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Applied Production Technology

Fundamentals of Corrosion Engineering


Objectives

Introduction to:
Types of corrosion which may occur in downhole environments
Methods to prevent corrosion
Methods to find corrosion
Provide enough background knowledge to allow you to question Corrosion
Decisions in an intelligent manner.

Contents

General corrosion principals


Corrosion expected in Oil and Gas facilities
Prevention
Materials selection guidelines
Monitoring and measuring

Applicable Applications Non-NACE

API 5CT / ISO 11960


Steel Pipes for Casing and Tubing of Wells
API 6A / ISO 10423 Wellhead and Christmas Tree Equipment
API 17D
Subsea Wellhead and Christmas Tree Equipment

Applicable Applications
Corrosion Engineers)

MR 0175

of

NACE

(National

Association

of

SSC resistant metallic materials for oilfield equipment


RP 0475
Selection of metallic materials to be used in all
phases of water handling for injection into oil-bearing
formations
MR 0176
Metallic materials for sucker rod pumps for
corrosive oilfield environment
TM 0177
Lab testing of metals for resistance to specific
forms of environmental cracking in H2S environments
RP 0273
Handling and proper usage of inhibited oilfield
acids
RP 0291
Care, handling and installation of internally
plastic-coated oilfield tubular goods
RP 0186
Application of Cathodic Protection for external
surfaces of steel well casings

Electrochemical cell

Figure 1: Schematics of electrochemical cell

We can test this prediction by adding a few chunks of mossy zinc to a

beaker of concentrated hydrochloric acid. Within a few minutes, the zinc metal
dissolves, and significant amounts of hydrogen gas are liberated.
The reaction has some of the characteristic features of oxidation-reduction
reactions.

It is exothermic, in this case giving off 153.89 kilojoules per mole of zinc
consumed.

The equilibrium constant for the reaction is very large (Kc = 6 x 1025), and
chemists often write the equation for this reaction as if essentially all of
the reactants were converted to products.

Zn(s) + 2 H+(aq)

Zn2+(aq) + H2(g)

It can be formally divided into separate oxidation and reduction halfreactions.

Oxidation:
Reduction:

Zn
Zn2+ + 2 e2 H+ + 2 eH2

By separating the two half-reactions, the energy given off by this reaction
can be used to do work.

According to the first law of thermodynamics, the energy given off in a


chemical reaction can be converted into heat, work, or a mixture of heat and
work. By running the half-reactions in separate containers, we can force the
electrons to flow from the oxidation to the reduction half-reaction through an
external wire, which allows us to capture as much as possible of the energy
given off in the reaction as electrical work.
We can start by immersing a strip of zinc metal into a 1 M Zn2+ ion
solution, as shown in the figure below. We then immerse a piece of platinum wire
in a second beaker filled with 1 M HCl and bubble H2 gas over the Pt wire. Finally,
we connect the zinc metal and platinum wire to form an electric circuit.
We've now made a system in which electrons can flow from one halfreaction, or half-cell, to another. The same driving force that makes zinc metal
react with acid when the two are in contact should operate in this system. Zinc
atoms on the metal surface lose electrons to form Zn 2+ ions, which go into
solution.
Oxidation:

Zn2+ + 2 e-

Zn

The electrons given off in this half-reaction flow through the circuit and
eventually accumulate on the platinum wire to give this wire a net negative
charge. The H+ ions from the hydrochloric acid are attracted to this negative
charge and migrate toward the platinum wire. When the H + ions touch the
platinum wire, they pick up electrons to form hydrogen atoms, which
immediately combine to form H2 molecules.
Reduction:

2 H+ + 2 e-

H2

The oxidation of zinc metal releases Zn 2+ ions into the Zn/Zn2+ half-cell.
This half-cell therefore picks up a positive charge that interferes with the transfer
of more electrons. The reduction of H+ ions in the H2/H+ half-cell leads to a net
negative charge as these H+ ions are removed from the solution. This negative
charge also interferes with the transfer of more electrons.
To overcome this problem, we complete the circuit by adding a U-tube
filled with a saturated solution of a soluble salt such as KCl. Negatively charged
Cl- ions flow out of one end of the U-tube to balance the positive charge on the
Zn2+ ions created in one half-cell. Positively charged K + ions flow out of the other

end of the tube to replace the H + ions consumed in the other half cell. The Utube is called a salt bridge, because it contains a solution of a salt that literally
serves as a bridge to complete the electric circuit.

