Design Criteria: Internal Corrosion

DESIGN CRITERIA
INTERNAL CORROSION
CORROSION PARAMETERS AND CLASSIFICATION OF THE

FLUIDS
02555.VAR.COR.PRG
Rev. 2
June 1995
2 General revision CESCOR STIN CORM 15.06.95

REV. DESCRIPTION COMP. VERIF. APPR. DATE
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Il presente documento è RISERVATO ed è di proprietà dell'AGIP. Esso non sarà mostrato a Terzi né sarà utilizzato per scopi diversi da quelli per i quali è stato inviato.
This document is CONFIDENTIAL and the sole property of AGIP. It shall neither be shown to third parties nor used for purposes other than those for which it has been sent.
02555.VAR.COR.PRG
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FOREWORD
Rev. 2 No. Sheets 47

June 1995
The type of document has been changed from “GENERAL SPECIFICATION”

to “DESIGN CRITERIA”.
The Normative References chapter has been revised and updated.
It has been deeply revised the paragraphs concerning the corrosion parameters
and the corrosion forms; corrosion evaluation criteria have also been updated.
With respect to the previous revision, it has been completely eliminated the
classification by corrosion environments. In this revision, fluids are defined
only in terms of “type of fluid” and “corrosivity class”.
A detailed list of definition has been introduced.
Definition of sour conditions in accordance to EFC - European Federation of

Corrosion, has been introduced.
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CONTENTS
1 GENERAL
1.1 Scope
1.2 Normative references
1.2.1 European normative references
1.2.2 Normative references of ISO, IEC and national organizations
1.2.3 Normative references of other organizations
1.3 Definitions
1.4 Abbreviations and conversion factors
2 FLUID TYPES AND CORROSIVITY CLASSES
2.1 Fluid types

2.1.1 Liquid hydrocarbons and multiphase
2.1.2 Gas and gas condensate
2.1.3 Glycol
2.1.4 Waters
2.2 Corrosivity classes
3 CORROSION PARAMETERS
3.1 Foreword
3.2 Temperature
3.3 Pressure
3.4 Water content
3.5 Gas Oil Ratio
3.6 Hydrodynamic conditions
3.7 CO2 molar fraction
3.8 H2S molar fraction
3.9 API Grade
3.10 Water chemical analysis
3.11 Sulphates-reducing bacteria
3.12 Sand and suspended solids
4 CORROSIVITY CLASSES
4.1 Liquid hydrocarbons and multiphase systems (I.L.)

4.1.1 Corrosion parameters
4.1.2 Corrosivity classes
4.2 Gas hydrocarbons and gas with condensates

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4.3 Glycol
4.4 Waters
5 CORROSION FORMS
5.1 General
5.1.1 Foreword
5.1.2 Materials
5.1.3 Corrosion morphologies
5.2 Water wetting conditions

5.2.1 Liquid and multiphase systems
5.2.2 Gas and gas with condensates system
5.3 O2 corrosion
5.4 H2S corrosion
5.5 Elemental sulphur corrosion
5.6 CO2 corrosion
5.6.1 Effects of chemical species in solution
5.6.2 De Waard and Milliams model.
5.6.3 Top of line corrosion
5.6.4 Prediction rules for CO 2 corrosion (Crolet Model)
5.6.5 Corrosion products
5.7 Galvanic corrosion

5.8 Pitting and crevice
5.8.1 Susceptible materials
5.8.2 Initiation conditions
5.9 Stress Corrosion Cracking (SCC)

5.9.1 Chlorides stress corrosion cracking
5.9.2 Polythionic Acids Stress Corrosion Cracking
5.10 Sulphide Stress Cracking (SSC)

5.10.1 Sour service conditions according to NACE
5.10.2 Sour service conditions according to EFC
5.11 Stepwise Cracking

5.11.1 Limits for initiation
5.12 Erosion corrosion

5.13 Sand erosion
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1 GENERAL
1.1 Scope
Scope of this document is provide criteria to classify, from the corrosion

viewpoint, the main fluids encountered in plants for oil and gas production.
The plants covered in this document are those ones from well head, excluded,
to the delivery of treated gas and stabilised oil. Refining plants are outside the
scope of this document.
For each type of fluid the parameters are indicated to be gathered to allow the
corrosion experts to assess the corrosivity and to select materials and corrosion
control methods.
The most common corrosion forms in oil and gas industry are reviewed and
proved criteria for corrosion prediction are indicated.
This document does not cover the corrosivity of the external environment
which the plant components are in contact with, as soil, sea water; also non
metallic materials such as elastomeric, ceramic, composites are not dealt with.
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1.2 Normative references
1.2.1 European normative references
No European normatives exist on the argument of this specification.
1.2.2 Normative references of ISO, IEC and national organizations
ISO 8044 “Basic Terms and Definitions on Corrosion”.
1.2.3 Normative references of other organizations
EFC O&G 93-1 “Guidelines on Material Requirements for Carbon

and Low Alloy Steels for H 2S Containing Oil and
Gasfield Service”
NACE MR0175 “Sulphide Stress Cracking Metallic Material for

Oil Field Equipment”
NACE TM0284 “Evaluation of Pipeline Steels for Resistance to

Stepwise Cracking”
API RP-14E “Design and Installation of Offshore Production

Platform Piping System”
ASTM 287-92 “Standard Test Method for API Gravity of Crude

Petroleum and Petroleum Products (Hydrometer
Method)”
ASTM G 78-46 “Standard Test Method for Pitting and Crevice

Corrosion Resistance of Stainless Steels and
Related Alloys by the Use of Ferric Chloride
Solutions”
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1.3 Definitions
Chloride Stress Corrosion Cracking - CSCC

Formation of cracks caused by stress corrosion in a water- and chloride ions-
containing environments (NACE MR0175).
Corrosion
Physicochemical interaction between a metal and its environment that results in
changes in the properties of the metal and which may often lead to impairment
of the function of the metal, the environment, or the technical system, of which
these form a part (ISO 8044).
Corrosion product
Substance formed as a result of corrosion (ISO 8044).
Corrosion rate
Corrosion effect on a metal per unit of time.
Corrosion resistance
Ability of a metal to withstand corrosion in a given corrosion system (ISO
8044).
Corrosion system
System consisting of one or more metals and all parts of the environment which
influence corrosion (ISO 8044).
Corrosive agent
Substance which when in contact with a given metal will react with it (ISO
8044).
Corrosive environment
Environment that contains one or more corrosive agent (ISO 8044).
Corrosivity
Ability of an environment to cause corrosion in a given corrosion system (ISO
8044).
Corrosivity class
In the present document, it is an attribute conventionally assigned to each type
of fluid in order to point out the most significant corrosivity features. For the
fluid designed: liquid hydrocarbons and multiphase (I.L.), gas and gas with
condensates hydrocarbon (I.G.) and glycol (G.), the corrosivity class is defined
on the base of CO 2 and H2S partial pressures as follows:
– N. non containing CO 2 and H2S
– C. containing CO 2
– S. containing H 2S
– CS. containing CO 2 e H2S
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Crevice Corrosion
Corrosion associated with, and taking place in, or immediately around, a
narrow aperture or clearance (ISO 8044).
Dew point temperature

It is the temperature, below which liquid condensation starts from gas phase at
a given pressure. On the state diagram condensation conditions are indicated by
the dew point curve. In particular the water dew point refers to condensation
conditions of water from gas.
Fugacity
It is thermodynamic function, in pressure units, that, when used in a
thermodynamic equation of an ideal gas in substitution of pressure, allows to
apply the same function to a non-ideal gas.
Hydrocarbon
− Gas: a mixture of hydrocarbons with 1 to 4 carbon atoms at a temperature
above the critical temperature. Gas can be in form of dry gas or gas with
condensates depending on thermodynamic conditions.
− Liquid: a mixture of hydrocarbons whose temperature is below the critical
temperature of the particular system of natural hydrocarbons that the mixture
contains; in the mixture the liquid phase, always present, can be combined
with a gas phase or an aqueous phase or both; in this cases the system is
called multiphase.
Hydrogen embrittlement
A process resulting in a decrease of the toughness or ductility of a metal due to
absorption of hydrogen. (ISO 8044).
Hydrogen Induced Cracking - HIC

