Low Temperature Corrosion

EDS 2004/Metallurgy 7-1

Outcomes

Define and describe the key features of

General corrosion
Galvanic corrosion
Crevice corrosion
Under deposit corrosion
Pitting
Environmental cracking

EDS 2004/Metallurgy 7-2

 Characteristics

Normally aqueous
Anodic reaction normally metal dissolution
Fe => Fe2+ + 2e-
Cathodic reaction normally oxygen or
hydrogen reduction
4e- + O2 => 2O2-
2e- + 2H+ => H2

EDS 2004/Metallurgy 7-3

General Corrosion

EDS 2004/Metallurgy 7-4

 Characteristics

Most common type of corrosion

Not necessarily biggest problem
Can be measured and predicted
If monitored, wont cause unexpected failures

EDS 2004/Metallurgy 7-5

General Corrosion

Metal Solution

Anode
m
2+
m
-
e
H2O

O2
Cathode +
H3O

Anode and cathode locations are almost random and

move with time

EDS 2004/Metallurgy 7-6

 Characteristics

Uniform
Metal may look new - but thinner
Non uniform
Shallow depressions and undulations
What many people call pitting
Not pitting in an electrochemical sense
Pits deeper than wide
Take care with descriptions of corrosion

EDS 2004/Metallurgy 7-7

Refinery Examples

Many locations
Liquid water
Acids or oxygen
Sites of condensation
Crude tower overhead
Exterior corrosion
Walkways
Handrails

EDS 2004/Metallurgy 7-8

 Control Techniques

Understand the environment

Understand the chemistry
Remember the trace contaminants
Monitor the environment and the corrosion
rate
Metallurgy upgrade AFTER understanding
problem

EDS 2004/Metallurgy 7-9

Remember

General corrosion is the only corrosion type for

which thickness measurements and (typically)
field electrochemical measurements are
reliable!!!!!

EDS 2004/Metallurgy 7-10

 Galvanic Corrosion

EDS 2004/Metallurgy 7-11

Characteristics

Preferential corrosion of one metal of two or

more electrically connected dissimilar metals
Requires an aqueous environment which is
corrosive to at least one metal
Wide separation on galvanic series intensifies
effect

EDS 2004/Metallurgy 7-12

 Galvanic Corrosion

Solution

Zn 2+
Zn
-
e
-
4OH
O2
Cu 2H O
2

EDS 2004/Metallurgy 7-13

Galvanic Series

Cathodic (dont corrode) Aluminum

Platinum Zinc

Gold Magnesium
Silver Anodic (Corrode)
Hastelloy C
Austenitic Stainless Active stainless steels and
Copper (brass bronze) nickel alloy are slightly
more cathodic than steel
Hastelloy B
Steel

EDS 2004/Metallurgy 7-14

 Example

Exit elbow from water wash column

Carbon steel
Bolted to Monel liner which is connected to
Monel deminster
Environment
CO2
Cl-
pH varies

EDS 2004/Metallurgy 7-15

Example

EDS 2004/Metallurgy 7-16

 Example

Monel essentially uncorroded

Accelerated corrosion on carbon steel near
connection with Monel
Flange corroded
Effect diminishes with distance
Wall thickens moving away from connections

EDS 2004/Metallurgy 7-17

What We Should Learn

In galvanic corrosion
Both metals continue to corrode
Anodic metal faster than if no galvanic couple
Cathodic metal slower than if no galvanic
couple
y May approach 0
Rate depends on
Corrosivity of the environment
Separation of metals on EMF or galvanic series
Other factors beyond the scope of the course

EDS 2004/Metallurgy 7-18

 Area Effects

Galvanic corrosion damage also depends on

anode and cathode areas
Big anode, little cathode not bad
Big cathode little anode causes trouble

EDS 2004/Metallurgy 7-19

Area Effects

EDS 2004/Metallurgy 7-20

 Area Effects

Coatings change the effective areas of the

anode and cathode
Painting the material which is more corrosion
resistant is sometimes effective

