3.0 Materials & Corrosion Engineering

3.
0
MATERIALS & CORROSION ENGINEERING
The Basics
Combined Course adapted from M183 (Materials & Corrosion
Engineering) & M273 (Advanced Refinery Corrosion)
by J. L. Hau
Shell Projects & Technology,
Westhollow
h ll Technology
h l Center
Copyright of Shell Brands International AG Shell Projects & Technology, Westhollow Technology Center November 2010 1
CONTENTS: Materials & Corrosion Engineering
General Corrosion
Localized Corrosion
Pitting
Pitti
Crevice
Other Forms of Localized Corrosion
Galvanic Corrosion
Environmental Stress Corrosion Cracking
Anodic Dissolution
Wet H2S-related
Liquid Metal Embrittlement
Fatigue/Fatigue-Corrosion
/
Erosion/Erosion-Corrosion
Cavitation/Cavitation-Corrosion
Cavitation/Cavitation Corrosion
Shell Projects & Technology, Westhollow Technology Center November 2010

2
GENERAL CORROSION
Definition:
Corrosion that proceeds uniformly without appreciable localization
off attack,
tt k which
hi h lleads
d tto relatively
l ti l uniform
if thinning
thi i on th
the entire
ti
exposed surface.
C
Corrosion
i observed
b d iin a wallll (C
(Carbon
b Steel)
S l) off a gasoline
li tankk
ELECTROCHEMICAL CELL
At the
h anode,
d an oxidation
d reaction occurs with
h a loss
l off
electrons and the formation of IONS in solution
ELECTROCHEMICAL CELL
At the cathode, a reduction reaction occurs with a gain of

electrons and evolution of H2 (gas) in an acidic environment
GENERAL CORROSION (Uniform Attack)
In any corrosion process, the Anode and Cathode reactions MUST both
occur simultaneously and at equal rate, with electrons released at the
anode
d being
b allll gained
d in the
h corresponding
d cathodic
h d reaction
In general corrosion cases, anode and cathode reactions exchange
places randomly at intervals
GENERAL CORROSION
Electrochemical Reaction:
It occurs att ambient
bi t to
t moderately
d t l elevated
l t d ttemperature
t
Presence of electrolyte required
Example:
E l Rusting
R i off carbon
b steell (Fe
(F combines
bi with
i h water and
d
oxygen to form rust)
L
Loss off thi
thickness
k per unitit titime = C
Corrosion
i rate
t
Corrosion Allowance/Corrosion Rate = Useful Life
Corrosion
C i AllAllowance =
Design life x Expected General Corrosion Rate
Examples: Corrosion by strong acids:
H2SO4, HCl, HF
SULFURIC ACID CORROSION
S lf i A
Sulfuric Acid
id C
Corrosion
i ChChartt
Copyright of Shell Brands International AG Shell Projects & Technology, Westhollow Technology Center 8
November 2010
Sulfuric Acid Corrosion Chart Corrosion Rate <= 20 mpy)

Chart is general guideline representing essentially quiescent corrosion

rates.
Carbon Steel used at concentration above 60%
Optimum conc. 98% (Zone 4 on graph)
High
Hi h corrosion
i ratet att 100%
Corrosion rate increases with temperature and velocity
Limited to 10
10°C
C (50
(50°F)
F) at 85% concentration; 52
52°C
C (125°F)
(125 F) at 98%
Limited to 0.9 m/s (3.0 ft/s) in straight section piping
Adverse Heat Treatment - Weld Areas
Require strict control of oxygen and moisture ingress
Other Materials: Alloy 20, Hastelloy C, Nonmetallics
Alloy 20 = 20-Cb-3, UNS N08020: 20Cr-33Ni-2.5Mo-3.5Cu+Cb
Hastelloy C = C276, UNS N10276, 57Ni-16Cr-16Mo-5Fe-4W-2.5Co
Copyright of Shell Brands International AG Shell Projects & Technology, Westhollow Technology Center November 2010
10
Corrosion of steel by sulfuric acid as a function of

temperature and acid concentration
HCl CORROSION
(Cast version of Alloy 20)
HCl CORROSION
Non-corrosive at low temperatures when dry (anhydrous), however,