A type of "stepwise cracking" in steels for pipes, or laminated products; cracks
on the same plane have the tendency to join with cracks in near levels forming
steps through the metallic wall, reducing its mechanical resistance.
Ionic strength
The ionic strength of a solution, µ, is defined as
1
µ= ∑ C i Z 2i
2
where Ci is the concentration of i -th ion with Z i charge.
Microbial Corrosion
Corrosion associated with the action of micro-organism present in the corrosion
system (ISO 8044).
Molar fraction
Measurement of the concentration of a chemical species expressed as ratio
between the number of moles of the given chemical species and the total
number of moles.
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Oil
In the present specification the terms oil and crude are considered synonymous
to indicate liquid hydrocarbons.
Passivity (passive state)

State of a corrosion system characterised by a reduced corrosion rate of a metal
as a consequence of the formation of corrosion products on its surface.
Pitting Corrosion
Corrosion resulting in pits, i.e. cavities extending from the surface into the
metal (ISO 8044).
Predicted corrosion rate

It is the corrosion rate, usually expressed quantitatively (in mm/y) and/or
qualitatively, determined: (a) after the corrosion study, applying all the
available knowledge and tools; (b) through laboratory tests, simulating the real
conditions; (c) on the base of field corrosion monitoring data applicable to the
case under study. The following categories are recommended to express in a
qualitative way the penetration rate for general corrosion forms: negligible,
low, moderate, severe, very severe.
Reservoir
− Dry gas: reservoir whose temperature is above the cricondetermical
temperature of the particular system of natural hydrocarbons that it contains.
The cricondetermical temperature is the highest temperature at which the
coexistence between liquid and gas phase is still possible.
− Gas with condensates: reservoir whose temperature is between critical and
cricondetermical temperatures of the particular system of natural
hydrocarbons that it contains. The condensation of the liquid phase from gas
takes place by reverse condensation, that is the phenomenon by which
decreasing the pressure below the dew point, there is initially an increase of
the liquid phase percentage and eventually a partial or total ri-evaporation of
the latter.
− Crude oil: reservoir whose temperature is below the critical temperature of
the particular system of hydrocarbons that in contains.
Residual corrosion rate

It is the corrosion rate after treatments with corrosion inhibitors.
Sour conditions
Conditions, usually with H 2S presence, that cause Sulphide Stress Cracking
occurrence in susceptible materials. The definition is according to NACE
MR0175 or EFC O&G 93-1.
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Specific gravity
It is the ratio between the weight of a given volume of liquid and the weight of
the same volume of water; for a gas it is the ratio between the weight of a given
volume of gas and the weight of the same volume of dry air in the same
standard conditions.
Stepwise Cracking - SWC

Formation of cracks, even in absence of mechanical solicitations, as a
consequence of diffusion of atomic hydrogen, produced in the cathodic reaction
in H2S containing environments, and the successive recombination to molecular
hydrogen inside the metallic lattice near microcracks, inclusions or defects.
Stepwise Cracking includes: “Stress Oriented Hydrogen Induced Cracking”,
“Blistering”, “Hydrogen Induced Cracking”.
Stress Corrosion Cracking - SCC

A process resulting from the combined action of corrosion and tension
mechanical solicitations due to residual or applied stresses; it causes the
formation of surface stress corrosion cracks; cracks are usually perpendicular to
the stress direction.
Sulphide Stress Cracking - SSC

Formation of cracks caused by stress corrosion, with a significant contribution
of H2S as a corroding agent.
Type of fluid
In the present document the following types of fluid are considered: liquid
hydrocarbons (I.L.); gas and gas with condensates hydrocarbons (I.G.); glycol
(G.); sea water (A.M.); fresh water (A.D.); brackish water (A.S.); formation
water (A.F.).
Wettability
Tendency of a fluid to disperse or to adhere to a solid surface in presence of
another insoluble liquid. Wettability is a measure of the preference of corrosion
products or metallic surfaces for water or oil.
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1.4 Abbreviations and conversion factors
Table 1.1 shows the corrosivity parameters mentioned in this document with
their abbreviations and measure units. Table 1.2 shows the main conversion
factors.
Tab. 1.1 - Corrosion parameters, abbreviations, and units.
PARAMETER Abbreviation Unit

operating pressure P MPa
operating temperature T °C
minimum temperature Tmin °C
maximum temperature Tmax °C
H2S molar fraction yH2S mole/mole%
CO2 molar fraction yCO2 mole/mole%
H2S partial pressure pH2S MPa
CO2 partial pressure pCO2 MPa
water cut percentage WCUT m³/m³ %
water oil ratio percentage WOR m³/m³ %
gas oil ratio GOR Nm³/m³
API grade API (-)
total salinity in the water phase TDS g.l-1
water chemical analysis
− chlorides concentration Cl- mg.l-1 (ppm)
− bicarbonates concentration HCO3- mg.l-1 (ppm)
− acetates concentration HAC mg.l-1 (ppm)
− sulphates concentration SO4-- mg.l-1 (ppm)
− sodium concentration Na+ mg.l-1 (ppm)
− potassium concentration K+ mg.l-1 (ppm)
− magnesium concentration Mg2+ mg.l-1 (ppm)
− calcium concentration Ca2+ mg.l-1 (ppm)
− iron concentration Fe2+ mg.l-1 (ppm)
oxygen in aqueous phase cO2 mg.l-1 (ppm) or ppb
water pH in situ pHin-situ (-)
water pH in air pHin-air (-)
elemental sulphur S yes/no
mercury Hg yes/no
average flow rate v m/s
applied load σ MPa
yield strength σYS MPa
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Tab. 1.2 - Conversion factors
PARAMETER from to multiplying

factor
concentrations:
− bicarbonates mg.l-1 (ppm) meq.l-1 0.016
− acetates mg.l-1 (ppm) meq.l-1 0.017
− sulphates mg.l-1 (ppm) meq.l-1 0.021
− sodium mg.l-1 (ppm) meq.l-1 0.043
− potassium mg.l-1 (ppm) meq.l-1 0.026
− magnesium mg.l-1 (ppm) meq.l-1 0.083
− calcium mg.l-1 (ppm) meq.l-1 0.050
− iron mg.l-1 (ppm) meq.l-1 0.036
− chlorides mg.l-1 (ppm) meq.l-1 0.029
pressure psi MPa 0.006895
pressure bar MPa 0.1
o o
temperature F C (°F-32)/1,8
volume barrel (US) m3 0.1589
gas/liquid ratio ft3/barrel Nm3/m3 0.178
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2 FLUID TYPES AND CORROSIVITY CLASSES
2.1 Fluid types
The following types of fluids are considered in this specification:
fluid types abbreviation
liquid hydrocarbons and multiphase systems I.L.

gas and gas with condensates I.G.
glycol G.
sea water A.M.
fresh waters A.D.
brackish waters A.S.
formation waters A.F.
The above listed types of fluids do not obviously cover the whole range of the
fluids met in oil and gas production plants, but only the main categories.
Particularly, all the fluids for decarbonation and desulphuration treatment are
excluded, as well as all chemical additives (corrosion inhibitors, fluidizers,
etc.).
2.1.1 Liquid hydrocarbons and multiphase
These fluids include oil, alone or in combination with gas phase and water
phase.
2.1.2 Gas and gas condensate
These fluids include gas, alone or in combination with condensates or water.

Reference is particularly made to fluids coming from dry gas and gas
condensate reservoirs.
2.1.3 Glycol
Reference is made to pure glycol, water and glycol mixtures, in gas dehydration
units and injected to prevent hydrate formation in gas lines.
2.1.4 Waters
They include all types of industrial water met in oil and gas production, and in
particular: fresh, brackish, formation and sea waters.
Fresh waters are usually shallow waters (from rivers or lakes) or waters from
shallow formations. Drinkable waters are characterised by a salinity below 1.5
g/l.
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Sea water has a salinity of 35 g/l, but locally can assume very different values.
Formation waters (brines) produced along oil and gas, are characterised by high
salinity. Sometimes they require to be re-injected into the formation, often after
an adequate corrosion control treatment.
The following criteria are used to define the different kinds of waters:
Fresh waters - A.D.

− shallow waters
− TDS < 2.0 g/l
Brackish waters - A.S.