EDS 2004/Metallurgy 7-21

Area Effects

Corrosive
Environment
Coating

Carbon Steel Stainless Steel

EDS 2004/Metallurgy 7-22

 Refinery Examples

Heat exchangers with different bundle/shell

metallurgies
Material changes in piping
Should be done in non corrosive area
Pump components / valve trim

EDS 2004/Metallurgy 7-23

Control Techniques

Consider the consequences of any bimetallic

connection
Fully isolate bimetallic bolted connections

EDS 2004/Metallurgy 7-24

Insulate Flanged Connections

Insulating
Washer

Flange

Bolt
Gasket

Flange

Insulating Nut
Sleeve

EDS 2004/Metallurgy 7-25

Crevice Corrosion

EDS 2004/Metallurgy 7-26

 Characteristics

Selective corrosion in a narrow gap

May or may not be accompanied by general
corrosion
Related to both pitting and under deposit
corrosion

EDS 2004/Metallurgy 7-27

Crevice Corrosion

High Oxygen
Low Oxygen
Cathode
Anode

Corroded Area Flange

Gasket

EDS 2004/Metallurgy 7-28

 Crevice Corrosion

Rolling
Grooves

Tube
Sheet

Tube

Crevices Crevices

EDS 2004/Metallurgy 7-29

Example

Drain valve
Environment
H2S, oxygen, chlorides, water
Narrow crevice accelerated attack
Note that the retaining bolts have been
completely corroded

EDS 2004/Metallurgy 7-30

Example

EDS 2004/Metallurgy 7-31

Example

EDS 2004/Metallurgy 7-32

 Refinery Examples

Anywhere where there is a crevice and

general corrosion may be expected
Flanged connections especially with fiber
gaskets
Threaded connections
Tube/tubesheet connections
Plate type heat exchangers

EDS 2004/Metallurgy 7-33

Control Techniques

Use materials less sensitive to pitting

Crevices are extremely bad in material
environment combinations such as 304 / Cl-
which tend to pit
Eliminate crevices - especially those with
porous gaskets
Eliminate threaded connections

EDS 2004/Metallurgy 7-34

Under Deposit Corrosion

EDS 2004/Metallurgy 7-35

Under Deposit Corrosion

Under deposit corrosion results from

Concentration cell
Anode reaction enhanced under deposit
Cathode reaction enhanced away from
deposit
Reverse possible not called under
deposit corrosion
Anode and cathode may be separated
Location of deposits not necessarily the same
as location of metal loss

EDS 2004/Metallurgy 7-36

 Water Drop

Water Drop

en

Hig
yg

De xyg

hO
Ox

cr
ea n

xyg
O
h
Hig

sin

en
O

g
e 2+ OH - 2
Fe
Fe2O3

e-

EDS 2004/Metallurgy 7-37

Location of Anodes and Cathodes

Consider a garden shovel partly covered with

wet dirt
Where will the rust stains be
Where will metal be lost from

EDS 2004/Metallurgy 7-38

Location of Anode and Cathode

Wet Dirt

EDS 2004/Metallurgy 7-39

Location of Anode and Cathode

rust

Metal Loss

EDS 2004/Metallurgy 7-40

 Example

FCC gas con stripper reboiler bundle

Low fin tubes
H2S
Cl-
Foulant material

EDS 2004/Metallurgy 7-41

Under Deposit Corrosion

EDS 2004/Metallurgy 7-42

 Under Deposit Corrosion

EDS 2004/Metallurgy 7-43

Refinery Examples

Any location in which in which scaling and/or

fouling occur especially if oxygen and chlorides
are present
Wet ammonium chloride deposits
Crude unit overheads
Hydrotreater effluents
Corrosion under insulation

EDS 2004/Metallurgy 7-44

 Control Techniques

Eliminate deposits
Metallurgy upgrade if deposits are corrosion
products
Anti foulant may help for other foulants
Stay within specified fluid velocities
Minimize interfaces
Liquid / vapor etc.