become highly corrosive at high temperatures
Extremely corrosive (general metal loss) when wet
Typical
yp material of construction for wet services are Non-metallic
materials, Hastelloy B, Zirconium, and Tantalum
Hastelloy B: 65Ni-28.5Mo-1.5Cr-1.5Fe-3Co-3W-3Mn+Al, Ti
Other materials such as Alloy 400 (67Ni-23Cu), Nickel 200, and
Titanium are only suitable in dilute concentration at low temperature
Presence of any oxidants significantly influences the corrosiveness of
HCl acid
HCl CORROSION
HCl CORROSION
Extremely corrosive (general metal loss) when wet
CHLORIDE (HCL) / CHLORINE (CL2) CORROSION
• Corrosion consumes a metal by progressive reaction with HCl or Cl2 at elevated

temperatures
• Reaction rates are a function of temperature and HCl or Cl2 concentration
• Resistance to corrosion in this environment is improved by using Ni-based alloys rich
in Cr and Co.
OTHER GENERAL CORROSION
• Acidic Sour Water Corrosion

• Ammonium Bisulfide (NH4HS) Corrosion
• Ammonium Chloride (NH4Cl) Corrosion
• Cooling Water Corrosion
• Wet CO2 (Carbonic Acid) Corrosion
• Organic Acid Corrosion
• Caustic Corrosion
• Amine (Lean & Rich) Corrosion
• Amine Hydrochloride
d hl d Salt l Corrosion
• Phenol Corrosion
• Phosphoric
Ph h i A Acid
id C
Corrosion
i
CAUSTIC CORROSION
Corrosion Mechanism
Fe + NaOH → NaFeO2
Other
Oth alkalines
lk li i l d PPotassium
include: t i H
Hydroxide
d id KOHKOH, S
Sodium
di C
Carbonate
b t
Na2CO3 (washing soda, soda ash), Sodium phosphate Na3PO4
Corrosion rate increases with increasing caustic concentration and
temperature
Beware of concentration mechanisms
Affecting mainly CS and to a lesser degree high alloys
Corrosion Rate Carbon Steel < 0.025 mm/y (1 mpy), caustic concentrations
<50%, ambient temperature
Corrosion
C i Rate
R t <0.5
0 5 mm/y
/ (20 mpy)) carbon
b steel
t l for
f <40%
40% caustic
ti up tto
100°C (212°F) and for 50% caustic up to 75°C (167°F)
If T>100°C (212°F) caustic is very corrosive to carbon steel at most
concentrations
i
Corrosion Rate Carbon Steel >12.5 mm/y (500 mpy) at 100°C (212°F) for
caustic exceeding 70%
CAUSTIC CORROSION
Areas of concern
Anywhere caustic (or alkaline) is used
Caustic
C ti treaters
t t and d downstream
d t units
it
Entrainment often the culprit
CWW systems
sys e s in CRUC U regenege a and d gas plant
pa
Caustic injection points (e.g. after desalters)
Boiler Feed water (BFW) systems
(Steam blanketing allows salts to concentrate on boiler metal surfaces. Localized boiling
beneath porous deposits on tube surfaces also concentrate salts)
Influential variables
Primary
Caustic
C ti concentration
t ti ((esp. local
l l concentration)
t ti )
Temperature (metal temperature!)
Presence of other corrosive,, oxygen,
yg , hypochlorides,
yp , etc.
CAUSTIC CORROSION
Prevention
Use of Proper Alloys
304/316 SS, Alloy 400, 825, 600/625 and C-276
[18Cr-8Ni, 18Cr-12Ni-2Mo, 67Ni-33Cu, 22Cr-43Ni-3Mo-2Cu-1Ti, 22Cr-58Ni-
9Mo-3.5Nb, 57Ni-16Cr-16Mo-5Fe-4W-2.5Co]
Alloy 200 (commercial pure nickel) is virtually immune

Avoid
A id concentrating
t ti mechanisms
h i
Avoid crevices
Avoid
A id evaporation
ti
Avoid “Steam Blanketing”
Limit caustic concentration
Use dilute caustic: 20% vs 50%
Use a carrier
CAUSTIC GOUGING
High levels of caustic dissolve the