General Corrosion Principles

Electrochemical in nature:
Involves the transfer of electrons
Requires electron path and ionic path
Requires two half reactions:
Production of electrons
Fe
Fe2+ + 2e Allows consumption of electrons 2H+ + 2e- H2
Must consider two aspects:
Thermodynamics willingness to corrode
Measured using potential difference (voltage)
Kinetics rate of corrosion
Indicated by electrical current flow
Increases with concentration / temperature / fluid velocity

Thermodynamics

Pourbaix diagrams
For particular conditions these demonstrate the stability of metals
They suggest different methods of mitigating corrosion
Lower potential
Raise pH
Raise potential
They do not say anything about the kinetics or rate of corrosion

Figure 2: Pourbaix diagram


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* Figure 2 shows the Pourbaix diagram for iron and shows that iron exhibits two
separate regions of corrosion, a region of passivity, and at the bottom, a region
of immunity. The 'Passive' region indicates that corrosion (though possible) is
less likely than the formation of a protective oxide layer on the metal surface.
The 'Immune' region implies that no corrosion will occur (this is the region
sought for cathodic protection of iron). Finally, the two 'Corrosion' regions signify
the release of iron ions into solution.

Galvanic Series

Electrochemical series indicates the relative thermodynamic stability of


metals under standard conditions.
Galvanic series indicate relative stability of metals in real environments
Note that joining dissimilar metals may lead to rapid attack of the
least noble one, however if there is no aggressive species corrosion
will not take place.
This forms the basis of Sacrificial Anode Cathodic Protection.
Galvanic attack mat also happen if there are significant
metallurgical differences in one piece of metal (e.g. heavy cold
working such as tong marks)

Figure 3: Galvanic series of metals in seawater

* The Galvanic Series of Metals can be used to determine the likelihood of a


galvanic reaction, andgalvanic corrosion or bimetallic corrosion, between two
different metals in a seawater environment.

The most Noble, metal lower in the Galvanic Series, will be the cathode while the
less noble, higher in the Galvanic Series, will act as an anode and it will
corrode.
The seawater galvanic series is used also to approximate the probable galvanic
effects in other environments for which there are no data.
However galvanic corrosion is a function of several different factors that needs
to be carefully evaluated when assessing the likelihood to have galvanic
corrosion.
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We suggest you to have a look also at our Galvanic Corrosion page and also
at Galvanic Corrosion Documents
The table below reports the Corrosion potentials or Galvanic Series of metals in
flowing sea water at ambient temperature.
The unshaded symbols show ranges exhibited by stainless steels in acidic water
such as may exist in crevices or in stagnant or low velocity or poorly aerated
water where Stainless Steel become active, while the shaded areas show the
potentials of Stainless Steel when is in passive state.

Electrochemical Measurements
Electrochemical measurement whether done in the lab or in the field, requires
three electrodes.
Sample
References
Auxilliary
They are used to determine:
Corrosion rates
Current required for Cathodic Protection
Polarization behaviour

Figure 4: 3-electrode scheme electrochemical measurement


*No explanation

Types of Corrosion

Figure 5: Various types of Corrosion

Unusual Types of Corrosion

Ring-worm corrosion
Localized corrosion around box end
Wireline attack (also in coated tubing)
Internal scratches along the tubular corrode rapidly
Caliper track corrosion
Similar to wireline attack but caused by the feelers of the caliper
tools
Sucker rod failure
Often caused by pitting, then fatigue
Tong damage
May lead to localized corrosion

Figure 6: Wireline damage

What makes Wells special.

