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The Corrosion


Understanding the corrosion

Different methods for corrosion control

Online Monitors
Inhibition programs
Any method be made more effective…
…When you understand the
effect of the corrosion

Corrosion rates vary with

process conditions
5.5% NaCl
5.5% NaCl, 5 atm
5.5% NaCl, 85 °C
5.5% NaCl, 10 °C, 15 atm
To interpret coupon
and monitor data…

It helps to know the effect

of variations in the field
To locate where
to place sensors &
Wait for a failure…?
Rely on past experience?
Online Monitors
Tell you what has already
happened, not what will
OLI tools can help
pH point
Understand what’s happening in your system

Active Corrosion (dissolution)

Protective Scale
Passive Film

Determine the rate limiting redox processes

Passive region
Determine pitting potential and max growth rate

No PittingÍ ÎPitting
Pro-active Analysis
¾Test Corrective Actions
• Determine optimum pH
• Screen alloys and inhibitors
• Assess process changes

¾Focus Lab work

¾Eliminate potential problems

before they occur
The Corrosion Analyzer
Tool for understanding the corrosion environment

¾ Mechanistically -based software tool

Kinetics of uniform corrosion
Partial anodic and cathodic
Transport properties
The Corrosion Analyzer
Based on the OLI Engine
¾ Complete speciation model for complex
ƒ Phase and chemical reaction equilibria
ƒ Accurate pH prediction
ƒ Redox chemistry
ƒ Comprehensive coverage of industrial
chemical and petroleum systems
The Corrosion Analyzer
Based on the OLI Engine

¾ Thermophysical properties prediction

¾ Phenomenological and unique aqueous

process models including kinetics and

¾ “Out-of-the-box” solution and technical

The Corrosion Analyzer
What It Does…

¾ Predict metal dissolution regime, passive films,

and surface deposits
¾ Predict uniform corrosion
rates and the potential for
pitting corrosion
¾ Generate real solution
stability (Pourbaix)
¾ Produce theoretical
polarization curves
The Corrosion Analyzer
So you can gain insight on …

¾ Corrosion mechanisms
¾ Rate -limiting partial processes for your operating
¾ Effects of process and materials changes

¾ Focusing lab time
¾ Reducing risky plant/field
¾ Managing design, operation,
and maintenance
Today’s seminar
Hands-on” and ““How-To”
¾ Using example problems
¾ Examining plots and
¾ Understanding the basis of
the predictions
Today’s Seminar
¾ Perform ““Single
Single point
point”” calculations
¾ Construct / interpret real solution Pourbaix Diagrams
¾ Calculate corrosion rates
¾ Evaluate the effects of pH, T, comp / flow

¾ Evaluate polarization curves

¾Gain insight to corrosion mechanisms
¾See rate limiting steps
¾Can I read them? Can I trust them?

¾ Determine the likelihood of pitting to occur

For your actual field or lab conditions

Welcome to the
Simulating Real World Corrosion
Gas Condensate Corrosion
¾ Scope
z Gas condensates from alkanolamine gas
sweetening plants can be highly corrosive.
¾ Purpose
z Diethanolamine is used to neutralize
(sweeten) a natural gas stream. This removes
carbon dioxide and hydrogen sulfide. The off
gas from the regeneration is highly acidic and
Gas Condensate Corrosion
¾ Objectives
z Determine the dew point of the acid gas
z Remove the condensed phase and perform
corrosion rate calculations
z Mitigate the corrosion
Sour Gas Absorber
Gas Sweetening

Acid Gas

Absorber liquor
Acid Gas Concentrations

Species Concentration (mole %)

H 2O 5.42
CO2 77.4
N2 0.02
H2S 16.6
Methane 0.50
Ethane 0.03
Propane 0.03
Temperature 38 oC
Pressure 1.2 Atm.
Amount 100 moles
Application Time
Dew Point

