Industeel

Duplex Stainless Steel Offer for Oil & Gas

Jean-Christophe Gagnepain
December 2012
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Application

Conclusion
Product Range
Market description

Corrosion Properties

temperature toughness

Industeel
Industeel Duplex Plates for Oil & Gas

Industeel new development: a low ferrite 2205 with improved low

1
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industry

Market Description

Industeel
Duplex Stainless Steel Offer for oil & gas

2
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Exploration
Production
The oil & gas chain
Market description

Processing
Industeel
Transportation

Duplex grades
Storage

3
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industry

Product range

Industeel
Duplex Stainless Steel Offer for oil & gas

4
 INDUSTEEL supplies a complete range of corrosion
resistant grades
CORROSION UNS NUMBERS
RESISTANCE
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Alloy 22

Alloy 276
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S 31266

S 32750/ N08926/N08367 N 06625

S32760 S 34565
S32520 S31254

S32205 N 08904
N 08825
S 31803
SUPERMAX80 317 LNM
S 32304
S41500 316
S 32202
410 304

MARTENSITIC DUPLEX AUSTENITIC NICKEL ALLOYS

STEELS STEELS
Industeel 5
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Yield Strength

304L
2202

316L
2304

Industeel
904L
2205

Corrosion Resistance
Yield Strength and Corrosion Resistance

2507

6Mo

6
Duplex family Typical chemical analysis (%)
Cannot be disclosed, used, or reproduced without prior written specific authorization of ArcelorMittal

UNS EN C Cr Ni Mo N Cu,W Mn PREN*

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22,5/
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UR 2202** S32202 4062 <0,03 2/2,5 0,3 0,21 0,2 1,3 26/27
23

UR2304
S32304 4362 <0,03 23 4 0,3 0,12 0,2 1 26/27

UR2205 S31803/ 22/ 0,16/

4462 <0,03 5/6 2,8/3,3 33/36
32205 22,5 0,18
Superdu- S32520 4410 1,5Cu
plex type S32750 4507 <0,03 25 7 4 0,25 - 1 40
2507 S32760 4501 .5Cu-.5W

* PREN = %Cr + 3.3%Mo + 16%N

** UR 2202 patented by INDUSTEEL(flat) and UGITECH(long products)
Industeel supplies the 3 main super duplex grades

Industeel 7
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0
100
200
300
400
500
600
(MPa)
Y.S.0.2%

304L
316L
2304
2202

3 reasons






904L

Industeel
2205
High strength of duplex stainless steels

6Mo

High ferrite content

2507

Fine grained dual structure

High Nitrogen (in austenite)
(Ksi)

0
29
58
87

14.5
43.5
72.5

8
Y.S.0.2%
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R e la t iv e a llo y s c o s t
e v o lu t io n s ( $ /T )

0
1000
2000
3000
4000
5000
6000

Mo
Ni
5
10
10
20
15
30
Comparison of relative prices

Industeel
20
40
Evolutions in function of raw materials

Alloy price $/kg

25
50
30
60
35
70
304L
316L

2202
2304

9
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Standards
Corrosion properties /

Industeel
Duplex Stainless Steel Offer for oil & gas

10
 Corrosion in Oil & Gas
Material issues  Stress Corrosion Cracking & Sulfide Stress Cracking
Cannot be disclosed, used, or reproduced without prior written specific authorization of ArcelorMittal

Cracking induced from the combined influence of tensile stress and a corrosive
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environment
SCC = stress + chloride ions
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SSC = stress + chloride ions + H2S gas

The stress level can be related to directly applied stresses and/or to residual
stresses generated by welding or heat treatment operations

Stress induces local deformation that destroy locally the passive layer and lead to
the formation of cracks

Effet of H2S:
promotes depassivation since HS- replaces OH- into the passive film
penetration of atomic hydrogen into the metal structure

Industeel 11
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Corrosion in Oil & Gas