Geometry
There are usually concentric strings of casing
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Direct corrosion monitoring is difficult, preferably non-intrusive (or


its usually high cost)
To certain extent the annulus environment can be controlled
Completion designs are determined by:
Tubing size required for flow performance
Mechanical integrity (principally tension, burst and collapse)
Life expectancy (typically the time to a workover, usually 10 years)
Tubing, casing and jewellery to be considered
Acidisation for stimulation may be a factor, or hydraulic fracturing

Potential Corrosion Sites in a well

Figure 7: Potential corrosion sites in a well

* External Casing Corrosion


External casing corrosion can occur for a number of reasons, such as exposure
to water zones, differences in formations the casing passes through, or when the
casing acts as an anode to other metals in the area (such as surface equipment
and other wells). Cementing the casing can prevent some of this corrosion, and
some wells are completely cemented for this reason. Cathodic protection (see
the prevention page)is another common method to reduce corrosion.
Internal and Annulus Corrosion
Corrosion in the annulus between the casing and the tubing is dependant on the
type of fluid in this area. When a well is completed with a packer, as in the
illustration above, this fluid is usually a combination of drilling mud, brine and
possibly produced oil or gas. The composition of this fluid determines the types
and the amount of corrosion. Packer fluids can be designed to meet the
corrosion mitigation needs of a particular well, for instance, using oil based
drilling mud can help prevent corrosion in the annulus. If the well is completed
without a packer, the annulus space is filled with wet gas above the fluid level
and produced fluids below. The composition of the fluids and the gas can cause
corrosion, especially if acid gasses are present. (see the section on H2Sfor more
information
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Internal Casing Corrosion

Internal casing corrosion can occur in the absence of a packer or if the


packer fails
Water can condense at cool areas on the casing and H 2S and/or CO2 can
corrode the steel
The tubing wouldnt necessarily be corroded at the same area because
fluid travelling along it may keep its temperature above the dew point.

Factors Influencing Corrosion

Aggressive species
Water plus
O2
CO2
H 2S
ClOthers
Pressure
Temperature
Flowrate
pH
Bicarbonate
Bacteria
Galvanic couples
Differential concentration
Dew point
Inhibitor
Coating / lining

Corrosion rates Species dependency

Figure 8

Common Corrosion Reactions

Sweet Corrosion
CO2 + Fe + H2O FeCO3 + H2
Half reactions:
CO2 + H2O 2H+ + CO32 Fe
Fe2+ + 2eSour Corrosion
H2S + Fe
FeS + H2
Half reactions:
H 2S
2H+ + S2- 2H+ + 2e- H2
Disassociation in water
Fe
Fe2+ + 2e-

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The Types of Corrosion Caused

Sweet
General corrosion (calculated using Shell Hydrocor, or Petronas
Corrosion Analyzer)
Pitting leaks, grooves
Scaling
Sour
Hydrogen Induced Cracks
Sulphide Stress Cracking (especially < 80C)
Blistering
Chloride
Pitting
Stress corrosion cracking of corrosion resistant alloys (especially
above 80C)

Mitigation Methods
Engineering
Permanent solution particularly for corrosion which can cause rapid /
sudden failure
Increases CAPEX
Operating
Adds to OPEX
Requires confidence in operations and commitment
Operations
Remove the corrosive species
Downhole dehydration?
Injection of chemicals to prevent or remove H 2S
Inhibit
Continuous
Batch
Cathodic Protection (for casing)
Impressed (continuous or pulsed for casing protection)
Sacrificial
Inhibitor Application: Batch
Tubing displacement and squeeze treatments
Inhibitor flowed through tubing
For displacement, the tubular is filled and the well shut-in. With
squeeze, the inhibitor is injected through the tubular into the
reservoir.
Typically shut-in for a day
Inhibitor residuals monitored at wellhead
Another treatment is necessary when ppm falls below a predetermined level
May require one treatment every 3 or 4 months
Squeeze protects below the packer

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Figure 10

Weighted inhibitors
Intended to fall to rat hole and slowly release
Encapsulation
Inhibitors encapsulated in polymer gel are introduced into the well,
either in a basket or in the rat hole.

Figure 11
Inhibitor Application: Continuous
Through the production annulus
Into the casing through a valve positioned in a side pocket
Its possible to inject into specific region of the string
Can simply fill the annulus with inhibitor and inject through a gas lift valve,
but lacks control.
Doesnt protect below the packer

Figure 12

Casing Cathodic Protection


Usually requires quite large currents
Is difficult to directly measure the effect of applying current
Often attenuation calculations are used to give a comfortable
feeling
Casing pressure survey may be used to measure success, provided
enough baseline data exists
Remote wellhead measurements are often used
Can cause interference with flowlines, other wells or surface equipment.
For this reason wellheads require good electrical insulation (also to
prevent galvanic problems)
Groups of wells are usually protected simultaneously
To ensure CP to the bottom of the casing, current is sometimes pulsed.