protective metal oxide layer on the
surface of the boiler tube
The oxide re-

re-forms but is immediatelyy
dissolved again
The result is a distinctive gouged

pattern of metal removal which
eventually leads to
failure
WET CO2 CORROSION
CO2 in dry gas phase is essentially non-corrosive
CO2 dissolved in water produces carbonic acid. General attributes of
wett CO
F 2 +corrosion
Fe H2SOi4 → FeSO
F SO4 + H2
General corrosion often minor
Forms iron carbonate (FeCO3) scale
Provides protection under stagnant/low velocity conditions
Rapid local corrosion if scale disturbed (inches per year)
T b l
Turbulence/impingement
/i i (Control
(C lVValves
l and
dSSteam TTraps))
Two phase flow (flashing)
CO2 concentration in initial “dew” depends
p on:
Temperature, maximum corrosion rate at ~70 °C (~160°F) in open systems
Partial pressure of CO2
Resistant materials - Stainless steels (12Cr/304SS/316SS)
Common problem in steam condensate systems
Often called “condensate corrosion” or “condensate return line corrosion”
22
CO2 CORROSION
F + H2SO4 → FeSO
Fe F SO4 + H2
HP WATER KO DRUM OVERHEAD PIPING
Process condensate entering this knock-out drum contains dissolved CO2. Condensate
was recycled
y back into the p
process but this resulted in this CO2 corrosion. The
condensate is now collected and routed directly to the deaerator where it is deaerated
and treated with neutralizer chemicals to remove and neutralize dissolved CO2 before
recycling as process wash water and BFW.
23
CONDENSATE RETURN LINE CORROSION
F + H2SO4 → FeSO
Fe F SO4 + H2
Effectt off condensate

Eff d t flflow and
d CO2 content
t t on th
the rate
t off corrosion
i off carbon
b steel,
t l usuall
cause of steam and return line corrosion, characterized by a general thinning of the pipe
wall or grooving. Source is thermal decomposition: 1 ppm bicarbonate (HCO3=) alkalinity
= 0.79
0 79 ppm CO2 & 1 ppm carbonate (CO3=) alkalinity = 0 0.35
35 ppm CO2
24
LOCALIZED CORROSION
Oxygen concentration cells

U d d
Underdeposit
it corrosion
i
Microbiologically Influenced corrosion (MIC)
M l which
Metals hi h show
h active-passive
i i b behavior
h i are most susceptible:
ibl
Most Stainless Steels
Aluminum
Al
Titanium
Zirconium
LOCALIZED CORROSION (PITTING)
Localized
l d Pitting off the
h Pipe Wall:
ll Once a pit is initiated
d there
h is a
strong tendency for it to continue to grow, even although the
majority
j y of the surrounding g steel is still untouched
PITTING BY CONCENTRATION CELLS
Definition: Localized corrosion caused by differences in concentration of
a corrosive species, typically an oxidant such as oxygen
Highly localized attack
Deep sharp-edged pits
Negligible corrosion of surrounding area
Where are they? (may be hidden)

Tight crevices (gaskets,
(gaskets tubesheet/baffles,
tubesheet/baffles threads,
threads sockets)
Under process deposits
Under corrosion product accumulations
Under scale nodules/tubercles
Most common problem environment

Aerated water with chlorides
Photo - Corrosion of ERW tube & Corrosion of SS welds
CONCENTRATION CELL CORROSION
Most susceptible materials
Chromium stainless steels (410 SS)
18-8 stainless steels (304SS, 316SS)
Nickel alloys
Carbon steel
Molybdenum increases resistance of stainless steels and nickel alloys

PRE = %Cr + 3.3x%Mo + 16x%N
(PRE = Pitting Resistance Equivalent Number)
Copper alloys have good resistance, but not immune
Brass/bronze
90/10 or 70/30 Cu/Ni
METAL ION CONCENTRATION CELL CORROSION
Long history of Al-Brass tube leakages, latest caused a delay on the
start up of the unit, bundle retubed completely and it failed after only 8
months in service.
Sea water used as coolingg water,, velocity