•Dew Point = 37.6 oC

•pH = 3.93
•ORP = 0.576 V
Corrosion Rates: Flow
¾ Flow conditions have a direct effect on
z Static
z Pipe flow
z Rotating disk
z Rotating cylinder
z Complete agitation
Application Time
Carbon Steel Corrosion @ Dew Point

Corrosion Rate = 0.7 mm/yr

Corrosion Potential = -0.43 V
H2CO3(aq)= ½ H+ + HCO3- -e
Repassivation Potential = > 2 V
Current Density = 60.5 μA/cm2

H2S(aq)= ½ H2 + HS- - e

HS-= ½ H2 + S2- - e

H+= ½ H2 - e
¾ Adjusting solution chemistry
¾ Temperature profiling
¾ Alloy screening
¾ Cathodic protection
Adjusting the Solution
¾ Changing operating pH
z Add acid or base
Application Time
Adjusting solution pH = 8.0
Screening Alloys
¾ Select an alloy that has a preferential
corrosion rate
z 13% chromium
z 304 Stainless
Application Time
13 % Cr Steel Corrosion @ Dew Point

Corrosion Rate = 0.06 mm/yr

Corrosion Potential = -0.32 V
Repassivation Potential = > 2 V
Current Density = 5.7 μA/cm2

H2CO3(aq)= ½ H+ + HCO3- - e

HS-= ½ H2 + S2- - e
304 Stainless Steel Corrosion @ Dew Point

Corrosion Rate = 0.0036 mm/yr

Corrosion Potential = -0.15 V
Repassivation Potential = > 2 V
Current Density = 0.3 μA/cm2
304 Stainless Steel Stability @ Dew Point

Passivation is possible due to

Why Iron Rusts
Explaining common observations
using Stability Diagrams
¾ Iron is inherently unstable in water & oxidizes via the
following reactions to form rust
3H2O + 3e− → 3 H2 + 3OH−
Feo → Fe+3 + 3e−
Feo+ 3H2O → Fe(OH)3 + 3 H2
¾ Its severity depends on (among others)
z Conditions (T/P),
z Composition,
z pH, and
z oxidation potential
¾ These four can be plotted on a single chart called a
stability diagram
Start example
Explaining the EH-pH diagram using Fe, showing solid and
dissolved species over range of pH’s and oxidation potentials

White area is region of Elemental iron (gray region) corrodes in water to form one of several phases, depending on
pH. At ~9 pH and lower, water oxidizes Fe0 to Fe+2 which dissolves in water (white region of
iron corrosion the plot). As the oxidation potential increases (high dissolved O2) Fe+2 precipitates as FeOOH,
or rust (green region). The lower the pH, the thicker the white region and the greater driving
force for corrosion
At higher pH (10-11), Fe0 forms Fe3O4, a stable solid that precipitates on the iron surface,
protecting it from further attack.
H2 O is o
Fe(III)3+ is the xidized to
O2 and H +
dominant ion Fe(
II) o
H 2 O is stable
and aer a
Fe(II)2+ is the Fe xidi ted Water Ox
idation Lin
2O and
3 red pre
dominant ion uce
s an cipi
dd tate
isso s as
lves Fe
in w 2O
at e
H2 O is s r
table an
d deaer FeO(OH), rust is stable in water at moderate to high pH’s
H2 O is re ated
duced to
H2 and O -
Water Re Fe3O4 coats the iron
duc tion Line surface, protecting it from
Elemental iron, Fe(0) oxidizes to Fe(II) in the presence of water

Elemental iron, Fe(0)o, is stable and will not

corrode in this region
Q: We all know O2 is bad…But how much is bad?