− shallow waters
− TDS > 2.0 g/l
Sea waters - A.M.

− TDS ≅ 35 g/l
Formation waters - A.F.

− reservoir waters (deep formations)
− TDS > 2.0 g/l
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2.2 Corrosivity classes
For each type of fluid, the following corrosivity classes are identified:
type class properties
I.L. I.L.N. non containing CO2 or H2S

I.L.C. containing CO 2
I.L.S. containing H 2S
I.L.CS. containing CO 2 and H2S
I.G. I.G.N. non containing CO 2 or H2S

I.G.C. containing CO 2
I.G.S. containing H 2S
I.G.CS. containing CO 2 and H2S
G. G.N. non containing CO 2 or H2S

G.C. containing CO 2
G.S. containing H 2S
G.CS. containing CO 2 and H2S
For waters in general (A.), the following corrosivity classes are defined:
type class properties
A. deaerated non containing O 2

aerated containing O 2
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3 CORROSION PARAMETERS
3.1 Foreword
Corrosivity assessment of the fluids is carried out considering a set of corrosion

parameters regarding the fluid itself and the operating conditions.
3.2 Temperature
Temperature has a complex effect on corrosion rate, increasing or decreasing

the aggressiveness of a fluid in different ways; the following effects are
mentioned:
− increase of the kinetics of corrosion reactions as the temperature rises;
− inhibition, as temperature rises, of the susceptibility to hydrogen
embrittlement in presence of H 2S;
− formation of protective corrosion products (for example FeS, FeCO 3 or
CaCO3) at high temperatures.
Operating temperature values, T, shall be collected, as well as maximum fluid

temperature, T max, and minimum temperature that the system or the examined
component can reach, also considering temperature of external environment.
Minimum temperature, T min, can be a key factor in selecting the proper
materials because of its effects on the resistance to brittle fracture.
3.3 Pressure
Partial pressure of gas corroding agents in water phase, as CO 2, H2S, O2

depends on total pressure P.
3.4 Water content
Water content in production fluids is a key factor in determining the actual

water wetting conditions on metallic walls. It can be expressed as:
− water cut percentage, WCUT, in m³/m³ %, that is water volume on total
volume of liquid phases,
− water oil ratio percentage, WOR, in m³/m³ %, that is water volume on total
volume of hydrocarbons in liquid phase
In liquid hydrocarbons and in multiphase systems water is present as formation

water; in gas systems water can be present as condensation water or formation
water dragged from the reservoir. In the latter case water has a high salinity.
Water is always associated to gas from reservoir.
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Conservatively, a gas whose temperature is at least 10 °C above its dew point

temperature, is considered non corrosive because of the absence of liquid water
phase.
3.5 Gas Oil Ratio
Gas Oil Ratio, GOR, is referred to the standard conditions (1 bar - 0.1 MPa and
25°C) and it is expressed as Nm³ (gas)/m³(oil).
Systems with high GOR show a high turbulence with probable contact between
the gas and the water phases with metallic walls.
3.6 Hydrodynamic conditions
For monophase fluids, gas or liquids, flowing in a pipe, the average flow rate
can be defined as ratio between flow and cross section of the pipe.
In multiphase systems, it is useful to define the surface flow rate as the velocity
that each phase would have if it flew alone through the entire section of the
tube. Surface velocity in multiphase systems, through horizontal or vertical
pipes, allows to determine the type of flow pattern.
Hydrodynamic conditions affects corrosion in the following modes:

− effects on phase transportation: high turbulence conditions, particularly in
correspondence of geometrical discontinuities (for instance protuberant
weld head), cause local water separation; on the other hand, stagnating
conditions or low flow rates promote water separation from oil;
− effects on transport phenomena in solution: turbulence affects mass
transport of corrosion reactions reagents and products;
− decrease in corrosion inhibitor efficiency in high flow rate conditions;
− mechanical effects in removing protective deposits (corrosion products or
scales) on metallic surfaces;
− mechanical abrasion effects on metallic walls in sand or solid particles
containing fluids.
The mentioned effects need, in the most complex cases, an evaluation to be

carried out by both corrosion and hydrodynamics experts.
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3.7 CO2 molar fraction
To evaluate the CO 2 corrosion, and to calculate the partial pressure, CO 2

content in the gas phase expressed as molar fraction, yCO 2.
The CO2 content in the gas phase can also be approximately expressed as
weight percent.
The CO2 partial pressure, pCO 2, is calculated as:
pCO2 = P ⋅ yCO2
For higher pressures, roughly above 100 bar (10 MPa), the fugacity, f, is used
to calculate partial pressure:
pCO2 = f ⋅ yCO2
3.8 H2S molar fraction
The H2S content is expressed as molar fraction in the gas. In ideal gas, molar
fraction and volume percentage are the same.
As in CO2 case, H2S molar fraction is used to estimate the H 2S partial pressure
as:
pH2S = P ⋅ yH2S
For higher pressures, roughly above 100 bar (10 MPa), the fugacity, f, is used
to calculate partial pressure:
pH2S = f ⋅ yH2S
3.9 API Grade
API grade, or API gravity, is a measure for fluid density (oil, water, natural gas)
(ASTM D 287-92). It is calculated with the following expression:
141, 5
° API = − 131, 5
γ
with:
γ = specific gravity at 15 °C.
Water has an API grade 10°, as raw oil's, while crude oil has values ranging
from 6° (very heavy) to 60° (very light). Usually oils range from 25° to 35°
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API grade. Oils are considered light when they have API grade values between
35° and 45°, and heavy when API grade is below 25°.
3.10 Water chemical analysis
To correctly evaluate corrosivity, a complete chemical analysis of the water

phase is required. Along the analysis all information regarding sampling
procedures shall be retained.
Some chemical composition parameters have primary importance and are

reviewed here below.
Total salinity
It is the solid residue after boiling, expressed in g/l.
High salinity, especially in presence of oxygen, enhances localised corrosion

forms, promoting separation between anodic and cathodic areas, and galvanic
coupling effects.
pH
pH has a significant effect on water corrosivity, through the hydrogen evolution

reaction; precipitation equilibria of protective scales also depend on pH.
In aqueous phase associated with hydrocarbon production pH, is determined by

the solubility equilibria of acid gas as CO 2 and H2S (and the following
dissociation and reaction equilibria). pH measurements at operating conditions,
called pH in situ, pH in-situ , have intrinsic difficulties. To obviate to this problem
some software programs based on temperature, pressure and water composition
are available to calculate the pH in situ (for instance “ CORMED” program
developed by ELF).
Acid environments (pH < 6) are more corrosive than neutral pH (from 6 to 8) or
alkaline (pH > 8) ones. Alkaline fluids with pH above 11-12 are not considered
corrosive for carbon steel.
Chlorides
Chlorides concentration affects localised corrosion forms, mainly through the

depassivation effect caused by chloride ions, especially with stainless steels.
Oxygen
Oxygen is dissolved in waters contacting with the atmosphere. It is absent in

reservoir fluids. Whenever oxygen is afterwards introduced into the fluid, i.e.
by contact with the atmosphere or through faulty seals or because it is
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contained in additives, its effect on corrosivity shall be carefully evaluated. In

H2S containing fluids, oxygen may cause H 2S oxidation to elemental sulphur,
tiosulphates etc., thus producing an aqueous phase acidification.
Organic acids
Organic acids (formic HCOOH, and acetic CH 3COOH) are often present in
production fluids containing CO 2. Their presence shall be considered in water
pH calculations.
Elemental sulphur
Elemental sulphur, that can be found in some reservoir, often in combination

with H2S, is a strong oxidant and it is extremely aggressive also for corrosion
resistant alloys.
3.11 Sulphates-reducing bacteria
Sulphates-reducing bacteria (SRB) grow in anaerobic conditions in presence of

sulphates ions, that are reduced to sulphides. The microbial corrosive attack is
characterised by formation of black deposits of sulphides-containing corrosion
products on the metal.
Bacteria are present in soil, natural waters and mud; they are not normally
found in hydrocarbon reservoirs, unless they are introduced there, for example,
during drilling or through water injection systems.
3.12 Sand and suspended solids
The presence of sand and suspended solids in the fluid causes erosion of
metallic surface, at a rate that depends on flow rate and density of the fluid and
on quantity, density and morphology of the solids present in the fluid.
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4 CORROSIVITY CLASSES
4.1 Liquid hydrocarbons and multiphase systems (I.L.)
Liquid hydrocarbons and multiphase systems are classified according to the

following corrosion parameters:
− CO2 partial pressure;
− H2S partial pressure;
− maximum and minimum operating temperature;
− water cut percentage or water oil ratio percentage;
− gas oil ratio;
− total salinity and/or chloride content of the aqueous phase;
− average flow rate;
− elemental sulphur;
− oxygen;
− sand.;
− water chemical analysis;
− water pH-in-situ;
− water pH-in-air;
− API grade;
− sulphates reducing bacteria;
− flow pattern.
Liquid hydrocarbons and multiphase systems are classified according the

following criteria:
Non containing CO 2 and H2S, I.L.N.