y too low,, allowed deposit
p to
form on the tubes. Metal-Ion Concentration Cells formed, the area
under the deposit becomes ennobled, dissolution occurred
immediately adjacent to the deposit at surfaces exposed to aerated
flowing seawater.
PITTING CORROSION
The tendency for a particular steel to be attacked by pitting corrosion can be
evaluated in the laboratory. A number of standard tests have been devised, the
most common of which is that given in ASTM G48. A graph can be drawn
gi ing the temperat
giving temperature
re at which pitting corrosion is likel
likely to occur
occ r
316L SS = 17Cr-12Ni-2.5Mo
17C 12Ni 2 5M (0(0.03%C
03%C max)) Alloy
All 255 = DSS 25.5Cr-5.5Ni-3.4Mo
25 5C 5 5Ni 3 4M (Ferrarium)
(F i )
2304 = DSS 23Cr-4Ni-0.1N (Mo Free) 6Mo = 20.6Cr-24.3Ni-6.3Mo-0.21N (Super Austen.)
904L = 21Cr-26Ni-4.5Mo-1.5Cu S32760 = DSS 25Cr-7Ni-3.5Mo (Super DSS)
2205
2205= DSS 22Cr
22Cr-5.8Ni-3.3Mo-0.15N
5.8Ni 3.3Mo 0.15N
CORROSION ERW TUBE IN C.W. SERVICE
- C
Corrosion
i off weld
ld - stitch
tit h
corrosion
- Poor QA/QC in ERW
welding/heat treating; and
- Improper water treating
LOCALIZED PITTING OF STAINLESS STEEL WELD
4-inch 304 stainless steel pipe

- New line intended for a p project
j ((cold service))
- Piping hydrotested and water was drained
- Failed after laying resting for about 4 months
- Notice the “aurora” of the rust stain and absence of corrosion elsewhere
- Emphasis the proper handling of SS SS, also to avoid MIC
MIC.
LOCALIZED CORROSION (PITTING)
Corrosive attackk limited
l d to a specific,
f relatively
l l smallll surface
f area.
The remaining area is largely unattacked.
Conditions within the p
pit become
acidic due to hydrolysis of metal
ions. Once the pit becomes well
established, walls do not
repassivate
p and the pprocess is
described as being autocatatytic
The rate of penetration can be

high
g as metal loss concentrates
at a small anode connected to a
much larger cathodic area
Autocatatytic
A t t t ti process occurring
i iin a corrosion
i pitit by
b aerated
t d NaCl.
N Cl Rapid
R id di
dissolution
l ti within
ithi th
the pit,
it while
hil
Oxygen reduction on adjacent surfaces
LOCALIZED CORROSION (MIC)
Microbiologically Induced Corrosion (MIC) also produces pitting

corrosion
MIC (Microbiologically Induced Corrosion)
Exact mechanism not well-understood
The strands of microbial materials are nearly infinite
The most common types are:
Sulfur reducing bacteria (SRB)
Acid p
producing
g bacteria (APB)
Most prevalent in stagnant conditions
Standing water in tank or vessel bottoms
Water
W t ““pools”
l ” iin piping
i i and
d equipment
i t after
ft hydrotesting
h d t ti due
d to
t insufficient
i ffi i t
draining
Affect all alloys materials
SS most vulnerable
Nickel alloys less affected
Affects cupper alloys as well
Creates a highly unique corrosion morphology
Pitting
g of SS SS Showing
g Undercut
Pitting corrosion on the I.D. of a 6-inch CS Oil line with MIC damage beneath tubercles
sour crude
d line
l after
f 2.5 years off service. Pits (
(source API 571))
are approximately 1-inch to 2-inch wide.
(source API 571)
CONTACT CORROSION
Contact corrosion combines elements of pitting, crevice and galvanic

corrosion, and occurs where small particles of foreign matter, in
particular carbon steel,
steel are left on a stainless steel surface
The attack starts as a galvanic cell - the particle of foreign matter is
anodic and hence likely to be quickly corroded away, but in severe
cases a pit may also form in the stainless steel,
steel and pitting corrosion
can continue from this point
The most prevalent cause is debris from nearby grinding of carbon
steel,
t l or use off tools
t l contaminated
t i t d with
ith carbon
b steel.
t l For
F this
thi reason
fabricators have dedicated stainless steel workshops where contact with
carbon steel is totally avoided
Iff stainless
l steell d
does b
become contaminated
dbby carbon
b steell d
debris
b this
h
can be removed by passivation with dilute nitric acid or pickling with a
mix of hydrofluoric and nitric acids
Hastelloy C-276 is immune to this corrosion mechanism
CREVICE CORROSION
Corrosion occurred Corrosion occurred just Corrosion occurred in

beneath the washer outside the washer both inside & outside the
washer
Nonmetallic washer creating crevice corrosion:
Classical form of crevice corrosion occurred beneath, due to extremely
low p
pH & increased Cl concentration causing g breakdown of passive
p film
In Cu-alloys, crevice corrosion may occur outside the crevice, believed to
be due to metal ion concentration cell corrosion
OTHER FORMS OF LOCALIZED CORROSION
There are other forms of localized corrosion but they may be due to
mechanisms other than pitting and crevice corrosion
Flow from right to left
Localized Naphthenic Acid Corrosion on Carbon Steel
Rich-Amine corrosion can also produce a similar type of corrosion

