Materials for sour environments

Dr. Ing. G. Re
Dipartimento Chimica, Materiali e Ingegneria Chimica “Giulio Natta”
 Material selection for sour service

Materials selection should be optimized and provide acceptable safety and

reliability. The main aspects that must be considered are:

ü  Corrosivity, taking into account specified operating conditions including

start up and shut-down conditions;
ü  Design life and system availability requirements;
ü  Failure probabilities, failure modes and failure consequences for human
health, environment, safety and material assets;
ü  Resistance to brittle fracture;
ü  Inspection and corrosion monitoring;
ü  Access for maintenance and repair.

Materials for sour environments

 Material selection for sour service

For the final materials selection, the following additional factors should be
included in the evaluation: priority should be to select materials with good
market availability, documented fabrication and service performance; the
number of different materials should be minimized considering stock, costs,
interchangeability and availability of relevant spare parts.

Materials for sour environments

 Material selection for sour service

The selected material must be evaluated for its resistance to corrosion. At a

minimum, this would include the following (e.g., according Norwegian standard
NORSOK M001 “Materials Selection”):
ü  CO2-content,
ü  H2S-content,
ü  oxygen content and content of other oxidizing agents,
ü  operating temperature and pressure,
ü  organic acids, pH,
ü  halides, metal ion and metal concentration,
ü  velocity, flow regime and sand production,
ü  biological activity,
ü  condensing conditions.

Materials for sour environments

 Material selection for sour service

In material selection, it must be taken into consideration that corrosivity of the

aqueous phase of a sour fluid increases when:
Ø  H2S partial pressure increases;
Ø  pH decreases;
Ø  Halides (chlorides) concentration increases.

As far as temperature is concerned, SSC has a maximum at about room

temperature, while chloride SCC of austenitic stainless steels increases with
increasing temperature.

Materials for sour environments

 Material selection for sour service

Material for an equipment to be used in sour environment must be selected

also taking into account the possible change of operational parameters in the
expected equipment life-time. In many cases even if the fluid is “sweet” at the
beginning of the production life of a field, materials suited for sour service are
adopted in order to take into account that field production often tends to turn
into sour conditions during service.

Materials for sour environments

 Materials for sour service

Materials for sour service must have some very general characteristics to
reduce their susceptibility to hydrogen attack:

ü  Cleanliness to avoid inclusions and segregation;

ü  Fine grain size to improve toughness;
ü  Homogeneity, composition, mechanical and metallurgical characteristics
evenly distributed;
ü  Stability, complete release of internal stress.

Materials for sour environments

 Materials for sour service

Banded ferritic-pearlitic structure Homogeneous bainitic structure

Materials for sour environments

 Materials for sour service

Carbon steels (CS) are used in the area of slightly to moderate sour service
and their possible use can be extended by using suitable inhibitors.
The reference standard for carbon steel pipes to be used in oil and gas
industry is:
ISO 3183-2012
“Petroleum and natural gas industries – Steel pipe for pipeline transportation
systems”.

In Annex H of this standard special requirements are given for pipes to be

used in sour service.

Materials for sour environments

 Materials for sour service

CS’s for sour service are characterized by:

ü  Mn content lower than 1,4 % to reduce the possible formation of the
central segregation band;
ü  Carbon level between ~0.04 and 0.08%;
ü  Small addiction of alloy elements such as Cr (<0.5%), Mo (<0.3%) and
Cu (>0.2%);
ü  Fine grained quenched and tempered (Q&T) microstructure consisting of
a ferritic matrix with a homogeneous, finely dispersed carbide
precipitation.

Materials for sour environments

 Materials for sour service

ü  Very low sulfur and phosphorus content (Low Sulphur Steel
0.01%>S>0.003% =30ppm, Ultra LSS S<0.003%) (P<0.01% = 100ppm).
ü  Control of the inclusion shape, that can be achieved by treating the steel with
calcium or with rare-earth metals, REM (Ce, La, Nd, Pr = Mishmetal). In this
way small, finely dispersed and spheroidal inclusions can be obtained that
are much less harmful to steel respect to the elongated ones.

20 µm

Materials for sour environments

 Materials for sour service

Control of hardness of carbon and low alloy steel welds within the limit given in
this figure has been found to correlate with prevention of SSC in sour
environments.