Industeel
Materials issues  Stress Corrosion Cracking & Sulfide Stress Cracking

12
 Corrosion in Oil & Gas
Material issues  relevant parameters
Cannot be disclosed, used, or reproduced without prior written specific authorization of ArcelorMittal

H2S partial pressure (from a few ppms to 15%)

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CO2 partial pressure

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Temperature (up to 482F/250C)

Chloride concentration (up to 250 g/l)

Water composition
All these
pH (from 2.5 to 6.5)
parameters
Oxygen contamination depend on the oil
Flow rate, abrasion & gas field

Industeel 13
 Oil &gas, a market described by different standards
Standards
NACE EFC
Cannot be disclosed, used, or reproduced without prior written specific authorization of ArcelorMittal

MR 0175 / ISO 15156 EFC Publication n16

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Material for use in H2S-containing Guidelines on Materials requirements for carbon

environments in oil and gas production and low alloy steels for H2S containing environments
in oil and gas production
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TM 0177
Laboratory testing of metals for resistance to
sulfide stress cracking and stress corrosion
cracking in H2S environments
NACE TM 0284
Evaluation of pipeline and pressure vessel
steels for resistance to hydrogen induced
cracking
EFC Publication n17
Corrosion Resistant Alloys for Oil and Gas
Production: Guidelines on General Requirements
and Test Methods for H2S Service
DNV-RP-F112
Design of duplex stainless steel subsea equipment
exposed to cathodic protection

NORSOK standards
developed by norwegian offshore operators and considered a good reference basis for engineering
materials in northern Atlantic conditions
Norsok qualifies producers of critical materials (duplex , superduplex , 6%Mo ) to avoid the use of
substandard products
Industeel 14
 Standards limit strongly the use of duplex
grades in sour environments
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An international contract has been launched with a strong

Industeel comittment
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Objective: to establish useful service limits of use for 22%Cr

and 25%Cr duplex stainless steels in H2S/Cl- containing
environments
in low pH media (low chloride and up to 50
g/l chlorides)  condensation water
in higher pH media (high chloride content up
to 150 g/l chlorides)  formation water

Selected literature and in house data (Industeel and Total

lab results) were gathered in order to establish useful
service limits
Published work : T. Cassagne et al., An Update on the Use of Duplex
Stainless Steels in Sour Environments, Nace 2012 conference
Industeel 15
 NACE MR0175/ISO15156
R&D study
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 NACE MR 0175/ISO 15156 standard strongly limits the use of duplex grades
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No lean duplex accepted in this standard (PRENmin = 30)

except S32003/ATI 2003 from Allegheny

S32304/UR2304 was proven to be resistant up to 5 kPa and could

be a good alternative to supermartensitic stainless steels

Industeel 16
 Trends and evolutions in oil & gas
R&D study
Cannot be disclosed, used, or reproduced without prior written specific authorization of ArcelorMittal

 NACE MR 0175/ISO 15156 standard: limits of use of duplex grades

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Acceptable partial H2S pressure according to lab tests

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10

1
pH2S (bar)

5 KPa
0,1

1 KPa  2202 to be tested

0,01
0.4 KPa

0,001
medium martensitic high martensitic UR2304
4,5Ni -1,5Mo 6,5Ni- 2,5Mo UNS S32304
Industeel 17
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R&D study

Laboratory tests
Laboratory tests
 50 kPa (7.3 psi)

 100 kPa (14 psi)

Industeel
Trends and evolutions in oil & gas

 NACE MR 0175/ISO 15156 standard: limits of use of duplex grades

18
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pH2S (kPa)

0,1
1
10
100
1000

4,5Ni -1,5Mo
medium martensitic
6,5Ni- 2,5Mo
high martensitic

Industeel
UNS S32304
UNS S31803
Annealed Materials - CLTests (100%YS)
100 000 ppm Chloride - Formation water
Lab results - Acceptable partial H2S pressure

