Corrosion

Control
 Common Steels in the
Wellbore
 Ferrous Alloys
– Low Alloy, Mild Steel
 AISI 4130, 4340 Are the Most Common Examples
 Used for Must Tubing and Casing Strings
 Common Steels in the
Wellbore
– Stainless Steels
 Austenitic Stainless Steel (AISI 302, 316)

– Gravel Pack Screens, Down Hole

Assemblies, Tools
 Martensitic Stainless Steels (13Cr, 9Cr-1Mo)

– CO2 Gas Well Tubing

 Duplex Stainless Steels (22Cr, 25Cr, 28Cr)

– Sour Gas Tubing

 Nickel Alloys (Niconel, Hastelloy)
 AISI Classification Method

 Four Digit Designation

 First Two Numbers - Major Alloy Elements
 Last Two Numbers -
– Nominal %C (0.01 increments)
 AISI 4140 = 1% Cr, 0.2% Mo, 0.4% C
Corrosion
 Corrosion
Corrosion is the deterioration of a
substance, usually a metal or alloy,
because of a detrimental reaction
with the environment

(often caused by chemical reactions)

 Corrosion Control

Applications
– Drilling Muds
– Packer Fluids
– Workover / Completion Fluids

NOT FOR PRODUCTION APPLICATIONS

 Corrosion Control

 Corrosion Cannot Be Totally

Eliminated

 It Can Be Controlled With Proper

Treatment of the Drilling Fluid and
Pipe
Methods for Reducing Corrosion

 Change the Environment

 Neutralize or Scavenge the

Contaminant

 Form a Protective Film on the Pipe

 Change the Metallurgy to a More

Corrosion Resistant Alloy
 Industrial Associations
M-I is associated with the following
technical organizations:
– NACE International
– API
– IADC
– ASM
– SPE
Try to identify corrosion problems and
develop economical solutions
 Product Line

 Inhibitors

 Scavengers

 Biocides
 Corrosion Inhibitors
– CONQOR 101

– CONQOR 202B

– CONQOR 303A

– CONQOR 404

– SI-1000
Chemical Scavengers

 Oxygen Scavenger
 SULF-X
 Biocides
 BACBAN III
 Glutaraldehyde
 Metallurgy

 Iron ore is processed (refined) to

produce pure iron

 Iron is reacted with carbon plus

chrome, nickel, phosphorus, etc. to
produce “steel” alloys
 Metallurgy
 Metals and alloys have granular
structures
 As a molten metal cools, crystals form
and expand until they contact adjacent
crystals forming a boundary
 This forms a strong microstructure of
grains and grain boundaries which have
different chemical compositions
 Metallurgy

Mechanical and chemical properties

depend on:
– Base metal
– Type and concentration of alloying additives
– Temperature - rate and method of cooling
– Subsequent heat treating - cold working
 Metallurgy

 Alloys are produced to have desirable mechanical and

chemical properties
 Corrosion can cause failure or reduce service life of
drilling equipment
 Alloys are chosen to maximize service life by optimizing
mechanical properties and corrosion resistance
 High tensile strength steel is mechanically harder but
chemically more susceptible to hydrogen embrittlement,
stress corrosion cracking, and sulfide stress cracking
(SSC) than milder alloys
 Economic Impact

 Corrosion damage in its many forms

costs our industry billions of dollars
per year

 Since we do not directly feel the

impact on our personal bank account
we are not usually “aware” of these
situations
 Corrosion Examples

 Metal rusting is corrosion in action

 Scale on metals can cause

“underdeposit” corrosion

 Metal failure due to corrosion fatigue

and/or sulfide stress cracking
 Corrosion Examples
Personal Situations

 Automobile corrosion of metal allowing

water leaks

 Metal objects stored outside without

waterproof coatings or paint for
complete protection from the
environment

 Bumpers rusting after re-chroming

 Tendency to Corrode

The iron and iron carbide in the alloy

prefer to dissolve in the water and
return to the original oxide form
(like rust)
 Cell Components

 Anode

 Cathode

 Electrolyte

 Metallic path
 Oxidation

 Oxidation occurs at the anode as electrons (-)

are released as the metal ionizes

 Iron ions (soluble) go into solution leaving tiny

pits or holes in the pipe

Feo - 2e = Fe2+ (soluble-rusty water)

 This action occurs at the anode as metal ions

are dissolved
 Reduction
 Reduction occurs at the cathode as
electrons (-) are combined with other
ions