Materials for sour environments

 Materials for sour service

In order to guarantee CS weldability in field some parameters can be

adopted which measure the hardening propensity of the material:

Mn Cr + Mo + V Ni + Cu I.I.W. Carbon Equivalent

CE = C + + +
6 5 15

Si Mn + Cu + Cr Ni Mo V Ito & Bessyo Critical Metal

PCM = C + + + + + + 5B
30 20 60 15 10 Parameter

In material requirement specification for sour service CS these parameters

are used to limit total amount of added elements, e.g.:
CE ≤ 0.38 or PCM ≤ 0.19.

Materials for sour environments

 Materials for sour service

If material hardenability is limited, it is possible to control maximum

hardness in the different microstructural areas of welded joint, in particular in
Heat Affected Zone (HAZ) even if welding is carried out using a low heat
input process.

HAZ

Base Metal, BM

Weld Metal, WM

Materials for sour environments

 Materials for sour service

Post Weld Heat Treatment, PWHT, is often recommended for two reasons:

ü  as a tempering process, it reduces the hardness of the weld deposit and
the heat affected zone;
ü  as a stress relieving process, it reduces residual stresses in the
weldment through stress relaxation.

Both of these effects tend to reduce the probability of failure due to SSC.

Materials for sour environments

 Materials for sour service

In industrial practice the maximum value yield strength for CS pipes to be

used in sour service is 450 MPa (=65 ksi), if a higher yield strength value is
needed alloy steels are used.

Low alloy steels, i.e. steels with a total content of alloy elements <10%, used
in sour environment are mainly Cr-Mo steels in quenched and tempered
(Q&T) conditions. A nickel content below 1% is often indicated by many
specifications.
Low alloy Cr-Mo steels typically used for sour service:
UNS G41XX0 (1 Cr, 0.2 Mo, 0.XX C) (AISI 41XX)
ASTM A182 F22 (2.25 Cr 1 Mo)

Materials for sour environments

 Materials for sour service

When the fluid corrosivity increases carbon and low alloy steels are no more
suitable for the service and Corrosion Resistant Alloys (CRA) must be used.
CRA have an increasing intrinsic resistance to acidic corrosion caused by
H2S and CO2 due to the high content of alloy elements such as Cr and Mo,
but higher alloy CRA are also insensitive to embrittling phenomena due to
the austenitic (fcc) microstructure.

Materials for sour environments

 Materials for sour service

Nickel superalloys

Iron superalloys

Duplex SS’s

Conventional SS’s

Materials for sour environments

 Materials for sour service

Martensitic stainless steels (SS) have been used in oilfield production for
many years, providing very good serviceability within their limiting conditions
of pH and H2S partial pressure.
These materials have been nominally 12%Cr (0.15%C) stainless steels
based in wrought AISI 410 or cast CA15 SS.
New grades of martensitic SS’s recently introduced contain 4 to 6% Ni and
1.5 to 2% Mo to improve corrosion resistance. In Q&T conditions these
materials have a yield strength up to 760 MPa (110 ksi).

Materials for sour environments

 Materials for sour service

Microstructure of stainless steels – Schaeffler’s Diagram

> 11% Cr

AISI 304

AISI 410
AISI 430

Materials for sour environments

 Materials for sour service

Microstructure of stainless steels – Schaeffler’s Diagram

20

15 Austenitic
%Ni equiv.

10 Duplex

PH
5

Martensitic Ferritic
10 15 20 25 30
%Cr eq.
Materials for sour environments
 Materials for sour service

Conventional austenitic SS’s, i.e. AISI 304 and 316, have a corrosion
resistance a little better than martensitic SS’s, but they have rather poor
mechanical strength that can be improved only by cold working.

Materials for sour environments

 Materials for sour service

High alloy austenitic SS’s are being introduced into H2S service application
primarily for use as high-strength tubular materials. These materials have
fully austenitic microstructure with high level of Ni, Cr, Mo and N. Their
structure is stable even after high level of cold working during processing.
Highly alloyed austenitic SS’s in tubular form can be cold worked in the
range of 30 to 50 percent cold reduction to strength level between 750 and
1,000 MPa yield strength.
There are many materials that fall into this classification which have varying
concentrations of Ni, Cr, Mo and N. Their corrosion behaviour is in general
very good but can vary substantially depending on actual composition.

Materials for sour environments

 Materials for sour service

The corrosion resistance of Alloy 825 (42Ni-22Cr-2Mo) in H2S/CO2 environments in

the absence of elemental sulphur. Corrosion rates of ≤0.05 mm/yr and no SSC or
SCC.

