of
of Chlorine
Chlorine
Source of Cl
- refused-derived fuels (mostly from PVC plastics)
- NaCl from seawater during transport
- contained in the coal (i.e., Illinois coals)
2 Fe + 3 Cl2 = 2 FeCl3
2 Fe + 6 HCl = 2 FeCl3 + 3 H2
Fe2O3 + 6 HCl = 2 FeCl3 + 3 H2O

FeCl3 melts at 280C, and it acts as a flux to promote the

formation
of liquids within the ash deposit.
FeCl3 may form even lower melting point compounds by
combining
with other ash constituents.

53

Required
RequiredProperties
Propertiesof
ofHigh
HighTemperature
TemperatureCoatings
Coatings

- Adherent, crack- and pore-free

- Microstructurally stable
- Thermal expansion compatible to substrate
- Predictable reaction & interdiffusion with substrate
- No effect on mechanical and structural properties
of substrate
- Locally repairable
- Cost effective

54

High
High Temperature
Temperature Coating
Coating Principles
Principles
- Dense and protective oxide formation
by reaction between the coating material
and environment
- Barrier effect against
inward diffusion of oxidants and
outward diffusion of cations
- Slow growing oxides for common coatings
Al2O3, Cr2O3, SiO2
55

Limitations
Limitations of
of Coating
Coating Oxides
Oxides

- Al2O3
Easy acidic fluxing
- Cr2O3
Evaporation at high PO2
- SiO2
Evaporation at low PO2
56