UNS S32520

19
 DNV recommendations
DNV-RP-F112 October 2008
Materials with a fine phase spacing have a greater resistance to cracking than
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materials with a coarse phase spacing

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Recommendation: austenite spacing < 30 m in base metal, weld metal and

Heat Affected Zone  not a strict limit, since the uncertainty of austenite spacing
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results often are of the same order as the results themselves

Average value 6
sigma (standard deviation) 5
2 10
under skin
Average + 2 16
Average - 2 -4
maximale value 31
Average value 9
sigma (standard deviation) 8
2 16
1/4 thickness
Average + 2 25
Average - 2 -7
maximale value 51
Average value 7
sigma (standard deviation) 6
2 12
1/2 thickness
Average + 2 19
Average - 2 -5
maximale value 35

Industeel Results (4 micrographs) 20

UR 2205 (20 mm thick) under skin
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Average valu es o f the austenite space (m )

0
10
20
30
40
50
60
70

UR 2507 -
ep. 125mm
Skin

80mm
UR 2205 -
DNV-RP-F112 October 2008

Standard deviation

57mm
UR 2507 -

Industeel
50mm
UR 2205Mo -
Trends and evolutions in oil & gas

20mm
UR 2202 -

Industeel plates qualified up to 80mm thick

20mm
UR 2205Mo -
7mm
UR 2205Mo -
Maximal value of 30m

21
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industry

toughness

Industeel
Performance with improved low temperature
Industeel new development: a duplex 2205 High
Duplex Stainless Steel Offer for oil & gas

22
 Since 20 years, progress in ferrite control in duplex
welds: S31803 S32205

0,13% 0,21%
Increased Nitrogen content
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HAZ Fused metal HAZ Fused metal HAZ Fused metal

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83% ferrite 76% ferrite 69% of ferrite

HAZ 0,07 mm width
0,20 mm width 0,18 mm width
Molten 95% ferrite
89% of ferrite 68% of ferrite
metal
100 m

Tests performed on UR 2205 duplex grade - Electron Beam welding As welded HAZ

Industeel 23
 Why go further?

Oil exploration in increasingly challenging environments

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API938 suggests Max Ferrite 65% in duplex HAZ

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Due to ice melting, oil fields in Arctic fields become more and more attractive
for oil companies

For standard duplex such as 2304 or 2205, suppliers accept warrantees such
as KVmin 40J (30 ft.lb) at 46C(-51F)

INDUSTEEL worked on a High Performance 2205 2205 H.P able to

support:
wider heat input range by keeping limited ferrite in HAZ
acceptable KV at lower temperature, by keeping duplex mechanical and
Corrosion Resistance properties

Industeel 24
 Microstructures comparison:
standard 2205 and new optimised 2205 (HP)
(1/4 thickness)
URANUS 2205 URANUS 2205 H.P
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200 200
m m
Ferrite (ASTM E562) = 49% Ferrite (ASTM E562) = 40%
After hot rolling and solution annealing with water quenching
Neither intermetallic phases nor carbonitrides
A lower ferrite content, due to higher Nickel content
Industeel 25
 Microstructure and Impact tests
Charpy V curve
H.P 25mm
2205 Arctic (25mm) 2205 (15mm)
Minimal value required (EN 10088-2) Average value required (EN 10088-2)
Cannot be disclosed, used, or reproduced without prior written specific authorization of ArcelorMittal

2205 Arctic (Formulinox forecasts) 2205 (Formulinox forecasts)

400
(295)
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350
(258.1)
Energy J (ft.lb)

300
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(221.2)
250
(184.3)
200
(147.5) Ferrite 40%
150
(110.6)
100
(73.7)
50
(36.8) Ferrite 49%
0
-200
(-328)
-150
(-238)
-100
(-148)
-50
(-58) (32)
0 50
(122) (212)
100

Temperature C (F)