H 2 O → 1 O2 + 2 H + + 2 e −
H2 O is o
xidized to
O2 and H +
H2 O is sta Water Ox
ble and a idation Lin

H2 O is s
table an
Pure water is here…
d deaerate
d No air, no acid, no base
H 2O + e → 1 H 2 + OH +H O is red

2 2 uced to H
2 and OH -
Water Re
duc tion Line

500 ppm O2 0.1 ppT H2

10 ppm O2 0.1 ppb H2

3 ppb O2 0.1ppm H2
80 ppm H2
0.1 ppT O2
Iron and water react because they are not stable together

The reaction generates 2OH-, which

increases the pH

2 H 2O + 2e − → H 2 + 2OH +
Fe o → Fe + 2 + 2e −
Fe o + 2 H 2 O → Fe + 2 + H 2 + 2OH +

Region of instability
The reaction generates H2, which puts
the EH near the bottom line

Elemental Iron (Feo)

Start example on Page 36-39
The reaction ends within the Fe3O4 region. Fe3O4 is a solid that
passivates the iron surface protecting it from active corrosion

Initial Conditions
DI water, no Feo
7pH, 0.4V
Final Conditions
1 ppm Feo added
9.38pH, 0.5V
0.9 ppb Feo
7.07pH, -0.27V

0.1 ppm Feo

8.48pH, -0.42V
Overlaying the Fe3O4 mass on the diagram – once the pH
reached 9, Fe3O4 began to precipitate

1.4 g Fe3O4 ppts from

1 Feo

with the stability curve

The ppt point lines up

Fe3O4 precipitates when 0.3 mg/l

Feo has reacted
Start example on Page 40-41
If a constant source of O2 is present, then the EH and pH do not
change, and we are stuck in the rust region

The EH and pH does not

change as Feo reacts with
aerated water
Why is Stainless Steel
Cr will oxidizes, but the reaction goes through a tough Cr2O3
protective layer.
Ni3Fe2O4 is stable in the corrosion region, and will also protect the
Welcome to the
Simulating Real World Corrosion
Corrosion in Seawater
¾ Scope
z Metals used for handling sea water face both general
and localized corrosion.
z Various grades of stainless steels have been used to
mitigate the problems.
z Stainless steels owe their corrosion resistance to a
thin adherent film of oxides on their surface.
z Disruption of the films can lead to localized corrosion
and premature failure.
Corrosion in Seawater
¾ Purpose
z Chlorine and oxygen in sea water can attack
the films used to passivate the steels.
z The CorrosionAnalyzer will be used to model
the effects of chloride and oxygen on the
rates of uniform corrosion and the possibility
of pitting on the surface of the metals.
Corrosion in Seawater
¾ Objectives
z Reconcile a sea water sample for
z Reconcile a gas analysis
z Calculate uniform rates of corrosion for
• 304 stainless steel
• 316 stainless steel
• S31254 stainless steel
Corrosion in Seawater
¾ Objectives (continued)
z Determine the probability of pitting using the
localized corrosion feature.
Kinetic Model of General
Corrosion: Mass-Transfer
¾ All reactions take place on the
metal surface.
¾ Films are a diffusion barrier to
corrosive species
Metal z Reduce mass-transfer-limited
film ¾ Mass-transfer from solution is
calculated from a concentration-
dependent diffusion coefficient.
¾ The rates of corrosion use a subset of the OLI
z Neutral Species
• H-2O, O2, CO2, H-2S, N2 and all inert gases, Cl2, SO2, So and
NH3, organic molecules that do not undergo electrochemical
z Anions
• OH-, Cl-, Br-, I-, HCO3-, CO3-2, HS-, S2-, SO42-, HSO4-, SO32-,
NO2-, NO3-, MoO42-, CN-, ClO4-, ClO3-, ClO-, acetate, formate,
Cr(VI) anions, As(III) anions, P(V) anions, W(VI) anions,
B(III) anions and Si(IV) anions.
z Cations
• H+, alkali metals, alkaline earth metals, Fe(II)
cations, Fe(III) cations, Al(III) cations, Cd(II)
cations, Sn(II) cations, Zn(II) cations, Cu(II)
cations, Pb(II) cations and NH4+.
Corrosion of 304 Stainless Steel in
Deaerated Sea Water