 Sometimes hydrogen gas is formed

 These actions must be isolated to

minimize corrosion
Reduction
Cathode Reactions

H2 Reduction in Acid Solutions

2H+ + 2e  H2
O2 Reduction in Acid Solutions
O2 + 4H+ + 4e  2H2O

O2 Reduction in Neutral and Alkaline Solutions

O2 + 2H2O + 4e  4OH-
Area Effect

 Because metal is removed at the

anode, it is preferable to have a large
anode and a small cathode

 If the anode was small and the

cathode was large, severe and rapid
corrosion would occur at the anode
Forms of Corrosion
 General
 Pitting
 Crevice
 Stress
 Sulfide Stress Cracking
 Galvanic
 Concentration Cell
 Erosion Corrosion
 Intergranular Corrosion
 Corrosion Fatigue
 Dealloying (parting)
General Corrosion
 Surface of metal is corroded in a
uniform manner
 Usually the least damaging form of
corrosion
 Corrosion rate measured with
drillstring coupons
 Corrosion rate expressed in lb/ft²/yr
 Maintain less than 2 lb/ft²/yr with NO
pitting
 Pitting Corrosion

 Localized corrosion forming pits or

cavities

 Undesirable form of corrosion

 Occurs when anode and cathode do not

shift location

 Corrosion is concentrated at specific

places (small portion of total surface)
 Crevice Corrosion

 Localized corrosion caused by a

concentration cell being formed in a
crevice

 Usually occurs at contact point of

metals and non-metals or two
metal surfaces
Stress Corrosion Cracking
(SCC)

 Cracking failure due to the

combination of high stress and
localized corrosion

 Metal may not appear to be

corroded, but will fail (or part)
when stressed

 SCC is frequently initiated at the

base of a pit
Sulfide Stress Cracking
(SSC)

 Brittle cracking failure due to the

combination of high stress in the
presence of hydrosulfuric acid (H2S in
water)
Galvanic Corrosion

 Occurs between dissimilar metals in a

conductive environment

 A potential difference exists between

dissimilar metals which causes electrons
to flow (corrosion)

 Anodic metal corrodes more rapidly

while cathodic metal corrodes very little
Concentration Cell

 Caused by differing ionic

concentrations within a closed “cell”

 Also referred to as shielding or

underdeposit corrosion

 Can occur under dried mud, pipe

scale, or drillpipe protectors
Erosion Corrosion

 Caused by high velocities of

corrosive fluid acting on metal
surfaces

 Any protective film may be eroded,

exposing a bare metal which is
susceptible to corrosion
Intergranular Corrosion

 Localized corrosion preferentially

along the grain boundaries
Corrosion Fatigue

 Fatigue failure by cracking of a

metal subjected to a combination
of cyclical stresses and corrosive
environment

 The endurance limit is the

maximum stress level where no
failure occurs, regardless of the
number cycles
Dealloying

 Localized corrosion where one of

the alloying additives is selectively
removed

 In some cases this is called

“parting”
Corrosion Accelerators

 pH

 Dissolved salts

 Temperature

 Scale

 Dissolved gases
pH

 Corrosion rates are higher at low

pH (below 7) than at high pH

 Normally 9.5 - 10.5 is adequate to

begin to reduce corrosion

 In some instances a higher pH

(approx. 12.0) is required
 Effect of pH on Corrosion
Dynamic Brine Study (200°F)
C
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6
0
0 p
H
8 1
0 1
2

4
0
0 3
%wt
N
aCl
3
%wt
2
0
0 KC
l

0
0 2 4 6
H
o
ur
s
 Dissolved Salts

 Dissolved salts increase the conductivity of

water, increasing the corrosion rate

 At high concentrations of salt (>25%), the

dissolved oxygen content is very low and
downhole corrosion rates are low (especially
with high pH)

 Seawater or 3% salt systems have the

highest potential for highest corrosion rates
 Effect of Salt on Corrosion
Relative Corrosion Rate

0
0 3 5 10 15 20 25 30
NaCl Concentration, wt %
Aerated System - room temperature
 Temperature
 Corrosion rates increase at higher temperatures
 Corrosion is most severe under downhole
conditions where temperatures are high and
oxygen cannot escape (closed system)
 Corrosion rates decrease at higher temperatures
for open systems where the oxygen can escape
(mud pits)
 Oxygen concentrations are higher in lower
temperature (colder) waters
Effect of Temperature
Open vs. Closed Systems
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Effect of Temperature on Brine
Corrosion Rate
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Effect of Salt & Temperature on Dynamic
Corrosion Rate
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l
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0
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Ho
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 Scale
 Severe corrosion (pitting) can occur under scale
on the drillpipe

