High Temperature

Corrosion
Don Tillack
Oxidation
 Effect Of Chromium On
Oxidation Resistance of Steel

2200

Maximum Metal Temperature, °C

Maximum Metal Temperature, °F

1200
For Oxidation Resistance

2000

1800 1000

1600
800
1400

1200
Normal Combustion Atmosphere 600
1000
0 4 8 12 16 20 24 28
% Chromium In Steel
 5 Cr - 0.5 Mo
350
9 Cr - Mo
Carbon Steel
Gain in Weight, mg/cm² 300 Carbon-0.5 Mo 12 Cr
2 Cr - 0.5 Mo
250 2.25 Cr - 1 Mo 12 Cr -Al
200
5 Cr-
150 0.5 Mo-
100 1.5 Si
17 Cr
50
18-8
0 18-8 Cb
1000F 1200F 1400F 1600F
538C 649C 760C 871C 18-8 Mo
18-8 Ti
Temperature
Amount of oxidation (scaling) of carbon,
low-alloy, and stainless steels in 1000 hours
in air from 1000° to 1700°F (538º to 926ºC)
 Effect Of Al And Cr Adjustment On 1000 Hours
Cycle Oxidation [Air – 5% H 2 0 At 1100°C (2012°F)]
∆ W, mg/ cm²

–20

–40

–60
0 200 400 600 800 1000
Time, Hours

Alloy Fe Cr Ni Al
N006600 7 15 Base —
N006601 14 23 Base 1.3
 Exposed 5 Hours at 2300°F (1260°C)

N06601 N08330
Alloy 601 Alloy 330
60Ni, 23Cr, 14Fe, 1.3Al 35Ni, 19Cr, 43Fe, 1.2Si, 1.5Mn
Cyclic Oxidation Resistance At 1800°F (982°C)
20
10 N06601
0
N06600
Weight Change, mg/ cm² -10
-20
-30
-40
-50
-60
-70
-80
N08330
-90
N08800
-100 S31000
-110 Cycles Consisted of
15 Minutes Heating And
S30900
-120
15 Minutes Cooling in Air
-130
-140
0 200 400 600 800 1000
Cyclic Exposure Time, hr
 500 Hour Static Oxidation Resistance
For Various Temperatures
(Samples Cooled And Weighed Every 50 Hours)
Temperature
2100°F 2200°F 2300°F
(1149°C) (1204°C) (1260°C)
0

-100
Weight Change, mg/cm²

9% Mo
-200

-300

-400

-500

-600 * 2300°F (1260°C) Discontinued After

50 Hours Due To Catastrophic Oxidation
-700
Carburization
Austenitic stainless
steel exposed to
carburizing conditions
Carbon combines with
chromium to form
chromium carbides
leaving behind Ni and
Fe, both of which are
magnetic
 Two alloys exposed to the same carburizing conditions

Top:
Alloy 601
(61% Ni)

Bottom:
Alloy 600
(76% Ni)
Effect of Si and Ni On Carburization Resistance
1832°F (1000°C) For 200 Hours in Carbon Granulate

2.8

2.4
% Carbon Absorbed

2.0

1.6
<.75 % Si
1.2

0.8 2% Si

0.4

0
0 10 20 30 40 50 60
Nickel Content
CARBURIZATION

• Occurs in CH4, CO and other hydrocarbon

environments at elevated temperatures
• It is highly embrittling
• Grain boundary and internal carbides form
• Reduction or prevention:
– Smooth surface finish
– Inject low levels of S compounds into the process
stream (to poison the carburizing reaction)
– Modify the composition:
¾ Increased Ni: reduces C diffusion
¾ Increased Si: forms SiO2 scale
¾ High levels (4%) of Al
¾ Minor element additions – Ti, Nb, W, Mo, rare
earths
CARBURIZATION

• Main cause of failure of ethylene

furnace tubes

• HP–Mod (25Cr, 35Ni +) is more resistant

than HK (25Cr, 20Ni)
Cast HP-Mod
ethylene
furnace tubes
after
magnetic
particle
inspection –
the dark
areas are
carburized

Note the
variability:
some sections
are heavily
carburized
other nearby
sections are
largely
unaffected
Same tubes as
previous slide
– longitudinal
sections
Note how uneven
the carburization
can be – it is
difficult to inspect
METAL DUSTING
• Catastrophic carburization – very rapid
• Occurs in CO, CO2, and H environments at
900-1650°F (480-900ºC)
• Stagnant areas are more prone to attack
• Round bottom pits
• Surface of remaining area is heavily
carburized
• Most alloys are attacked
• Unpredictable
• Steam and S additives are sometimes
effective controllers
 Unaffected Perforation Complete metal loss