Species Concentrati ¾ LabAnalyzer used

on (mg/L)
Cl- 19000 to reconcile
Na+ 10700 electroneutrality
Mg+2 1300
¾ NaOH/HCl Used
Ca+2 400
SO4-2 2750 to adjust pH
HCO3- 150
pH 8.0
Temperatu 25 oC
Pressure 1 atm.
Application Time
Screening Considerations
¾ Some alloys do not perform well in
¾ We will evaluate 3 stainless steels
z Uniform corrosion rates
z Pitting possibility
¾ Considering both deaerated and aerated
Corrosion of 304 Stainless Steel in
Deaerated Sea Water

300 years to lose 1

mm of metal

.0033 mm/yr @ 25 oC
Corrosion of 304 Stainless Steel in
Deaerated Sea Water

Repassivation Potential
Large difference
means that pits are Corrosion Potential
unlikely to form Difference = 0.05 V

Or if a pit forms,
then it will passivate
What’s on a Polarization Curve?

Standard Tafel Behavior
Transition to mass-transfer
Potential V(SHE)

limited current density




1.0E-09 1.0E-06 1.0E-03 1.0E+00 1.0E+03 1.0E+06 1.0E+09

|Current Density| μA/cm2

What’s on a Polarization
The curve is only valid in aqueous
2 systems and will be bounded by the
Net Current decomposition of water.
1.5 Hydrogen Evolution
Oxygen Evolution
H + + 4location
→ O2 + 4indicates
2 H 2OIntersection e − of the
Potential V(SHE)

0.5 corrosion potential


2 H 2O → H 2 + 2OH − − 2e −
Current density at corrosion
-1 potential also read at intersection

1.0E-09 1.0E-06 1.0E-03 1.0E+00 1.0E+03 1.0E+06 1.0E+09

|Current Density| μA/cm2

What’s on a Polarization
Hydrogen Evolution
Net Current
Oxygen Evolution
Potential V(SHE)



Basic polarization curve with water
decomposition and corrosion
-1.5 reaction

1.0E-09 1.0E-06 1.0E-03 1.0E+00 1.0E+03 1.0E+06 1.0E+09

|Current Density| μA/cm2

What’s on a Polarization
1.5 Hydrogen Evolution

Polarization curve with water

H2CO3 Reduction
1 H+ reduction
Oxygen Evolution decomposition, corrosion reaction
Potential V(SHE)

0.5 and two mass-transfer-limited





1.0E-09 1.0E-06 1.0E-03 1.0E+00 1.0E+03 1.0E+06 1.0E+09

|Current Density| μA/cm

What’s on a Polarization Curve?

This is what is
Transpassive region
Passive region

Active Corrosion

Corrosion Potential and

Corrosion current
What’s on a Polarization
Forward Sweep
1.5 Reverse Sweep Transpassive
Potential V(SHE)



Polarization curve demonstrating a galvonostatic sweep. Active
The arrows indicate
-1.5 how the potential is changing as
one moves along the line.
0.001 0.1 10 1000 100000 10000000

|Current Density| μA/cm2

There are many processes that
make up the polarization curve.
Fe = Fe+2 + 2e-


H2O + e- = ½ H2+OH-

H+ + e- = ½ H2
The Polarization Curve for 304
SS in Deaerated Water
Oxidation of water to O2

polarization curve

Breakdown of water to H2

Peak Current density

in the pit with the
highest corrosion rate
Open circuit
potential and Corrosion of 304 ss
current density
Kinetic Model of General
Corrosion: Phenomena
¾ Partial electrochemical processes in the active state:
z Cathodic reactions (e.g., reduction of protons, water molecules,

oxygen, etc.)
z Anodic reactions (e.g., oxidation of metals)

¾ Adsorption of species on the metal surface

¾ Active-passive transition influenced by
z Acid/base properties of passive oxide films

z Temperature

z Additional species that influence the dissolution kinetics of

oxide layers
¾ Synthesis of the partial processes according to the mixed
potential theory
May 20, 1997 OLI Systems, Inc,
Application Time
Corrosion of 316 SS in
Deaerated Water