 The isolated area under the scale forms a

“concentration cell”

 Scale occurs most often in high pH fluids with

high calcium where CaCO3 and CaSO4
precipitate and deposit on the drillstring
 Dissolved Gases

 Dissolved oxygen, carbon dioxide, and

hydrogen sulfide increase corrosion
rates

 Dissolved gases come from:

– Make-up water
– Pit system equipment (hoppers/mixers)
– Degradation of mud additives
– Formation (water/gas/oil)
 Dissolved Oxygen
 Leading cause of corrosion
 Even traces of oxygen cause pitting and
corrosion problems
 Dissolved oxygen content is higher at cold
temperatures
 Oxygen increases corrosion caused by carbon
dioxide and hydrogen sulfide
 Polymer mud systems tend to entrain air and be
more corrosive
Typical Dynamic Response
Pressurized 3% NaCl or KCl System
C
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°
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4
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Sal
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%Na
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Effect of Oxygen Scavenger on Brine
Corrosion Rate (3% KCl Brine 200°F)
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6
0
0

O
P
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2
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H
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 Dissolved Carbon Dioxide

 Carbon dioxide is acidic and will lower pH

and increase corrosion

 Carbon dioxide attack results in pitting

and grooving

 Treatments of lime [Ca(OH)2] in

combination with an inhibitor will control
carbon dioxide corrosion
 Carbonate Equilibrium
1 1
0
0

0
.
8H HCO3- CO3= 8
0
2CO3

0
.
6 6
0

%
0
.
4 4
0
ConcetraionFraction

0
.
2 2
0

0 0
4 6 8 1
0 1
2
p
H
• Carbon dioxide (CO2) dissolved in water forms
carbonic acid (H2CO3), then bicarbonate (HCO3-)
and carbonate (CO3=), depending on pH
 Hydrogen Sulfide
 Hydrogen sulfide is poisonous at very low
concentrations
 Hydrogen sulfide is acidic and will lower pH and
increase corrosion
 Hydrogen sulfide attack can cause hydrogen
embrittlement, sulfide stress cracking, and pitting
underneath iron sulfide scale
 Treatment for H2S includes maintaining the pH
above 11.0 with lime or caustic and using a sulfide
scavenger which precipitates the sulfide
 Sulfide Equilibrium
P
e
r
ce
nt
ofT
ot
alSu
l
f
ide
1
0
0 -
H
S
2 H
S
1
0

0
.
1

- 2
0
.
01 S
3 6 9 1
2
p
H
• Hydrogen sulfide (H2S) dissolved in water forms
hydrosulfuric acid then hydrosulfide (HS-) and sulfide
(S2-), depending on pH
 Neutralization of
Hydrogen Sulfide
pH % H2S % HS- + S2-
6.0 90.000 10.000
7.0 50.000 50.000
8.0 10.000 90.000
9.0 1.000 99.000
10.0 0.100 99.900
11.0 0.010 99.990
12.0 0.001 99.999

• Divide % by 100 for multiplying factor

• For a 10 pH, multiply measured sulfides by 0.001
 Neutralization of
Hydrogen Sulfide
 Hazardous H2S can be neutralized into less harmful
HS- and S2- by maintaining a high pH (>11.0)

 This reaction is reversible - a decrease in pH will

convert HS- and S2- back into H2S

 If the Garrett Gas Train measures 100 ppm in a

mud with a 10 pH, only 0.1 ppm exists as H2S

100 ppm x 0.001 = 0.1 ppm

C
OR
RO
SI
O N
CO
NT
RO
L
O
2

H2S
CO 2
M
ON
I
TOR

S
CA
LE ®
I
N H
I
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TOR
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p
 Monitoring Corrosion
 Monitoring is essential to controlling corrosion

 Corrosion coupons are placed inside the box at

the Kelly Saver Sub and in the last tool joint
before the collars

 Coupons are evaluated and changed on the

first trip after 100 hours of exposure

 Visual, chemical, and weight analysis of

coupons identify rate and type of corrosion
 Coupon Analysis
 Exposed coupons should be lightly wiped and
dried then wrapped in original papers for
transportation to lab for evaluation
 Visual inspection will identify scale, pitting, and
color as indications of the cause of corrosion
 Iron sulfide (FeS) test solution (acid arsenite) is
used first, and forms a bright yellow precipitate
resembling “miniature scrambled eggs” when
iron sulfide is present
 Coupon Analysis