pCO2 < 0.001 bar (0.0001 MPa), and
pH2S < 0.0035 bar (0.00035 MPa).
containing CO 2 I.L.C.
pCO2 > 0.001 bar, and
pH2S < 0.0035 bar.
containing H 2S I.L.S.
pCO2 < 0.001 bar, and
pH2S > 0.0035 bar.
containing CO2 and H2S I.L.CS.

pCO2 > 0.001 bar, and
pH2S > 0.0035 bar.
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4.2 Gas hydrocarbons and gas with condensates
Gas hydrocarbons and gas with condensates are classified according to the
following parameters:
− maximum and minimum operating temperature;
− water cut percentage or water oil ratio percentage;
− total salinity and/or chloride content of the aqueous phase;
− elemental sulphur;
− average flow rate of the fluids;
− oxygen;
− sand and suspended solids;
− water chemical analysis;
− water pH-in-situ;
− water pH-in-air;
− sand;
− flow rate;
− sulphates reducing bacteria.
Gas hydrocarbons and gas with condensates are classified according the
following criteria:
Non containing CO 2 and H2S, I.G.N.

pCO2 < 0.001 and
pH2S < 0.0035
containing CO2 I.G.C.

pCO2 > 0.001 and
pH2S < 0.0035
containing H 2S I.G.S.
pCO2 < 0.001 and
pH2S > 0.0035
containing CO2 and H2S I.G.CS.

pCO2 > 0.001 and
pH2S > 0.0035
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4.3 Glycol
Glycol are classified according to the following corrosion parameters:

− water percentage;
− operating temperature;
− dissolved oxygen;
− water salinity;
− sand and suspended solids;
− pH.
The eventual presence of oxygen, i.e. from contact between glycol and
atmosphere, with water presence in glycol, causes a high corrosivity, even
when there is no CO 2 or H2S.
Similarly to gas hydrocarbons, liquids and multiphase systems, glycol are

classified according the following criteria:
Non containing CO2 and H2S G.N.

pCO2 < 0.001 and
pH2S < 0.0035
containing CO 2 G.C.
pCO2 > 0.001 and
pH2S < 0.0035
containing H 2S G.S.
pCO2 > 0.001 and
pH2S < 0.0035
containing CO2 and H2S G.CS.

pCO2 > 0.001 and
pH2S > 0.0035
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4.4 Waters
Waters are classified according to the following corrosion parameters:

− dissolved oxygen;
− pH;
− H2S content;
− operating temperature;
− total salinity aqueous phase;
− sulphates reducing bacteria;
− hydrodynamic conditions;
− chemical analysis;
− conductivity.
Waters are classified according to the following corrosivity classes
deaerated waters
cO2 <0.010 mg.l -1 (10 ppb)
deaerated waters
cO2 <0.010 mg.l -1 (10 ppb)
The following conditions are individuated for waters:
waters with low pH: 3 < pH < 6

waters with high pH: pH > 6
H2S containing waters; H2S < 1 mg.l -1 (1 ppm)
H2S non containing waters; H2S < 1 mg.l -1 (1 ppm)
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5 CORROSION FORMS
5.1 General
5.1.1 Foreword
In this section the most common corrosion forms occurring in oil and gas
production are reviewed.
For each corrosion form, the relevant definitions are reported and the criteria to
predict corrosivity are illustrated.
5.1.2 Materials
The main metallic materials families utilised in oil industry are the following:
− carbon steels
− low alloy steels
− stainless steels
− ferritic
− martensitic
− austenitic
− ferritic-austenitic (duplex)
− nickel alloys
− cobalt alloys
− titanium and titanium alloys.
Stainless steels, nickel and cobalt alloys and titanium are generally defined
CRA, which stands for “corrosion resistant alloys”.
5.1.3 Corrosion morphologies
Corrosion forms can be divided into the following fundamental types,

according to the morphology of the attack:
general corrosion: it occurs on the whole surface of the metal in contact with
the environment; it can be uniform, with a generalised and regular loss of metal
on the exposed surface, or non uniform, with corrosion penetration varying
from area to area.
localised corrosion: it happens in a limited portion of surface in contact with the

environment. The morphology of localised corrosion changes considerably,
depending on material and environment. The entity of the damage does not
depend on the total quantity of oxidised metal.
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The following classes can be used for to express the penetration rate of general
corrosion forms:
− negligible <50 µm/y
− low 50-100 µm/y
− moderate 100-500 µm/y
− severe 500-1000 µm/y
− very severe >1000 µm/y
5.2 Water wetting conditions
Below 400 °C corrosion can occur:

– in presence of liquid water and
– if water is, even only temporarily, in direct contact with the metallic
surface;
those conditions define the water wetting of the metallic surfaces.
Water stabilises ionic species in solution that participate, as reagents, products

or intermediates, in the electrochemical corrosion reaction, and it activates local
micro cells on metallic surfaces. In particular situations, other solvents such as
methanol, can acquit a similar function, even if with different effectiveness.
5.2.1 Liquid and multiphase systems
In multiphase systems corrosion is directly proportional to the fraction of time

the metal is microscopically wetted by the aqueous phase. In multiphase
systems, water separation and transportation of the aqueous phase in contact
with the metallic wall (wetting), depend on:
− nature of the phases and repartition;
− phases composition;
− hydrodynamics;
− geometry.
The content of formation water in crude oil is quite variable. When water
fraction is very low, below a few percents, the metallic walls are always oil-
wetted; when water is the pre-eminent phase, water wetting conditions prevail;
when water concentration is intermediate, there is an intermittent water wetting.
Local water wetting conditions can occur in presence of geometrical

discontinuities, which cause turbulence and water separation from the oil phase,
even if water content is quite low. Significant cases are extruding weld beads or
valves. In stagnant conditions, as in tanks or in horizontal pipes in laminar
regimen, where water phase spontaneously separates on the lower part of the
pipe or at the tank bottom, even a low percentage of water is enough to produce
water wetting conditions.
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5.2.2 Gas and gas with condensates system
In gas and gas with condensates reservoirs, gas is saturated with water, in
equilibrium with the liquid water in the reservoir. During production, the gas
expands and cools: when it reaches the water dew point, water starts to
condensate from gas; gasoline, when present, can condensate before or after
water condensation.
Without reliable information on the presence of water or on condensation

conditions, it is convenient to assume that an aqueous phase is always present
in contact with the metallic surface. On the contrary if operating temperature is
at least 10 °C above the water dew point temperature, the presence of liquid
water can be excluded.
Beyond condensation water, also formation water, mechanically dragged by the

gas can be produced. In case of condensation water, salinity is very low, while
in formation waters it can be quite high; usually the most common situation is
an intermediate one, with a water composition diluted in comparison to
formation water, due to condensation water.
Water is conventionally assumed to be a formation water when the ionic

strength is higher than 0.5.
Water, depending on hydrodynamic conditions, can be present as small drops

dispersed in the gas or as a liquid film that wets the walls while flowing,
dragged by the gas. The thickness of the liquid film is tens or hundreds of
micron class, and decreases as the quantity of liquid produced decreases and as
the gas flow rate increases. Corrosion rate presumably increases as the
thickness of the liquid film and its flow rate increase.
The liquid film can be constituted by water, hydrocarbons or a mixture of both.