Transition shifted to lower temperatures for 2205 H.P which is usable for
Arctic conditions

Industeel 26
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Maximal ferrite in the H.A.Z. (%)

50
55
60
65
70
75
80

0
FORMULINOX prediction

For a 15mm thick plate

to standard 2205

3,2
20
2205

40

1,7
35C/s 2kJ/mm

Industeel
1,2
60
Cooling rate at 700C (C/s)
An improved weldability compared

H.P

0,9
80
2205 Arctic

GTAW
H.I (kJ/mm)
100

27
 An improved weldability compared
to standard UR2205

Welding conditions: GTAW with niobium free 625 (Phyweld NCW) filler metal
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One deposit with 2,0kJ/mm on 15mm thick duplex plate => Cooling rate: 35C/s
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UR2205 Standard UR2205 H.P

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*Metallographic measurements of the ferrite content according to the ASTM E562, with x1000 magnification for the HAZ

Measured ferrite content*: 78% Measured ferrite content*: 68%

70%max ferrite content in HAZ could be acceptable whatever the welding

conditions

Industeel 28
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KCV Joule (ft.lb)

(184,39)

(36,87)
(73,75)
(147,51)

(110,63)

0
50
100
150
200
250

Base
metal
HAZ

2205H.P
Toughness properties at -100C (-148F)

Ni

Industeel
weld
base

metal
Base
metal

HAZ

HAZ2205
weld
2209

metal
UR2205HP welded joint for subzero application

29
 THANKS TO LOW FERRITE CONTENT, 2205 H.P IS A ALSO A
GOOD CANDIDATE FOR USE IN REFINERIES (API 938)
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To replace carbon steels

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suffering corrosion by :
S , Cl- , CO2 , NH3 , NaOH ,
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Atmospheric , soil

To replace 304 / 316

in chloride containing waters

We promotediscussions
at API committee to
bring Max Ferrite in HAZ at
70%. 65% cant be achievable
in some welding configurations if
properly measured

Industeel 30
 UR 2205HP
maintain high properties:
Corrosion resistance,
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Tensile properties.
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enhance the Toughness properties in:

Base metal
HAZ,
In the weld metal with nickel base filler material.
For very low temperature applications: Up to 100J (74ft.lb) at -
100C (-148F) could be accepted

helps to a good control of max ferrite in HAZ, making it consider for use in
refinaries
Industeel 31
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industry

Applications

Industeel
Duplex Stainless Steel Offer for oil & gas

32
Examples of duplex application in oil & gas
Offshore production platform
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Gas
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Coolers

Separators Oil
Piping
Manifold
Sea water
system

Sea water Sea level Legs

lift

Riser tube
Sea floor

Well head
equipment Subsea equipment skid
Flow lines
Down hole tubing Industeel 33
 Offshore existing applications
of duplex stainless steels
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WHICH WHAT ELSE

WHERE ? WHY ?
DUPLEX ? IS ALSO USED ?
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Blast walls Mechanical properties

structures utilities Metallic (resist to fire) UR 2304 316L
Low maintenance costs UR 2205 316LN
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Competitive cost

Flow lines Mechanical properties UR 2304 (low H2S) Weldable martensitics

Corrosion resistance to UR 2205 X65 + 316L/825 CLAD PLATES
CO2 + H2S + Cl UR 2507/2507Cu/2507W Bimetallic pipes (316L, 825)
Outside protection less critical X60 + inhibitors/coatings
Ductile enough for pipe laying

Risers Mechanical properties UR 2507 type Flexible pipes

Resistance to impact Titanium (TA 6V)
Corrosion resistance Nickel alloys
Fatigue resistance X65 + 825 CLAD PLATES
Process vessels separators Weight savings UR 2205 SE 500+904LN/316L CLAD
Oil/gas coolers External protection possibly reduced UR 2507 type Weld overlay on SOLID PLATES
Heat exchangers Better safety than 316L (equiv to 904) Solid 904 (UR B6)
Scrubbers