.00053 mm/yr @25 oC

1886 years to lose 1 mm

of metal

Much better
corrosion rate than
304 ss
Corrosion of 316 SS in
Deaerated Water

Difference = 0.086 V
Application Time
Corrosion of 254 SMO in
Deaerated Water

Corrosion rate = 0.00033 mm/yr @ 25 oC

> 3000 years to lose

1 mm of metal
Corrosion of 254 SMO in
Deaerated Water

Difference = 2.7 V
Summary in Deaerated Water

Stainless Rate @ 25 Potential

oC (mm/yr) difference

304 0.0033 0.05

316 0.00053 0.086

254 SMO 0.00033 2.7

Adding Air/Oxygen

¾ The CorrosionAnalyzer
allows you to add a gas Species Partial
phase based only on (atm)
partial pressures N2 0.7897
¾ You can set the O2 0.21
water/gas ratio CO2 0.0003
WGR 0.01 bbl/scf
Application Time
304 SS in Aerated Solutions
304 SS in Aerated Solution

The corrosion
potential is greater
than the passivation
potential = .37 V at
max O2

Pitting will occur

304 SS Polarization in
Aerated Water

8 ppm O2

Corrosion potential
shifted anodically of
the repassivation
potential. 0 ppm O2

The surface will

couple galvanically
with the pits to
increase their rate of
Application Time
316 SS Corrosion in Aerated

Pitting occurs at
higher oxygen
concentrations =
.21V at max O2
Application Time
S31254 Corrosion in Deaerated

Pitting should not

Stability Diagram for 316L SS
Stability Diagram for 316 L
Nickel Only
¾ Change Alloys
z S31254 seems the best at 25 oC
z S31254 increased potential for pitting at higher
¾ Cathodic Protection
z Shifting of potential to less corrosive potentials via a
sacrificial anode.
z Analyzers do not model CP
z Polarization curves can help determine the change in
Welcome to the
Simulating Real World Corrosion
Dealloying of Copper Nickel
¾ Scope
z A copper-nickel pipe made of Cupronickel 30
has been preferentially dealloyed while in
contact with a 26 weight percent calcium
chloride brine. It appears that the nickel in the
alloy has been preferentially removed.
Dealloying of Copper Nickel
¾ Purpose
z The OLI/CorrosionAnalyzer will be used to
show the relative stability of nickel and copper
in the cupronickel alloy in an aqueous
solution. It will show that protective films were
not present as originally thought.
Dealloying of Copper Nickel
¾ Objectives
z Input information into the software and
perform calculations
z Use stability diagrams to display information
about the alloy and the protective films
z Change the diagrams to view different
aspects of the stability of the alloy
Application: Dealloying of
Copper-Nickel Alloys
¾ A cupronickel 30
pipe (30 mass %
copper) was used.
¾ 26 wt % CaCl2
solution was in
contact with the
Dealloyed cupronickel pipe.
¾ Nickel was
¾ Why did the nickel dealloy from the pipe?
¾ What could we do to prevent this from
¾ Which tools are available to understand
this phenomenon?
Which Tools are Available?
¾ A Pourbaix diagram can help us determine
where metals are stable.
z CorrosionAnalyzer™
Creating the First Stability
¾ We will use the CorrosionAnalyzer ™ to create a
stability diagram for this system.
¾ Features of CorrosionAnalyzer ™ diagrams
z Real-solution activity coefficients
z Elevated temperatures
z Elevated pressures
z Interactions between species and overlay of
The Pourbaix Diagram
Application Time