Materials for sour environments

 Materials for sour service

Nickel based alloys offer extremely high resistance to SSC and corrosion
due to their alloy composition that contains high level of Ni, Cr and Mo.
These materials typically have between 5 and 20 % iron.
High strength Ni-base alloys may exhibit environmental cracking in H2S
environments at temperatures ranging from 25 to higher than 220 °C.
However the material condition where HEC is observed is limited to
hardness in excess of HRC 40 produced by cold working or heat treatment
and may vary with alloy composition and microstructure.

Materials for sour environments

 Materials for sour service

Two groups of Ni-base alloys are being employed in equipment primarily for
use in service environments containing high H2S partial pressures. The
distinction between the two groups is made on the basis of how the high-
strengthening is obtained:

Ø  For tubular goods, Ni-base alloys can be cold worked to strength level in
excess of 1,000 MPa yield strength.
Ø  For other components, such as valves and specialized equipment which
often require more complex shapes or welding, precipitation hardened
NI-base alloys, which obtain their strength via aging heat treatments, are
available with nearly the same strength level.

Materials for sour environments

 Materials for sour service

The corrosion resistance of Inconel 625 (22Cr-9Mo-2Fe) in H2S/CO2 environments in

the absence of elemental sulphur. Corrosion rates of ≤0.05 mm/yr and no SSC or
SCC.

Materials for sour environments

 Materials for sour service

Duplex SS’s are a mixture of two microstructural constituents, ferrite and

austenite. They can be produced in both cast and wrought conditions and
typically have 22 to 25 % Cr with yield strengths of 350-620 MPa when in
the cast or annealed conditions. These steels derive their microstucture and
mechanical properties from a balanced chemical composition which
contains alloying additions of Cr, Ni, Mo and N.
Wrought duplex SS’s are produced with strength capabilities between 400
and 900 MPa yield strength. Unlike low alloy steels and martensitic SS’s,
duplex SS’s can be strengthened by cold working. This cold working has a
generally negative effect on susceptibility to environmental cracking, but this
effect is limited in tubular goods when cold reduction is contained within
30%.

Materials for sour environments

 Materials for sour service

Duplex SS’s have a corrosion resistance generally superior to those of the

martensitic SS’s in H2S, CO2 and brine environments together with a
material strength greater than conventional austenitic SS’s.

Materials for sour environments

 Materials for sour service

CRA cost much more than carbon or low alloy steels and often their
mechanical properties are poorer then their selection must be considered
very carefully.

A possible solution is offered by cladding or lining, i.e., structural steels

having high mechanical characteristics and relatively low cost can be
cladded or lined with a thin layer of high cost CRA.

Materials for sour environments

 Testing

Resistance of metallic materials and in particular of carbon and low alloy

steels to hydrogen damage depends on many parameters and it should be
evaluated specifically for any different kind of damage, it isn’t even possible
to simply state that a material is “resistant to hydrogen damage” but it is
better to say that it is resistant to HIC or SSC or SOHIC a.s.o.

Materials for sour environments

 Testing

It is not possible to guarantee that a material meets specified corrosion

resistance for sour service only on the basis of its composition or
mechanical properties and metallurgical characteristics, but, in order to
demonstrate their capability to resist to different forms of hydrogen damage,
materials and weldments must be tested during qualification, production and
construction phases.
These tests must be carefully designed as far as regards:
Ø  test method;
Ø  test environment;
Ø  materials and specific microstructural features to be tested;
Ø  interpretation of the test results and acceptance criteria.

Materials for sour environments

 Testing

EFC Publ. Nr. 16 and, more recently, NACE MR0175/ISO 15156 provide a
comprehensive guidance on test procedures for SSC, SOHIC and HIC
including suggested acceptance criteria.

NACE Standard TM0284-2003 “Evaluation of Pipeline and Pressure Vessel

Steels for Resistance to Hydrogen-Induced Cracking” and TM0177-2005
“Laboratory Testing of Metals for Resistance to Sulfide Stress Cracking and
Stress Corrosion Cracking in H2S Environments” provide guidelines on the
manner in which hydrogen-induced cracking and environmental cracking
tests should be conducted in sour environments.

Materials for sour environments

 Testing NACE TM0284-2003

NACE TM0284-2003 testing solutions:

Ø  Solution A: 5.0 weight % NaCl (Sodium chloride) and 0.50 weight %
CH3COOH (Acetic acid) in distilled or deionized water, initial pH 2.7 ± 0.1.
Ø  Solution B: synthetic sea water (ASTM Standard D 1141), pH = 8.1 – 8.3.

Solutions must be purged with pure nitrogen to eliminate oxygen, then

saturated with H2S at atmospheric pressure.