*Corrosion Control Methods (for oilfield)


Cathodic Protection
Sacrificial Anode
Impressed Current Cathodic Protection
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Protective coatings
Chemical inhibitors
Plastic or cement liners
Use of special alloys
Removal of corrosive gases
Dehydration

Multilateral Wells
FIGURE 13
Completions and Multilateral Team
Advanced completion design
Multilateral well technology
Casing exiting using milling / explosives
Novel multilateral junction designs
Expandable systems, monobore completions, slim wells
Materials selection / new materials / preparation of standards
Materials advice
Testing procedures / Industry standards
New Coiled-tubing technology
Amorphous bonding
Use of CRA with orbital TIG ?????
ML database / newsletter / website
Dissemination of latest completions technology
Http://swwrij.siep.shell.com/cc/dw/cmlt/home.htm
Kinetics
Evans diagram and related Potential/Current graphs
Illustrates the speed of a reaction
Illustrates how exposure to different environments can create a galvanic
cell
Can be used to demonstrate how changes in the environment may affect
the corrosion rate
Can be determined for simulated conditions and used in the materials
selection process
Illustrates a way to measure corrosion instantaneously in the field.
FIGURE 14
E log I for Cathodic Protection Equipment
Well casings may need cathodic protection
Obtaining E lg I data is an accepted method of determining current
requirements
Instant off reading should be used
The reference electrode should be remote from the wellhead
Note the similarity between this wet up and that shown earlier regarding
determination of corrosion rate and V-I graphs.

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FIGURE 15

Results look similar to lab tests on small coupon


The change in gradient as the Tafel portion of the slope is reachedgives an
indication of current
However it is only an indication and should be supported by other
techniques to provide greater confidence
FIGURE 16

Monitoring & Measuring


Split into two categories
Intrusive
Those which require production to stop
Non-intrusive
Can be done without interrupting flow
Downhole calipers. Mechanical, magnetic, ultrasonic
Video cameras
Downhole CP logging tools
Weight loss coupons
Electrochemical techniques (LPR, EIS, potentiodynamic)
Hydrogen probes
Electrical resistance probes
Field signature monitoring
Intelligent pigging of pipelines
Conventional non-destructive techniques e.g. UT
Monitoring & Measuring: Intrusive
Downhole calipers, mechanical, magnetic, ultrasonic
Video cameras
Weight loss coupons / Electrical resistance probes
Electrochemical techniques (LPR, EIS, potentiodynamic)
Downhole CP monitoring using logging tools (casing potential profile tool)
Inspection of recovered tubing
Pressure testing

FIGURE 17
*Kinley mechanical caliper tool (www.kinley.com)
FIGURE 18
*Kinley caliper Fingers
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FIGURE 19
*Kapuni caliper corrosion
FIGURE 20
*Kapuni caliper corrosion

Ultrasonic Corrosion Inspection Tools (http://www.connect.slb.com)


FIGURE 21

Rotating pulse-echo transducer gives 360 coverage


High resolution-focused transducer quantifies even small defects on both
internal and external casing surfaces.
Precise first echo time gives accurate and detailed internal radius
measurement.
Second time echo gives casing thickness
Internal and external surface echo amplitudes give a qualitative visual
image of casing condition
Well site presentation is corrected for tool ex-centralization effects
Detailed examination of both inner and outer casing surfaces, ranging in
diameter from 4 to 13 3/8 in
Multifinger calipers can examine only the internal surface and may even
damage the casing. Flux leakage instruments presently offer limited
accuracy and coverage.
Good resolution of the UCI tools is due to the very high transducer
frequency of 2 MHz. The signal is however attenuated by the bore hole
fluid, and for best results brine, oil or very light muds should be used (no
solids)
Logging rate is 425 to 3000 ft/hr depending on sampling rate
Not much use if solids are present in the fluids (noise)
FIGURE 22

The UCI takes 180 highly focused measurements during each revolution
of the ultrasonic sensors.
It has up to 5 rotations every inch of travel inside the casing and can
measure pits and other anomalies down to diameters of approximately 8
mm on either the inside and outside surfaces.