In the last case, water wetting depends on the quantity of the produced water,
and, in particular, by the water fraction in the liquid.
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5.3 O2 corrosion
Oxygen corrosion of carbon and low alloy steels occurs in aerated

environments as general corrosion. Corrosion rate is directly proportional to the
amount of oxygen available at the metal solution interface, i.e. the oxygen flux.
This depends on:
1. environmental conditions:
- oxygen concentration;
- hydrodynamic conditions:
- temperature.
2. the steel surface conditions.
In stagnant aerated water and at room temperature, corrosion rate, expressed in

µm/y, is about 20 times the oxygen concentration expressed in ppm.
In non-stagnant conditions this value shall be multiplied by a factor

approximately equal to the square root of the flow rate (in m/s) for laminar
flow, and equal to the flow rate (in m/s) for turbulent flow.
In aerated waters with flow rate above 1 m/s and temperature above 30°C, the
following equation can be applied to predict corrosion rate of carbon and low
alloy steels:
vcorr = 0.020 ⋅ cO2 ⋅ 2(T-30)/30 ⋅ vn
where:
− vcorr corrosion rate, µm/y
− cO2 oxygen concentration, ppb
− v flow rate, m/s (it is assumed to be v=1 if v<1)
− T temperature, °C
− n 0.5 for laminar flow and 1 for turbulent flow.
In deaerated waters, with oxygen concentration below 10 ppb, the following

formula has been proposed by Oldfield et al. to predict oxygen corrosion rate in
steel pipes:
v’corr = 5.29 ⋅ cO2 ⋅ (v7/d)1/8 ⋅ exp(T/42.6)
where:
− v'corr corrosion rate, µm/y
− cO2 oxygen concentration, ppb
− v flow rate, m/s
− T temperature, °C
− d internal diameter of the pipe, m.
The predicted values v’ corr, represent the maximum corrosion rates occurring on
steel surface in absence of any protective products. The actual corrosion rate,
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after formation of partially protective scales, is approximately an order of

magnitude lower.
5.4 H2S corrosion
H2S promotes localised corrosion forms on carbon and low alloy steels.
The maximum corrosivity occurs when the content of H 2S in solution is

between 100 and 1000 ppm, approximately corresponding to 0.02-0.2 bar
(0.002-0.02 MPa). At 60°C, the penetration rate can be as high as 1 mm/y; at
higher temperatures corrosion rate decreases, but the risk of localised corrosion
increases.
Localised corrosion is enhanced by the galvanic coupling effect between steel

and iron sulphide corrosion products: iron sulphide, in fact, is an electronic
conductor and it behaves cathodically with respect to steel.
5.5 Elemental sulphur corrosion
Elemental sulphur is present in a few reservoirs, often combined with H 2S.
Sulphur is a strong oxidant: at a low temperature (<120°C), elemental sulphur

reacts with carbon or low alloys steels, or with their oxides, to form sulphides.
At normal temperature, in presence of chlorides, general corrosion rate is very
severe, even above 20 mm/y. As temperature increases, corrosion rate grows,
but not by orders of magnitude. At temperatures above 120°C corrosivity grows
in relation to H 2S, sulphuric acid (4S+4H 2O=3H2S+H2SO4) and polysulphanes
(H2Sx) formation. Above 150 °C there is a decrease of the corrosion due to
partially protective scales; however corrosion rate remains very high (8-10
mm/y a 180°C).
Corrosion rate increases sensibly in presence of salts like NaCl and Na 2SO4 and
it is substantially independent from presence of H 2S.
CRA in presence of elemental sulphur are susceptible to localised attacks. Low

nickel austenitic stainless steels (AISI 304) and austenitic-ferritic stainless
steels are particularly sensible to elemental sulphur presence, with corrosion
rates as high as those ones observed on carbon steels and low alloy steels.
Corrosion resistance to elemental sulphur increases in high alloyed material:
nickel, chromium and molybdenum have a beneficial effect; high nickel
austenitic stainless steels, nickel alloys and cobalt alloys can be susceptible to
localised attack, as pitting, crevice or stress corrosion cracking, in particular
above 150°C and in presence of chloride ions.
Nickel-chromium-molybdenum alloys with Ni>50%, Mo>12% and Cr>15%

are resistant to elemental sulphur corrosion.
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5.6 CO2 corrosion
CO2 is one of the main corroding agents in oil and gas production.
CO2 corrosion occurs with quite different morphologies, often designed with
specific terms as: “mesa corrosion”, “pitting corrosion”, “ring worm corrosion”.
Prediction of CO 2 corrosion is based on the following parameters:

− water phase composition;
− pH;
− temperature;
− hydrodynamic conditions
− presence of H 2S.
5.6.1 Effects of chemical species in solution
Chemical composition of the water phase in contact with steel, has a great
influence on CO 2 corrosion rate, especially through the modification of local
pH (pHin-situ); corrosion rate, in fact, is negligible, or low, when pH in-situ is above
5.5-5.6.
The effect of the main chemical species that influence the phenomenon are
briefly reviewed here below.
Bicarbonates. In waters with high alkalinity (HCO 3- = 30÷150 meq/l), corrosion

rate is low or moderate. Also the Ca 2+/HCO3- ratio affects the water
aggressiveness: in alkaline waters, with HCO 3->>Ca2+, corrosion rate is low or
moderate as above said; when Ca 2+/ HCO3- is high (>1000 meq/meq), pH is
low, but corrosion results uniform, since separation of anodic and cathodic
areas cannot occur. Furthermore, when the content of Ca 2+ ions in solution is
high, precipitation of a protective layer of CaCO 3 can occur in relation to local
pH conditions.
Acetates. Several reservoir fluids contain volatile organic acids, in particular

acetic acid (CH 3COOH). With the term “acetates”, the sum of all organic acid
in solution, expressed as meq/l, is normally intended; when bicarbonates are
determined through titration, a part of acetates is expressed as bicarbonates.
According to some authors, CO 2 corrosion depends on the acetate concentration

in solution; in particular CO 2 corrosion is predicted to be low when the acetates
content is low (<1 meq/l).
Presence of acetates affects the equilibria that determine the pH in-situ; moreover
acetates are strong complexant and, from this viewpoint, they could be an
obstacle to the formation of protective corrosion products.
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Fe2+ ions. The contamination of Fe 2+ ions, coming for instance from steel
corrosion, causes an increase of pH (compared with the pH determined by CO 2
dissolution alone) due to the formation of FeCO 3 and Fe3O4. Corrosion
products, through the modification of pH, affect corrosion rate, with a decrease
effect.
Variation of pH, when Fe 2+ saturation conditions are reached, is between 0.5

and 1.6. The saturation pH for FeCO 3 and Fe3O4 can be calculated as a function
of temperature and CO 2 partial pressure data.
H2S. Presence of H 2S in solution, even in very small quantities, highly modifies

the chemistry of the solution and the corrosion behaviour of steels. The
formation of a protective film of iron sulphide, FeS, passivates the steel thus
reducing its corrosion rate. However the risk of localised corrosion (pitting ) is
higher: iron sulphide, in fact, is an electronic conductor and causes an increase
of free corrosion potential.
5.6.2 De Waard and Milliams model.
Base equation. In presence of water with a very low salt content (i.e.
condensation water) CO 2 corrosion rate can be calculated with the De Waard
and Milliams base equation.
1710
Log( v corr ) = 5.8 − + 0. 67 ⋅ Log( pCO2 )
T
where:
− vcorr corrosion rate in mm/y;
− T temperature in °K;
− pCO2 CO2 partial pressure in bar;
− Log logarithms are decimal.
At high pressure, approximately above 100 bar (10 MPa), the ideal gas model
is not applicable and fugacity shall be used instead of pressure in calculating
the CO2 partial pressure.
Fugacity is calculated from pressure through the fugacity coefficient “a”:
f=a⋅P
The values of corrosion rate predicted by the base equation are often much
higher than the corrosion rates actually observed. For this reason, some
correction factors have been introduced to take into account of specific effects
on corrosion rate.
Formation of protective corrosion products . Above a certain temperature,

named scaling temperature (T scale), the actual corrosion rate is lower then
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predicted by the base equation due to formation of protective corrosion