Time to start working with the OLI Corrosion Analyzer

The Pourbaix Diagram
¾ There are quite a few things to look at on this
z Stability field for water
z Stability fields for nickel metal and copper metal
z Stability fields for nickel and copper oxides
z Stability fields for aqueous species.
¾ We will now break down the diagram in to more
manageable parts.
Stability Diagram Features
¾ Subsystems
z A base species in its neutral state and all of its
possible oxidation states.
• Cuo, Cu+1, Cu+2
• Nio, Ni+2
z All solids and aqueous species that can be
formed from the bulk chemistry for each
oxidation state.
Stability Diagram Features
¾ For each subsystem
z Contact Surface
• Base metals
• Alloys
z Films
• Solids
z Solid Lines
z Aqueous Lines
Stability Diagram Features
¾ Natural pH
z Prediction based on the bulk fluid
z Displayed as a vertical line
¾ Solids
z All solids included by default
z The chemistry can be modified to eliminate
slow forming solids.
Stability Diagram Features
¾ Passivity
z Thin, oxidized protective films forming on
metal or alloy surfaces.
z Transport barrier of corrosive species to metal
z Blocks reaction sites
Water Stability
¾ Water can act as an oxidizing agent
z Water is reduced to hydrogen, H2
¾ Water can act as a reducing agent
z Water is oxidized to oxygen, O2
¾ To be stable in aqueous solution, a
species must not react with water through
a redox process.
Water Stability

4 H + + O2 + 4e − → 2 H 2O
E = 1.23 − 0.059 pH

2 H + + 2e − → H 2
⎛ 1 ⎞
E = 0 − 0.059 Log ⎜⎜ + ⎟⎟ = −0.059 pH
[ ]
⎝ H ⎠
Water Stability – Natural Waters

Surface water

Ocean water
Bog water Organic rich lake

Organic rich
waterlogged soils

Organic rich saline

Copper Pourbaix Diagram

Oxidized Species
E Independent acid
and base chemistry

pH dependent redox
pH independent
Reduced Species
Copper Pourbaix Diagram

Aqueous species Stability field for

passivating film

Equilibrium between
species in contact with a

Natural pH
Equilibrium between speciesStability field for base metal
or alloy
Copper Pourbaix Diagram

Stable copper metal in alloy

extending into water stability Copper pipes are used for
field. potable water for this reason.
The solution pH is in a region
where the copper metal will
be stable.
Nickel Pourbaix Diagram

No Nickel metal extends into

The solution pH is in a region
the water stability field
where nickel is expected to
Ni Overlaid on Cu

We need to know the

Oxidation/Reduction potential

CuCl(s) may form to protect Since the nickel is part of a

the alloy at the solution pH. copper-nickel alloy, it is
possible that copper could
provide a protective film
Application Time
CorrosionAnalyzer Calculation
CorrosionAnalyzer Calculation

The oxidation reduction

potential is 0.463 V
Ni Overlaid on Cu

The potential of 0.463 V lies

above the passivating film.
Dealloying can occur.
¾ Why did dealloying occur?
z No protective film at the operating pH and
oxidation/reduction potential of the process fluid.
z Copper lies within the region of water stability
z Nickel does not lie within the region of water stability
z The presence of Cu+ ions in equilibrium with copper
metal promotes replating of copper metal driven by
the oxidation of nickel.
¾ Standard OLI Chemistry
z 7400 components
z 9100 individual species
z 82 Elements of the Periodic Table fully
• 8 additional elements partially covered.
¾ Stability diagrams have access all of this
¾ Alloys
z 6 predefined classes supported
• Cu-Ni
• Carbon Steels – Fe, Mn, and C
• Ferritic Stainless steels – Fe, Cr, Ni, Mo and C
• Austenitic stainless steels - Fe, Cr, Ni, Mo and C
• Duplex stainless steels FCC phase - Fe, Cr, Ni,
Mo, C and N
z User defined alloys
Limits to the Standard OLI
Aqueous Phase

XH2O > 0.65

-50oC < T < 300oC
0 Atm < P < 1500 Atm
0 < I < 30
Non-aqueous Liquid
Currently no Activity Coefficient Model (i.e., no NRTL,
Fugacity Coefficients are determined from the Enhanced SRK
Limitations of Pourbaix
¾ No information on corrosion kinetics is provided.
z Diagram is produced from only thermodynamics.
¾ Diagram is valid only for the calculated
temperature and pressure
¾ Oxide stability fields are calculated
thermodynamically and may not provide an
actual protective film.
¾ Dealloying cannot be predicted from the diagram