Sea water piping Corrosion resistance to sea water up to UR 2507 type 6Mo (B25/B26)
30C CuNi 9010
Mechanical properties
Manifolds, Mechanical properties UR 2205 6 Mo (B25/B26)
Process piping Corrosion resistance UR 2507
Compatibility with other materials

Industeel 34
 Examples of duplex application
Offshore production platform
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Risers and flowlines

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Risers
- UR2507Cu

Flowlines
- UR2304 (if low H2S)
- UR2205
- UR2507Cu
Why duplex in the 2000s ?
Corrosion resistance
Mechanical properties
Fatigue resistance for risers
Industeel 35
 Examples of duplex application
Offshore/onshore production platform
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Separators, coolers, heat exchangers

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Separator (duplex)

Manifold (superduplex)

Why duplex ?
Mechanical properties
Weight saving
Corrosion resistance
Industeel
Cooler (duplex) 36
 Classical duplex applications in oil & gas
Typical dimensions
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Equipment Tons Thickness (in) Thickness (mm)

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Flowlines 200 to 2000 0.20 to 0.79 5 to 20

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Separators 50 to 500 1.97 to 19.7 30 to 150

Industeel deliveries in oil & gas since 2003 (all equipments)

Industeel is an experienced supplier of
UR2304/S32304: 1200 t duplex and super duplex plates
since more than 50 years

S32205/S31803: 27000 t
INDUSTEEL is NORSOK approved and
S32750/UR2507: 7000 t accepts all customer audits for
specific qualifications
Industeel 37
 Potential areas of progress in material selection
for oil & gas
Economic alternatives to protected carbon steel (storage
Cannot be disclosed, used, or reproduced without prior written specific authorization of ArcelorMittal

tanks)
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Lean duplex UNS S32304 (1.4362), UNS32202 (1.4062)

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Cheaper stainless steels

904L Duplex 2205 (EN 1.4462)
6Mo grade Superduplex 2507, UNS S34565 (EN 1.4565)

Replacing more expensive CRA

Ni Base alloy, Ti UNS S31266

Industeel 38
 Lean Duplex for Petroleum Products Storage
Tank
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INDUSTEEL has developed a Software CALRES for cost comparaison of

storage tanks (investments and life cycle costs)
Multi partner contract dedicated to tanks: results will be presented at NACE 2013
Industeel 39
 Lean Duplex for Petroleum Products Storage
Tank
Main parameters :
Cannot be disclosed, used, or reproduced without prior written specific authorization of ArcelorMittal

Tank diameter : 40m (131.2 ft)

Tank height : 20m (65.6 ft)
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Fluid density : 0.8

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Labor cost : 19/h (25$/h)

Life cycle cost : 20 years

Grades :
Carbon steel (with external painting and internal coating 10 USD/ft)
Austenitic grades 304L and 316L
Lean duplex grades UR2202 and UR2304

Industeel 40
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Cost (x1000 USD)

0
1000
2000
3000
4000
5000
6000
Tank

A516
304L
Investment and life cycle costs

Industeel
UR2202
316L
Lean Duplex for Petroleum Products Storage

Pickling

Material
Welding
Painting

Forming

UR2304
Maintenance

41
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industry
Conclusion

Industeel
Duplex Stainless Steel Offer for oil & gas

42
 Duplex use in oil & gas: Trends and evolutions

Use of lean duplex grades for storage tanks 

Cannot be disclosed, used, or reproduced without prior written specific authorization of ArcelorMittal

2202/2304
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Arctic conditions: need of grades that are

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resistant at very low temperatures  Industeel

developped an optimized 2205 H.P

2202/2304 are usable for low H2S conditions

(substitution to supermartensitic grades)

2205 and 2507 could be used in

widely more severe conditions than those
suggested by NACE/ISO standards

Industeel 43