products effects, provided that hydrodynamic conditions do not cause their
removal.
The scale temperature, T scale, is given by the following equations:
2400
Tscale (K) =
6.7 + 0.6 ⋅ Log(fCO2)
and the correspondent multiplying factor, F scale, is:
2400
Log(Fscale) = − 0.6Log(fCO2 ) − 6.7
T
The new corrosion rate, v’ corr , is:
v’corr = vcorr ⋅ Fscale
Fe2+ and pH effect. As previously seen, in absence of other buffering chemical

species, contamination of the solution with Fe 2+ ions causes, at constant
temperature and CO 2 partial pressure, a reduction of corrosion rate, connected
to a local pH variation.
When the scaling factor, F scale, is not applicable to modify (i.e. reduce) the
corrosion rate calculated by the base equation (T < T scale or Fscale = 1), the pH
effect is considered as shown here below.
The saturation pH, pH sat, for Fe3O4 and FeCO 3, is calculated with the following
equations:
1307
pHsat = 136
. + − 017
. Log(fCO2 )
T
corresponding to the formation of Fe 3O4, and:
pHsat = 5.4 − 0.66Log(fCO2 )
corresponding to the formation of FeCO 3.
The corrosion product with the lowest saturation pH is the most stable and that
one with the highest probability of formation.
The following parameter is then defined:
∆pH = pHsat - pHin-situ
and the correction factor F pH is calculated through the following procedure:

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if: pHsat ≥ pHin-situ:
Log(FpH ) = 0.32(pHsat − pHinsitu)
if: pHsat < pHin-situ
Log(FpH ) = −0.13(pHinsitu − pHsat )1.6
In fluids containing CO 2 and small quantities of H 2S, the following expression

has been proposed for F pH:
FpH = 1 -0.34 ⋅ ∆pH
The new corrosion rate, V” corr , corrected for pH is then calculated as:
V”corr = Vcorr ⋅ FpH
Effect of glycol. In presence of glycol and in oxygen free environments, a

significant reduction of corrosion rate is observed, as a consequence of an
inhibition effect.
The relevant correction factor for the corrosion rate calculated from the base
equation A.1. is given by the following formula:
Log(Fglyc ) = A ⋅ (Log(W%) − 2)
where:
− W% is the weight percentage of water in the glycol;
− A is a constant which depend on type of glycol; it is
normally
assumed A=1,6.
The correction is applicable for a water content above 10% in weight; the
corrected corrosion rate, V’” corr , is given by:
V”’corr = Vcorr ⋅ Fglyc
5.6.3 Top of line corrosion
It can occur in pipes where the gas phase flows over a liquid water vein. On the
upper side, condensing water is saturated by CO 2 eventually present: corrosion
rate in this situation, where the efficiency of corrosion inhibitor may result
limited, depends on the rate of water condensation from gas.
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If the fluid flow in the conduct is slug type, the passage of liquid slugs modifies
favourably the pH of water (removing or diluting the condensation water film)
and eventually filming the metallic wall with liquid hydrocarbons.
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5.6.4 Prediction rules for CO 2 corrosion (Crolet Model)
A completely different approach to predict the corrosivity of CO 2 containing

fluids has been proposed by Crolet for corrosion in oil and gas wells. The
predictive model is part of a software program, named “ CORMED”, (by the
same author) for the calculation of in-situ pH.
Prediction of corrosivity is expressed using the following classes of corrosion-

risk:
− very low;
− medium;
− high.
No corrosion rate values are associated to such classes, but reference is made to
an approximate operating life, which is considered acceptable, equal to 8-10
years.
The rules to predict the risk of CO 2 corrosion consider the following

parameters:
− type of produced water, formation or condensation;
− in-situ pH;
− potential corrosivity (PC): it is a parameter which can be calculated with
“CORMED” program; alternatively, corrosion rate calculated with the base
equation of De Waard and Milliams model can be used;
− in situ acetic acid content;
− Ca2+/HCO3- ratio.
The prediction rules are reported here below.
Condensation water
corrosion risk is very low if:

− pCO2 < 0.05 bar (0.005 MPa) or
− PC < 0.2 mm/y or
− pCO2 < 0.2 bar (0.002 MPa) and in situ acetic acid < 0.1 meq/l
corrosion risk is medium if:

− 0.2 < pCO 2 < 5 bar (0.02<pCO 2<0.5 MPa) and in situ acetic acid< 0.1 meq/l
in every other condition the corrosion risk is high
formation water
corrosion risk is very low if:

− pCO2 < 0.05 bar (0.005 MPa) or
− PC < 0.2 mm/y or
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− in situ pH > 5.6 or

− 0.05 < pCO 2 < 10 bar (0.005<pCO 2<1 MPa) and in situ acetic acid < 0.5
meq/l
corrosion risk is medium if:

− PC < 1 mm/y
− in situ acetic acid < 0.1 meq/l
2+ -
− Ca /HCO3 < 1000
in every other condition the corrosion risk is high.
5.6.5 Corrosion products
Prediction of corrosion products on steel in CO 2 containing fluids may prove

useful for predicting the morphology of the corrosion attack. The following
criteria are applicable:
− T<60°C and pCO 2 < 5 bar (0.5 MPa): formation occurs of amorphous FeCO 3
with scarce adherence;
− 60°<T<100°: formation of a protective layer of FeCO 3 occurs;
− T>100°: the layer increases considerably its protectiveness and formation of
Fe3O4 occurs.
The protective effect of corrosion products is strictly related to hydrodynamic

conditions.
5.7 Galvanic corrosion
Galvanic corrosion occurs when metallic materials with different nobility -

different electrochemical potential - are in electrical contact and exposed to an
aggressive environment. On less noble metal - the one with the most negative
potential - accelerated anodic corrosion processes take place, while the more
noble metal becomes a cathode, without corroding.
The presence of galvanic coupling gives place to an increase in corrosion rate

or to localised corrosion only if the environment is corrosive and with sufficient
electric conductivity. Corrosion rate of the less noble metal of the couple results
higher compared to the one exhibited by the same metal if uncoupled; the
intensification factor depends on the ratio between the two metal surfaces.
Depending on the configuration of the aqueous phase, if it is present as a layer

or as a bulk, the coupling is possible between anodic and cathodic areas
geometrically separated: the higher are the water phase conductivity and the
available cross section of the flux tubes, the higher is the distance between
electrically coupled areas.
Galvanic contact effects can also occur between metal and scales, fragments or
corrosion products with electronic conductivity It is the case, for instance, of
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magnetite scales or of iron sulphide corrosion products, both showing a

cathodic behaviour with respect to carbon or low alloy steel.
Severe situations of galvanic contact can be observed in salt waters, with high
conductivity and aerated, as for instance sea water.
Negative effects can be observed also on the more noble metal. This is the case
of coupling between CRA (stainless steel or nickel alloy) with carbon or low
alloy steel in deaerated environments, where the main cathodic reaction is
hydrogen evolution: hydrogen embrittlement is possible on the more noble
metal if it is susceptible; low temperatures and presence of H 2S promote these
situations.
The following table summarises the different situations.
environment (T) galvanic coupling effects
carbon steel - anode CRA - cathode
Ecorr less noble Ecorr more noble

low temperature − general corrosion − hydrogen
(< 60 °C) − pitting and crevice embrittlement
medium-high − general corrosion − cathodic protection
temperature − pitting and crevice
(> 60 °C) − stress corrosion
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5.8 Pitting and crevice
Pitting and crevice are localised corrosion forms typical of metals showing an
active-passive behaviour, characterised by formation of a galvanic macro-cell
between a passive area of the metal, where the cathodic process takes place,
and an active one, where anodic dissolution occurs.
The surface fraction interested is always very low, compared to the total
exposed area.
In pitting corrosion, the anodic area is the bottom of the pit, while in crevice
corrosion it is the shielded metal surface within the crevice.
5.8.1 Susceptible materials
The susceptible materials are those ones that normally operate in passive
conditions; in particular:
− stainless steels;
− nickel alloys;
− copper alloys;
− titanium alloys (crevice corrosion).
To express comparatively the pitting resistance of nickel alloys and of stainless

steels, in particular the austenitic and austenitic-ferritic types, specific indexes
have been proposed, based on alloy composition.
The index named P.R.E. (Pitting Resistance Equivalent) is calculated according

to the chemical composition, and in particular to the content of Cr, Mo and N,
as:
P.R.E. = Cr% + 3.3 Mo% + 16N%
Another formula has also been proposed which takes into account of the
presence of tungsten in the alloy:
P.R.E. = Cr% + 3.3 (Mo% + 0.5W%) + 16N%
For crevice corrosion, the following index, named “Critical Crevice Index”,
C.C.I., has been proposed:
C.C.I. = Cr% + 4.1Mo% +27N%
The pitting and crevice indexes are often utilised as absolute values, but the
most appropriate use is as ranking parameters of different materials.
Another evaluation parameter is the critical pitting temperature (C.P.T.)