Casing Potential Profile Equipment


A casing potential profile is a measurement of the difference in potential
between two points inside the casing not a measure of the casing to soil
potential which is indicative of the likelihood of corrosion.
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Typically the contacts are 3 to 10 meters apart with wires brought up to


surface and connected across a voltmeter.
The tool is moved along the inside of the casing with potential difference
measurements taken as needed.
FIGURE 23

Casing Potential Profile Results


It is usual to run the tool without CP to get baseline data and then with CP
A positive shift indicates current flow up the casing
In the example from the diagram, the entire casing appears to be
receiving current
Note that the tool does not indicate the casing to soil potential and
therefore does not provide direct information about external corrosion
FIGURE 24
Corrosion Monitoring Application Limits
FIGURE 25
Downhole Corrosion Monitoring
FIGURE 26

Monitoring & Measuring: Non-Intrusive


Wellhead and remote CP monitoring (external casing)
Inspecting tubulars retrieved for some other purpose
Iron, Mn or bacterial counts
Inhibitor concentration monitoring
Annulus pressure monitoring
Monitoring of flowlines and/or other surface equipment using conventional
methods to infer well conditions
Electrical resistance probes
Electrochemistry
UT etc
Mitigation Methods
Corrosion allowance
Remove the corrosive species
Prevent ingress / gas blanket
Scavenge
Kill bacteria
Cathodic Protection
Impressed current (continuous or pulsed for casing protection)
Sacrificial
Resistant materials
Solid Corrosion Resistant Materials (CRA)
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Clad CRA (low alloys to nickel alloys)


Coatings / linings
Composite materials (fibre reinforced plastics)
Inhibitors
A combination of these methods

Sweet & Sour Corrosion: Damage


Sweet corrosion
Pitting pin hole
leaks
Deep grooves along
wetted areas of gas
lines may lead to
rupture
Often
accompanied
by severe scaling
Susceptibility
increases
with:
Increasing pp(CO2)
Increasing velocity
Increasing
Temperature
Presence
of
particulates

Sweet & Sour Corrosion: Prevention

17

Sour corrosion
Hydrogen Induced Cracking
Sulphide
Stress
Cracking
Step-wise cracking
Blistering
Hydrogen-assisted
ductile failure
FeS dust can also block gas
line filters
Susceptibility increases with:
Increase pp(H2S)
Increasing hardness/strength
Decreasing pH/temperature
Increasing stress (residual or
applied)

Sweet corrosion
Dehydration
Corrosion resistant materials
13 Cr or better
Non-metallic

Use inhibitor
Prefer
continuous
application
Batching is possible
Require
test
to
determine
most
effective
Need to ensure it gets
to correct location
Coat / line
Insert
line
into
new/existing
line
(particularly for water
disposal)
Coat with GRE/FBE/PE
(sometimes used ofr
downhole equipment)

Sour corrosion
Dehydration
Resistant materials
SSC NACE qualified
materials bear in
mind the potential for
other kinds of failures
Request qualification:
slow strain and ripple
strain tests now used
Apply inhibitor
Coat/line
(isolate
from
environment)
Remove hydrogen sulphide
(use NACE criteria)

FIGURE 27

Factors Influencing the Choice of Materials


Mechanical properties required
Dimension and strength of material governed by well characteristics
Corrosion allowances are not normally used
Require life cycle cost (often emphasise is on capex)
Corrosion which may cause sudden failure (e.g. SCC, SSC) must be
designed out.
Cost of failure (offshore vs onshore)
Worst case composition, pressure, temperature and flow velocity of fluids
Differences between tubing/casing/wellhead
Internal and external
Confidence in ability to operate within boundary conditions
How accurate is the well data (esp. during engineering phase)
Can inhibition continuity be guaranteed
Will water breakthrough occur, will H2S level increase with age

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NACE MR 0175-02 Criteria for Sour Service (H2S)

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