immediatelyy downstream the weld cap
p protruding
p g the pipe
p p ID and hence
causing turbulence
HYDROGEN GROOVING
Fe + H2SO4 → FeSO4 + H2
Iron sulfate film is relatively weak and can be disturbed by high acid velocities or other disturbances in
the liquid. Hydrogen bubbles cause the disturbance in this case. Corrosion rate as high as 300 mpy
(7.5 mm/y) y have been reported
p in these g
grooves. Locallyy higher
g rates can also result from Turbulence
and Impingement (such as weld caps)
41
SULFURIC ACID DILUTION
Vapor-phase
h attackk may occur when
h moisture enters the
h vapor space and
d
dilutes the sulfuric acid to more aggressive concentrations
Specific
Gravity
1.84
Sagging in this run of pipe may have been sufficient to allow acid being trapped in the
middle and to remain there while idle. The concentrated sulfuric acid remaining idle
inside this pipe absorbed moisture at the surface and thus formed a corrosive weaker
acid on the surface that caused this severe grooving just below the liquid-vapor
i
interface.
f
42
HYDROGEN GROOVING
F + H2SO4 → FeSO
Fe F SO4 + H2
Hydrogen grooving of a carbon steel pipe elbow, located at the top of a vertical run.
This line remained full of acid, corrosion formed hydrogen bubbles that produced the
grooving. Stagnant conditions, often combined with solar heating, promote hydrogen
grooving
43
DEW POINT CORROSION
Localized corrosion where a liquid phase (water or other electrolyte)
condenses on a metal surface and contains or absorbs an acid gas from
the vapor
F + phase
Fe H2SO4 → FeSO
F SO4 + H2
Most common problem in heat exchangers
Mayy occur in other equipment
q p or p
piping
p g due to heat loss
Cold wall effect
Dead legs
C
Common acid
d gases involved
l d
Sulfur trioxide (SO3)
Sulfur dioxide (SO2)
Hydrogen chloride (HCl)
Hydrogen sulfide (H2S)
Carbon dioxide (CO2)
44
DEW POINT CORROSION
F + H2SO4 → FeSO
Fe F SO4 + H2
FCCU CO Boiler Carbon Steel Tube externally corroded by sulfur oxide corrosion
45
DEW POINT CORROSION
F + H2SO4 → FeSO
Fe F SO4 + H2
Acid dew point as function of Sulfur Content in the fuel

46
GALVANIC CORROSION
Corrosion of metal when it is coupled to a more noble metal or

conducting nonmetal in the same electrolyte.
Dissimilar tubes
t bes and tubesheets
t besheets in untreated
ntreated cooling water exchangers.
e changers
Dissimilar metal joints in conductive corrosive media
Relative cathodic/anodic areas
Refer to the Galvanic Series.
GALVANIC CORROSION
Seawater
shell side High Pressure
Hydrocarbon Gas
Condensate +
Water
http://www.hse.gov.uk/offshore/alerts/sa_01_06.htm
GALVANIC CORROSION
GALVANIC CORROSION
Crude Overhead exchanger, with crude overhead vapor going

through
g shell side and naphtha
p through
g tube side
GALVANIC CORROSION
Galvanizing: Zinc deposited by either immersion of electrolytically on carbon

steel provides corrosion protection of substrate metal by acting as sacrificial
anode
PREFERENTIAL WELD METAL CORROSION
Selective corrosion occurring at the weld metal (carbon