 Effervescence (bubbling) also occurs in this

acid when carbon dioxide (CO2) corrosion is
present

 Inhibited 15% HCl acid is used to clean and

remove corrosion byproducts from coupons

 Corrosion byproducts which do not quickly

dissolve in acid are usually iron oxides from
oxygen corrosion
Corrosion Control

 pH

 Inhibitors

 Scavengers

 Bactericides
 pH Control

 Maintaining an alkaline pH > 9.5 is

essential to corrosion control

 An alkaline pH reduces the reactivity of

acid gases, bacterial activity, and
corrosion in general

 Under severe conditions, pH values as

high as 12.0 may be necessary
 Corrosion Inhibitors

CONQOR 404 All-purpose organophosphorus

passivating inhibitor

CONQOR 101 Dispersed packer fluid filming

amine

CONQOR 202B Direct application filming amine

CONQOR 303A Brine soluble filming amine

SI-1000 Organic phosphate scale inhibitor

 CONQOR 404

 All-purpose passivating inhibitor

 Treatment: 2-5 gal/100 bbl

 Aerated mud applications: 10-12 gal/100 bbl

 Not for packer fluids, mud must be circulating

for CONQOR 404 to work

 Must be used in sufficient concentration

Filming Amines

Protect steel by displacing water and

forming protective oil-wet film

CONQOR
101
CONQOR
202B
CONQOR
303A
CONQOR 101

 Oil-soluble, water-dispersible filming

amine for dispersed packer fluids

 May flocculate high solids or lightly

treated muds

 Treatment: 0.5 gal/bbl

 Forms a protective oil-wet film on steel

surfaces
 CONQOR 202B
 Persistent film-forming amine which must be
directly applied to pipe or used as a batch
treatment (slug)

 Used when CONQOR 404 is not available or

applicable

 Protection / coating will diminish with

circulation and time

 May cause foaming

CONQOR 303A

 Water and brine soluble amine for brines

and workover and completion fluids

 Treatment: 55 gal/100 bbl

 Forms a protective film on steel surfaces

 Not effective in zinc brines

 Scale Inhibitor

 SI-1000 limits scale buildup on drillstring

 Prevents precipitation and deposition of

scale on metals

 Organic phosphate based chemistry

 Treatment: 1 gal/200 bbl initial, with 5

gal/tour maintenance
 Chemical Scavengers

Oxygen Scavenger Reduces dissolved oxygen

SULF-X Precipitates sulfides from H2S

 Oxygen Scavenger

 Ammonium bisulfite based chemicals

SO32- + ½ O2  SO42-

 Meter into pump suction with injection pump

(pump suction connection needs shut-off valve)

 Maintain 300-500 ppm sulfites at flowline

 0.5 - 2.0 gal/hr typical consumption

 SULF-X
 Zinc based H2S scavenger
Zn2+ + S2-  ZnS 
 Special high surface area zinc oxide
 80.3% by weight zinc
 Treatment: 1 lb/bbl can remove up to 1,100 mg/l
sulfides detected
 Pretreat with 1 lb/bbl
 May flocculate mud increasing viscosity
 Bactericides
BACBAN III
 BACBAN III microbiocide adsorbed into inert
granular material
 Treatment: 1½ - 3 jugs (6 lb/jug) per 100
bbl (0.10 - 0.18 lb/bbl BACBAN III)

Glutaraldehyde
 Glutaraldehyde (25% active) liquid
microbiocide for severe bacteria problems
 Treatment: 8 gal 25% glutaraldehyde/100
bbl (maximum 2,000 mg/l)
 Helpful Hints

 Biocidescan be used to kill

bacteria in the make-up water
before salting up.
 Always use a soluble chemical
biocide.
 Water-Based Packer
Fluids
 Condition the drilling mud to form a
stable fluid with a high pH

 Use biocides to reduce bacterial

activity

 Use inhibitors to aid in coating the

pipe
 Oil-Based Packer Fluids
 Condition for optimum long-term
emulsion stability

 Increase electrical stability

 Raise Pom with lime for high alkalinity

 Circulate sufficient length of time to

adequately mix all treatments

 No inhibitors are used in oil-based fluids

General Treatment
Guidelines

 When a problem is first noted, react

with the appropriate M-I corrosion
chemical and other techniques to
minimize the corrosion rate

 Monitor and adjust treatments and

chemicals based on corrosion coupon
analysis
 Summary
 Monitor corrosion rates with coupons

 All water-based drilling fluids can be corrosive,

it is only a matter of degree !

 Many fluids are highly corrosive due to the

salinity, dissolved gases, and the environment

 Be aware of the potential for corrosion and use

precautions along with M-I products and
techniques to keep corrosion under control
Document corrosion control programs
and follow-up with good case histories
to share successes with others