experimentally determined by immersion tests in FeCl 3 (see ASTM G48-76) or
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by electrochemical methods. A good relationship between C.P.T. and P.R.E.

has been found for austenitic and austenitic-ferritic stainless steels.
In the same way, critical crevice temperature (C.C.T.) is determined for crevice
corrosion.
5.8.2 Initiation conditions
Initiation of pitting and crevice corrosion occurs in presence of chloride ions in

solution. 200 ppm is the threshold for chloride ions concentration to avoid risks
of pitting or crevice initiation of austenitic stainless steels (types AISI 304 and
316).
Availability of a cathodic process, i.e. oxygen reduction; hydrogen evolution;

elemental sulphur reduction, is needed for propagation to occur.
Hydrodynamic conditions have a great influence on pitting initiation: AISI 316

stainless steel, for instance, is resistant to pitting corrosion in sea water
provided that flow rate is above 1.5 m/s, while in stagnating conditions pitting
corrosion occurs.
Temperature has a strong influence too: tendency to pitting and crevice

increases as temperature increases.
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5.9 Stress Corrosion Cracking (SCC)
In addition to stress corrosion in presence of H 2S (SSC), the following types of

stress corrosion cracking can take place in oil and gas production plants:
− SCC of stainless steels in chloride containing environments;

− SCC in presence of polythionic acids.
5.9.1 Chlorides stress corrosion cracking
It concerns mainly the austenitic stainless steels of the 300 series (i.e. AISI 304
and 316), austenitic-ferritic stainless steels are also susceptible, while nickel
alloys are practically immune.
Austenitic stainless steels. SCC in austenitic stainless steels type AISI 304 and
316 is observed in the following conditions:
o
− T > 60 C;
-
− Cl >10 ppm;
− applied or residual stress state, σ > 150 MPa (σ > 30% σYS).
With respect to temperature and chloride concentration, which are the most
influencing parameters, the following limits can be assumed for stainless steels
type AISI 304 or 316:
o
− T < 50 C Cl- concentration without limits
o
− 50 < T <100 C Cl- < 100 ppm
o
− 100 < T < 150 C Cl- < 30 ppm
o
− T > 150 C Cl- < 10 ppm
However, the indicated limits for Cl - concentration have to be used very

carefully, because of unexpected local concentration phenomena. practically,
the use of austenitic stainless steels is recommended only for temperature below
50 oC.
Austenitic stainless steels characterised by a higher nickel content (above 15%)

show a resistance to SCC which increases as the content of alloying elements
increases.
Other influencing parameters are:

− content of dissolved oxygen in solution: it reduces the time to failure;
− pH: low pHs reduce the time to failure (it shall be mentioned that below pH
2 general corrosion prevails and the conditions for SCC, that is coexistence
of active and passive surfaces, vanish);
− stress state: high applied or residual loads determine a reduction of the time
to failure;
− cold-working: it has a beneficial effect until a certain degree of cold working
has been reached (around 20%), after which the susceptibility to SCC
increases sensibly;
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− alloying elements: the nickel content (above 10%) has a beneficial effect;
other beneficial elements are: silicon (the effect is quite evident above 2%)
and carbon (above 0.10%); the harmful elements are: phosphorus and
nitrogen, which that have a synergetic negative effect; their content shall be
limited: P < 0.005% and N < 0.02%;
− welds are preferential sites for SCC initiation because of residual stress
conditions and because of their own criticality.
Ferritic and martensitic stainless steels . Stainless steels with ferritic or

martensitic microstructure are less susceptible to stress corrosion, although not
immune, because of the low nickel content (Ni < 1%). The low nickel content,
in fact, leads to a lower stability of the passive film and promotes uniform
corrosion.
Austenitic-ferritic (duplex) stainless steels . Biphasic austenite-ferrite stainless

steels offer higher resistance to SCC, compared to ferritic and austenitic types.
The optimum resistance conditions are obtained when the two phases are
present in balanced quantities an for the highest nickel contents.
Nickel alloys. Nickel alloys are quite resistant to chloride stress corrosion;
alloys with nickel contents above 45% are practically immune.
5.9.2 Polythionic Acids Stress Corrosion Cracking
In correspondence to the periodical shut down of the plants, because of

entrance of air and humidity, polythionic acids (H 2SxO6 with x = 3, 4 or 5) can
form by oxidation of iron sulphide:
8FeS + 11O 2 + 2H2O = 4Fe2O3 + 2H2S4O6
Polythionic acids stress corrosion has been found mostly in refinery plants, and
particularly in desulphuration units. Austenitic stainless steels, especially if
sensitised, are quite susceptible. Failure occurs by crack formation, mostly
intergranular; transgranular cracks may be present, caused by chlorides.
Austenitic-ferritic stainless steels are more resistant than austenitic types; nickel
alloys (800 and 600 series) do not seem to be prone to the phenomenon.
Prevention is based on operation control in correspondence to the plant shut

downs, for instance foreseeing nitrogen conditioning of the equipment to
prevent sulphide oxidation.
Recommended materials are stabilised stainless steels (AISI 321 and 347) and
weld stabilisation heat treatments (900 oC for at least 20 minutes).
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Sheet 42
5.10 Sulphide Stress Cracking (SSC)
Sulphide Stress Cracking (SSC) occurs on susceptible materials when specific

environmental conditions are met, characterised by presence of H 2S and
mechanical stresses, applied or residual.
In oil and gas production, sour service are defined those conditions that give
place to SSC on susceptible materials, in particular carbon or low alloy steels.
In sour service conditions SSC resistant materials shall be selected.
5.10.1 Sour service conditions according to NACE
With reference to the NACE MR0175 Standard, sour conditions are defined as
follows:
gas systems (see also fig. 1)

− P > 5 bar (0.5 MPa) and
− pH2S > 0.0035 bar (0.005 MPa)
multiphase systems (see also fig. 2)

− P > 20 bar (2 MPa) and pH 2S > 0.0035 bar (0.00035 MPa)
− 5 < P < 20 bar (0.5<P<2 MPa) and pH 2S > 0.65 bar (0.065 MPa)
− P < 5 bar (0.5 MPa) and yH 2S > 0.15
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02555.VAR.COR.PRG
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Sheet 43
1000
Sour Service
Total Pressure (bar)
100
10
1
0.0001 0.001 0.01 0.1 1 10
H2S molar fraction (yH 2 S) in gas fase (%)
Fig. 1. - Sour service conditions for gas systems according to NACE.
1000
Total pressure (bar)
Sour Service
100
10
1
0.0001 0.001 0.01 0.1 1 10 100
H2S molar fraction (yH 2 S) in gas fase (%)
Fig. 2. - Sour service conditions for multiphase systems according to NACE.
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02555.VAR.COR.PRG
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Sheet 44
5.10.2 Sour service conditions according to EFC
Definition of sour service conditions according to EFC takes into account also
the in-situ pH of the water phase; in-situ pH values can be calculated using
algorithms, nomograms or software programs, based on chemical analysis of
the aqueous solution.
According to EFC, the following fields are defined (see also fig. 3):
sour conditions
− pH ≤ 3.5
− pH2S < 0.01÷1 bar (0.001÷0.1 MPa) and pH ≤ 5.5 + log pH 2S (bar)
− pH2S > 1 bar (0.1 MPa) and pH ≤ 5.5
sour / non-sour transition zone