steel), in HF alkylation service, depropanizer feed line
Attributed to:
a kind of galvanic corrosion due to difference in chemical
composition
residual element g
greater than about 0.15-0.2 %
to lack of Post Weld Heat Treatment
Residual Elements being = Cu+Ni+Cr
PREFERENTIAL WELD METAL CORROSION
F + H2SO4 → FeSO
Fe F SO4 + H2
Metall lloss d
due to preferential
f l corrosion off the
h weld
ld in sulfuric
lf acid
d environment
LIQUID METAL CRACKING
A form of environmental cracking
Require direct contact with a low melting metal:
Mercury,
M C
Cadmium,
d i Zi
Zinc, Ti
Tin, Copper
C
Common Causes of LMC’s
Mercury cracking of aluminum “cold cold box”
box exchanger
Cracking of steels/stainless steel during heat treatment,
welding, brazing, and soldering
Welding electroplated or hot dipped galvanized (Cd, Zn, or Tin) steel
components to austenitic stainless steels
Operating
O i electroplated
l l d or h hot di
dippedd galvanized
l i d (Cd,
(Cd Zn,
Z or Tin)
Ti )
steel equipment at high temperature
During fire
fire, molten copper (from electrical wires) and zinc (from
galvanizing)
Rotation shaft in contact of bearing if loss of lubrication
Pipe split open during Cat Feed Hydrotreater Fire due to LME when copper
wires melted on a pressurized stainless steel header
Alloy 400 (Monel 400)

Naphtha reflux piping
suffered extensive cracking
at the 6 o’clock position in a
crude distillation unit (CDU).
Crackingg was due to Liquid
q
Metal Embrittlement (LME) by
Mercury (Hg)
Copyright of Shell Brands International AG 57

Shell Projects & Technology, Westhollow Technology Center November 2010
Two highest
peaks Sulfur
p
and Mercury
NH3 Injection CS Shell with

Alloy 400 strip Alloy 400 piping
Alloy 400 (Monel 400) lining
p
Naphtha reflux piping
pp g Carbon
Gases
suffered extensive cracking Steel 50°C

(122°F)
CS Vessel lined
internally fiber
Piping
at the 6 o’clock position in a 130°C
(266°F)
Seawater as cooling water glass
crude distillation unit (CDU).

Cracking was due to Liquid Alloy 400 piping
Alloy 400 piping
Metal Embrittlement (LME) by Alloy 400
Mercury (Hg) Alloy 400 pump
CS Shell strip
lined with Alloy
400 strips Liquid Metal
Embrittlement Failure
Alloy 400 pump
of Alloy 400
Copyright of Shell Brands International AG 58
MECHANICAL FATIGUE
Some materials do not

exhibit endurance limit
Most fatigue
f fractures
f start at
stress concentrations
Stresses are higher
g than
away from stress
concentrations
MECHANICAL FATIGUE
Hydrogen Line Failure due to mechanical fatigue
CORROSION FATIGUE
Premature fracture of simultaneous corrosion and repeated cyclic
loading at lower stress levels or fewer cycles than would be
req ired in the absence of the corrosi
required corrosivee en
environment
ironment
Commonly occurs in boiler feed water deaerators
CORROSION FATIGUE
Typical characteristic cracking produced by corrosion fatigue in steam/BFW service.

Cracks have multiple shapes, sometimes blunt but always oxide filled, occurring on
the water wetted wall. Currently referred to as SAC
CORROSION FATIGUE
Tube failures at economizer section of a boiler due to what is currently referred to

as SAC. In this case, high thermal cyclic stresses play a major role
CORROSION FATIGUE
Flue gases iinside
Fl id
boiler environment
continuously
heating this
membrane tends to
cause thermal
W ld
Weld expansion
Crack
Tubes ID continuously
y
cooled down by the flow
of water tends to cause
thermal contraction
Tube failures at economizer section of a boiler due to what is currently referred to

as SAC
SAC. In this case,
case high thermal cyclic stresses play a major role
EROSION
Flow Direction
Localized Erosion Wear Flow Direction
Carbon Steel: the erosion occurred while handling the slurry flow containing
diatomaceous earth (DE)
EROSION-CORROSION
TTube
b lleak
k iin Ai
Air Conditioning
C di i i Condenser
C d that
h uses sea water as cooling
li water
70-30 Cu Ni tube Integral Externally Finned Seamless Tube, ½” (12.7 mm) ID split into two
to reveal the nature of the penetration. The close-up view on the right-hand side shows
corrosion-erosion
corrosion erosion features
A rubber plug lodged near the penetration from brushes used for cleaning. It should have been removed but
was left on the brush. While pulling it out of this particular tube, the rubber plug inadvertently lodged inside
and was left in the tube. Water managedg to ggo through
g the crevice between the rubber p plug
g and the inside
tube surface, exceeding the allowable velocity, locally removing the protective passive film and hence
resulting in corrosion-erosion type of damage
EROSION-CORROSION
Condensate from the isobutane heater (shell side) discharges to the drain in a tee, caused erosion corrosion
by drop impingement on the wall of the tee.
CAVITATION
Damage associated with collapse of cavities in
the liquid at conditions of severe turbulent flow.
Typically observed in rotating equipment (eg.:
Impellers) but also observed in fixed equipment
components
Top
M h
Methanol
lSStripper
i M
Makeup
k W
Water N
Nozzle
l
CAVITATION-CORROSION
HF acid vaporizer with Alloy 400 tubes experienced cavitation