Materials for sour environments

 Testing NACE TM0284-2003

Materials for sour environments

 Testing NACE TM0284-2003

Materials for sour environments

 Testing NACE TM0284-2003

Acceptance criteria according NACE MR0175-ISO 15156

Materials for sour environments

 Testing NACE TM0177-2005

NACE TM0177-2005 testing solutions:

Ø  Solution A: 5.0 weight % NaCl (Sodium chloride) and 0.50 weight %
CH3COOH (Acetic acid) in distilled or deionized water, initial pH 2.7 ± 0.1.
Ø  Solution B: 5.0 weight % NaCl (Sodium chloride), 2.50 weight %
CH3COOH (Acetic acid) and 0.41 weight % CH3COONa (Sodium acetate)
in distilled or deionized water.
Solutions must be purged with pure nitrogen to eliminate oxygen, then
saturated with H2S at atmospheric pressure.

Ø  Test solution C is a buffered (0.4 g/L CH3COONa) aqueous brine solution
with a chloride content, H2S partial pressure, and pH specified by the user
or purchaser to simulate the intended service environment.
Test gas shall consist of a mixture of H2S and carbon dioxide (CO2), with H2S
content sufficient to produce the specified H2S partial pressure of the intended
service environment.

Materials for sour environments

 Testing NACE TM0177-2005

NACE TM0177-2005 describes four test methods with four different test
specimen geometries and different loading frames:

Ø  Tensile Test;

Ø  Bent-Beam Test;
Ø  C-Ring Test;
Ø  Double-Cantilever-Beam Test.

This standard may provide a quantitative measure of the product’s

environmental cracking resistance for research or information purpose.

Materials for sour environments

 Testing NACE TM0177-2005

Materials for sour environments

 Testing NACE TM0177-2005

Example of graphical representation of test results.

Materials for sour environments

 Testing NACE TM0177-2005

DCB specimen

Materials for sour environments

 Testing NACE TM0177-2005

Using fatigue pre-cracked DCB specimen (Standard Test Method D) it is

possible to measure KISSC, i.e., the fracture mechanics parameter which
gives a quantitative information on the resistance of the product to sulfide
stress cracking.

Materials for sour environments

 Case study

Design parameters of an off-shore/on-shore gas pipeline:

Ø  Sour gas H2S = 16%, pH = 3.5;

Ø  Possible presence of water with chlorides (≤100 mg/L);
Ø  Design pressure range 80/100 barg, pH2S = 12.8/16 Bar;
Ø  Pipe diameter range 24/30” (DN600/750);
Ø  Maximum gas flow = 0.5*106 stdm3/d;
Ø  Temperature range -40/+70 °C.

Materials for sour environments

 Case study

7.5
0.0035 bar
(0.05 psi)

SSC Region 1
6.5 (Slightly Sour Service)

SSC Region 2
(Moderately Sour Service)
5.5 SSC Region 0
In-situ pH

(Sweet Service)

4.5

SSC Region 3
(Severely Sour Service)

3.5

2.5
0.0001 0.001 0.01 0.1 1 10 100
Hydrogen Sulphide Partial Pressure (pH2S - bar)

Materials for sour environments

 Case study

Some material properties needed for the project:

Ø  Resistance to severe sour environment;

Ø  Resistance to chloride attack;
Ø  Weldability with manual and automatic welding processes;
Ø  Resistance to brittle and ductile fracture initiation;
Ø  Resistance to brittle and ductile fracture propagation;

Materials for sour environments

 Case study

Candidate materials:

Ø  Carbon steel according ISO 3183;

Ø  CRA cladded carbon steel;
Ø  Solid CRA material.

Materials for sour environments

 Case study

Carbon steel: possible grades L360 (X52), L415 (X60), produced according
ISO 3183 + Annex H for sour service and Annex J for offshore service with
more stringent requests for:
ü  Chemical composition (lower limits for some alloying elements, e.g. C,
Mn and for Pcm and CE);
ü  Hardness (maximum value below the limit of 248 HV10 indicated by ISO
3183);
ü  HIC and SSC tests (test environment simulating the real one and stricter
acceptance criteria);
ü  Number of tests during production (increased).

Materials for sour environments

 Case study

Solid CRA materials guarantee the suitable resistance to sour environment

but:
ü  Their cost is much higher than CS;
ü  They require more critical handling during pipeline construction (storage,
laying, welding, hydrotesting, a.s.o.).

Materials for sour environments

 Case study

Cladded materials guarantee the suitable resistance to sour environment

but:
ü  Their cost is higher than CS;
ü  A more complex welding procedure is needed during pipeline
construction;
ü  Their toughness properties are lower than CS.

Materials for sour environments