pH2S = 0.001÷0.01 bar (0.0001÷0.001 MPa) and 3.5 < pH ≤ 5.5 + log pH 2S
(bar)
pH2S > 1 bar (0.1 MPa) and pH = 5.5 ÷ 6.5
Conditions outside these ones are defined non-sour and also susceptible
materials can be used.
In sour service conditions, materials resistant to SSC shall be used.
Sour / non sour transition conditions are considered as sour.
7.5
6.5
"Non Sour Service" Transition Region
Solution pH
5.5
4.5
3.5 Sour Service
2.5
0.0001 0.001 0.01 0.1 1 10
Hydrogen Sulphide Partial Pressure (pH2S - bar)
Fig. 3. - Sour service conditions according to EFC
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02555.VAR.COR.PRG
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Sheet 45
5.11 Stepwise Cracking
The term Stepwise Cracking refers to metal damages which occur as surface
blistering or as formation of internal stepwise microcracks, even in absence of
mechanical solicitations. Other terms are often used, as “Stress Oriented
Hydrogen Induced Cracking”, “Blistering”, “Hydrogen Induced Cracking” to
describe the same phenomenon.
Formation of microcracks or blisters is caused by atomic hydrogen produced on

the corroding metal surface which, in presence of H 2S, diffuses into the metal
lattice. The atomic hydrogen eventually gathers in correspondence of inclusions
or segregation bands of the microstructure and recombines to molecular
hydrogen, producing a very high internal pressures and the mentioned metal
damages.
Materials susceptible to Stepwise Cracking are carbon and low alloy steels
produced by lamination and containing inclusions, and in particular C-Mn
steels with manganese sulphide inclusions, MnS type II.
5.11.1 Limits for initiation
The following limits are applicable for stepwise cracking initiation:

− pH2S > 0.1 bar (0.01 MPa);
− T < 80°C;
− pHin-situ < 6.
In case of fluids containing both CO 2 and H2S, the following limits applies (see
also fig. 4):
− pH2S > 0.1 bar (0.01 MPa) if pCO2 < 0.5 bar;
− pH2S > 0.1107-0.0214 ⋅pCO2 (bar) if 0.5 < pCO 2 < 5 bar;
− pH2S > 0.0035 bar (0.00035 MPa) if pCO2 > 5 bar.
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02555.VAR.COR.PRG
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Sheet 46
"Stepwise Cracking"
0.1 (T < 80°C - pH < 6)
H2S partial pressure (bar)
0.01
0.001
0.0001
0.01 0.1 1 10
CO2 partial pressure (bar)
Fig. 4 - Limits for initiation of Stepwise Cracking.
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02555.VAR.COR.PRG
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Sheet 47
5.12 Erosion corrosion
It is a corrosion form where there is the concurrence of electrochemical

corrosion with mechanical removal of the corrosion products caused by the
high flow rate.
It occurs on all the metallic materials. Whenever the aggressiveness conditions

are particularly severe it becomes necessary to make use of hard coatings with
high corrosion resistance, such as stellites or ceramics.
In absence of solid particles, corrosion-erosion initiates if the fluid velocity is

above a critical value. In API RP-14E the following formula is given for the
calculation of critical rate v c:
C
vc =
ρm
where:
− vc = erosion critical velocity
− C = erosion constant
− ρm = fluid density at operating conditions
The erosion constant can take different values depending on the material
(carbon steel or CRA), the type of service (continuous or intermittent) and the
inhibitor injection.
In the S.I. system, the units for the C constant are (kg/ms 2)1/2, while in the
American system units are (lb/fts 2)1/2 ; the conversion factor from the American
system to S.I. is 1.22.
The following values for the C constant, expressed here in the S.I. units, are
recommended:
− C = 122 carbon steel, corrosive fluids, continuous service;

− C = 152 carbon steel, corrosive fluids, intermittent s ervice;
− C = 183-244 carbon steel, non corrosive fluids, continuous service;
− C = 305 carbon steel, non corrosive fluids, intermittent service;
− C = 183-244 carbon steel, corrosive fluids, continuous service,
continuous corrosion inhibitors injection;
− C = 305 carbon steel, corrosive fluids, intermittent service,
continuous corrosion inhibitors injection;
− C = 183-244 CRA alloys, continuous service;
− C = 305 CRA alloys, intermittent service.
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02555.VAR.COR.PRG
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Sheet 48
5.13 Sand erosion
The API formula for predicting corrosion-erosion rate shown in previous

paragraph is not applicable when sand or solid particle are present in the fluid.
Sand erosion rate is related to the following parameters:

− content of solid particles in the fluid;
− flow rate;
− fluid density;
− fluid viscosity;
− density of solid particles;
− dimension of solid particles;
− morphology of solid particles;
− dimensions and geometry of the metallic component.
The calculation of sand erosion rate can be estimated by the use of algorithms
based on the influence parameters previously seen.
According to a model proposed by “Erosion Corrosion Research Centre” of the

Tulsa University, the ratio between mass of metal lost by erosion and the mass
of the solid particles produced, defined as “base erosion rate”, ER b (kgm/kgp), is
given by the following formula:
ERb = 1.73 ⋅ 10-7 ⋅ VL1.623
where:
VL = impingement rate of particles; it depends on system geometry, on fluid
and particles density, and on flow rate; it is expressed as m/s.
kgm = eroded mass of metal, in kg.
kgp = mass of sand produced, in kg.
The calculated value for ER b shall be further corrected by multiplying factors to

take into account of the other parameters reported above.
To carry out the calculation procedure a software program, E/CRC Software

Version 1.0, prepared by Erosion/Corrosion Research Centre, is available.
–––––––––––––––––––––––––––––

Design Criteria: Internal Corrosion

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DESIGN CRITERIA

CORROSION PARAMETERS AND CLASSIFICATION OF THE

2 General revision CESCOR STIN CORM 15.06.95

Rev. 2 No. Sheets 47

The type of document has been changed from “GENERAL SPECIFICATION”

The Normative References chapter has been revised and updated.

A detailed list of definition has been introduced.

Definition of sour conditions in accordance to EFC - European Federation of

2 FLUID TYPES AND CORROSIVITY CLASSES

2.1 Fluid types

2.2 Corrosivity classes

4.1 Liquid hydrocarbons and multiphase systems (I.L.)

4.2 Gas hydrocarbons and gas with condensates

5.2 Water wetting conditions

5.7 Galvanic corrosion

5.9 Stress Corrosion Cracking (SCC)

5.10 Sulphide Stress Cracking (SSC)

5.11 Stepwise Cracking

5.12 Erosion corrosion

Scope of this document is provide criteria to classify, from the corrosion

1.2 Normative references

1.2.1 European normative references

No European normatives exist on the argument of this specification.

1.2.2 Normative references of ISO, IEC and national organizations

ISO 8044 “Basic Terms and Definitions on Corrosion”.

1.2.3 Normative references of other organizations

EFC O&G 93-1 “Guidelines on Material Requirements for Carbon

NACE MR0175 “Sulphide Stress Cracking Metallic Material for

NACE TM0284 “Evaluation of Pipeline Steels for Resistance to

API RP-14E “Design and Installation of Offshore Production

ASTM 287-92 “Standard Test Method for API Gravity of Crude

ASTM G 78-46 “Standard Test Method for Pitting and Crevice

Chloride Stress Corrosion Cracking - CSCC

Dew point temperature

Hydrogen Induced Cracking - HIC

Passivity (passive state)

Predicted corrosion rate

Residual corrosion rate

Stepwise Cracking - SWC

Stress Corrosion Cracking - SCC

Sulphide Stress Cracking - SSC

1.4 Abbreviations and conversion factors

Tab. 1.1 - Corrosion parameters, abbreviations, and units.

PARAMETER Abbreviation Unit

Tab. 1.2 - Conversion factors

PARAMETER from to multiplying

2 FLUID TYPES AND CORROSIVITY CLASSES

2.1 Fluid types

The following types of fluids are considered in this specification:

fluid types abbreviation

liquid hydrocarbons and multiphase systems I.L.

2.1.1 Liquid hydrocarbons and multiphase

2.1.2 Gas and gas condensate

These fluids include gas, alone or in combination with condensates or water.

Fresh waters - A.D.

Brackish waters - A.S.

Sea waters - A.M.

Formation waters - A.F.

2.2 Corrosivity classes

type class properties

I.L. I.L.N. non containing CO2 or H2S

I.G. I.G.N. non containing CO 2 or H2S

G. G.N. non containing CO 2 or H2S