cavitation-corrosion
corrosion. Concentrated
HF acid in tube side and steam/condensate on the shell side
CAVITATION-CORROSION
Bubbles nucleate at discrete
surface imperfections on the
tube ID
Some bubbles collapse at the
surface causing cavitation
damage
HF acid corrosion contributes
when fresh metal is exposed to
the acid
HF acid vaporizer with Alloy 400 tubes experienced cavitation

cavitation-corrosion
corrosion. Concentrated
HF acid in tube side and steam/condensate on the shell side
DEALLOYING
Cross section of a silicon

silicon-brass
brass alloy A zone of denickelification in a Monel
C87500 pump impeller from stagnant fire- valve plug (at the port), due to oxygen
water service. Layer-type dezincification contamination in hot hydrofluoric acid.
depleted the zinc and left this porous red (source API 571)
color
l off the
th copper. Mag.
M 50x
50 (source API 571)
Shell Projects & Technology, Westhollow Technology Center November 2010 72

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Shell Projects & Technology, Westhollow Technology Center November 2010

At the cathode, a reduction reaction occurs with a gain of

Sulfuric Acid Corrosion Chart Corrosion Rate <= 20 mpy)

Chart is general guideline representing essentially quiescent corrosion

Corrosion of steel by sulfuric acid as a function of

(Cast version of Alloy 20)

 Non-corrosive at low temperatures when dry (anhydrous), however,

Extremely corrosive (general metal loss) when wet

• Corrosion consumes a metal by progressive reaction with HCl or Cl2 at elevated

• Acidic Sour Water Corrosion

 Alloy 200 (commercial pure nickel) is virtually immune

High levels of caustic dissolve the

The oxide re-

The result is a distinctive gouged

HP WATER KO DRUM OVERHEAD PIPING

Effectt off condensate

Oxygen concentration cells

Where are they? (may be hidden)

Most common problem environment

 18-8 stainless steels (304SS, 316SS)

Molybdenum increases resistance of stainless steels and nickel alloys

 90/10 or 70/30 Cu/Ni

Sea water used as coolingg water,, velocity

4-inch 304 stainless steel pipe

The rate of penetration can be

Microbiologically Induced Corrosion (MIC) also produces pitting

 Contact corrosion combines elements of pitting, crevice and galvanic

Corrosion occurred Corrosion occurred just Corrosion occurred in

Flow from right to left

Localized Naphthenic Acid Corrosion on Carbon Steel

Rich-Amine corrosion can also produce a similar type of corrosion

Acid dew point as function of Sulfur Content in the fuel

Corrosion of metal when it is coupled to a more noble metal or

 Relative cathodic/anodic areas

 Refer to the Galvanic Series.

Crude Overhead exchanger, with crude overhead vapor going

Galvanizing: Zinc deposited by either immersion of electrolytically on carbon

 Selective corrosion occurring at the weld metal (carbon

Alloy 400 (Monel 400)

Copyright of Shell Brands International AG 57

NH3 Injection CS Shell with

suffered extensive cracking Steel 50°C

crude distillation unit (CDU).

Some materials do not

Hydrogen Line Failure due to mechanical fatigue

Typical characteristic cracking produced by corrosion fatigue in steam/BFW service.

Tube failures at economizer section of a boiler due to what is currently referred to

Tube failures at economizer section of a boiler due to what is currently referred to

HF acid vaporizer with Alloy 400 tubes experienced cavitation

HF acid vaporizer with Alloy 400 tubes experienced cavitation

Cross section of a silicon

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3.0 Materials & Corrosion Engineering

3.0 Materials & Corrosion Engineering

Non-corrosive at low temperatures when dry (anhydrous), however,

Alloy 200 (commercial pure nickel) is virtually immune

18-8 stainless steels (304SS, 316SS)

90/10 or 70/30 Cu/Ni

Contact corrosion combines elements of pitting, crevice and galvanic

Relative cathodic/anodic areas

Refer to the Galvanic Series.

Selective corrosion occurring at the weld metal (carbon