EDS 2004/Metallurgy 7-45

Control Techniques

Design equipment to minimize deposition

Avoid dead legs on the bottom of horizontal
piping
Avoid low flow areas in exchangers through
good baffle design
Keep insulation dry
Weather shielding

EDS 2004/Metallurgy 7-46

Baffle Design

EDS 2004/Metallurgy 7-47

Baffle Design

EDS 2004/Metallurgy 7-48

 Pitting

EDS 2004/Metallurgy 7-49

Pitting Characteristics

What inspectors call pitting and actual pitting

are sometimes different
Pitting is normally discrete pits that are
deeper than they are wide
Pitting is most common on the tops of
horizontal surfaces and rare on the bottoms
of horizontal surfaces

EDS 2004/Metallurgy 7-50

Example

EDS 2004/Metallurgy 7-51

Example

EDS 2004/Metallurgy 7-52

 Example

Type 304 Austenitic Stainless Steel

EDS 2004/Metallurgy 7-53

Factors Affecting Pitting

Normally found in active/passive metals in

passive state
Requires incubation time for pit to initiate
Some crevice corrosion is pitting in a
preformed pit (crevice)

EDS 2004/Metallurgy 7-54

 Refinery Examples

300 Stainless + chlorides

Under chloride leaching insulation
Seawater cooling systems

Remember that not all of what is reported to

be pitting actually is

EDS 2004/Metallurgy 7-55

Control Techniques

Understand environment
Avoid material/environment combinations
prone to pitting
If unavoidable or exist in present design watch:
velocity
temperature
cleanliness

EDS 2004/Metallurgy 7-56

Environmental Cracking

EDS 2004/Metallurgy 7-57

Environmental Cracking

Two forms
Specific metal environment interaction
Usually involves marginal passivation of
an active passive metal
Hydrogen charging
Hydrogen from aqueous corrosion

EDS 2004/Metallurgy 7-58

A Few Problem Combinations

300 series stainless - chlorides

Carbon steel hydroxides (caustic)
Brass - ammonia
Aluminum chlorides
Monel HF
Hard, stresses, cold worked

EDS 2004/Metallurgy 7-59

Chloride SCC Crack

EDS 2004/Metallurgy 7-60

Chloride SCC Crack

EDS 2004/Metallurgy 7-61

Caustic Cracks

EDS 2004/Metallurgy 7-62

 Caustic Cracks

EDS 2004/Metallurgy 7-63

Cracking Due to Hydrogen

Can accompany any wet corrosion involving H+

Normally associated with carbon steel
Often involves H2S

EDS 2004/Metallurgy 7-64

 Cracking Due to Hydrogen

Four forms
Hydrogen blistering (not actually cracking)
Hydrogen induced cracking
Stress oriented hydrogen induced cracking
Sulfide stress cracking
Hydrogen embrittlement
Does not require a blister to initiate as
others do

EDS 2004/Metallurgy 7-65

Cracking Due to Hydrogen

Appearance of cracking varies with

Stress
Tensile strength of steel
Impurities in steel
Hardness of steel

EDS 2004/Metallurgy 7-66

Hydrogen Blistering

H0 H+
Void
or H2
Inclusion
H0 H+
H2
H0 H+

S2-

H0 H+
Steel Solution

EDS 2004/Metallurgy 7-67

Hydrogen Blister

EDS 2004/Metallurgy 7-68

 Hydrogen Induced Cracking

H2

H2

H2

EDS 2004/Metallurgy 7-69

Stress Oriented Hydrogen Induced Cracking

Stress Stress

EDS 2004/Metallurgy 7-70

 Sulfide Stress Cracking,
Hydrogen Stress Cracking

Stress Stress

High Strength Steel

For steels with hard heat affected zones, crack will be in HAZ

EDS 2004/Metallurgy 7-71

Sulfide Stress Cracking,

Hydrogen Stress Cracking

EDS 2004/Metallurgy 7-72

 Control Techniques

Avoid problem combinations

Minimize wet corrosion in presence of a
recombination poison such as H2S
Use Killed or HIC (hydrogen induced
cracking) resistant steels
Minimizes sites for blisters to form
Post weld heat treat welds to below Rc22
(BHN 200)

EDS 2004/Metallurgy 7-73