HP-Mod cast ethylene furnace tube showing metal dusting

Note its localised nature
HP-Mod cast furnace tubes Note how rounded (hemispherical)
the attack can be

Perforations
EFFECT OF CO/CO2 RATIO ON METAL DUSTING IN CRITICAL
TEMPERATURE RANGE VERSUS STEAM/HYDROGEN RATIO
(AS APPLICABLE TO STAINLESS 304 AND ALLOY 800)

10.0

CATASTROPHIC
Carbon Activity (CO/CO2 Ratio)

5.0
SEVERE
2.0 SEVERE
ATTACK
1.0
INTERMEDIATE
ATTACK
0.5

LOW or
0.2 LOW NO ATTACK

0.1
0 0.5 1.0 1.5 2.0 2.5
Oxidizing Potential (Steam Hydrogen Ratio)
METAL DUSTING CAN RESULT IN SEVERE
ATTACK IN CERTAIN TEMPERATURES
Metal Dusting Severity, Weight Loss

2CO = CO2 + C

Type 304
Increasing Loss

Stainless Steel

Alloy 800

500 600 700 800 900°C

900 1,100 1,300 1,500 1,700°F

Temperature
 CHROMIUM EQUIVALENTS
VARIOUS WROUGHT AND CAST ALLOYS
Cr eq = Cr% + 3 x (Si% + Al%)

UNS Alloy Composition (wt %) Metal Dusting

Number Cr Ni Si Al Cr eq Resistance
Wrought alloys
N08810 800H 20 32 .3 .3 22 poor
S31000 310SS 25 20 .3 - 26 fair
N06600 Inc. 600 15 72 - - 15 fair
N06601 Inc. 601 22 60 - 1.5 27 good
Kanthal APM 22 - - 6.0 40 best
Cast alloys
J94204 HK-40 25 20 1.0 - 28 good
N08705* HP-mod 26 35 1.5 - 30 good
Manoir XTM 35 48 1.5 - 40 best
Nitridation
 cracks in the
brittle nitrided
layer stop at the
more ductile
base material

Type 304 stainless steel transfer pipe in an ammonia plant

Grey area is the nitrided layer
NITRIDATION

Resistance improves with increasing

nickel content

• 300 Series stainless steels – Resistant

• Alloy 800 -- Better
• Alloy 600 -- Best
NITRIDATION

• Ammonia-bearing environments at high

temperatures (atomic nitrogen)
• Embrittling
• Fe, Cr, and Al — strong nitride formers
• Ni and Co resist nitriding
• Molecular nitrogen – usually inert
• Alloy 600 – industry standard for nitriding
resistance
Sulfidation
 Oxidation
Sulfidation
Unaffected

material
base

Austenitic stainless steel showing sulfidation (grey phase)

S combines with the Ni and Cr, leaving behind Fe which is
not oxidation resistant, causing oxidation on the surface
Result: combined oxidation and sulfidation
SULFIDATION

• S is an impurity in fuels / feedstock

• Fe, Ni, Co, Cr all form sulfides
• Reducing conditions
– Most severe (H2S)
• Oxidizing conditions (SO2)
– Less severe
– Oxide barrier layer formed
SULFIDATION

For increased sulfidation resistance:

• High Al, Si, Fe and Cr

• Presence of some oxygen

• Low Ni / Fe ratio

High Ni content not generally desirable for sulfidation resistance

Exception: high Ni + high Cr together
eg. 50Ni, 50Cr wrought INCONEL alloy 671; cast IN-657
SULFUR
Causes metal loss & scaling in:

• Crude units

• FCC (fluid catalytic cracking) units

• Cokers
MOLTEN SALT CORROSION

Low melting point compounds

destroy the protective oxide film

• Vanadates, tri-sulfates
BURNING HIGH SULFUR FUELS
WITH VANADIUM

• Formation of vanadium pentoxide

• V205 forms low melting point

eutectics which melt at 1200°F
(650ºC) and cause catastrophic
oxidation
FACTORS TO CONSIDER IN HIGH
TEMPERATURE CORROSION

• Material Selection
– Strength
– Environmental resistance
– Life cycle costing
• Environmental Variations
– Temperature
– Concentrations
– Contaminants
• Design
• Fabrication
• Cost (life cycle)