Stainless Steel World 99 Conference

Stainless Steel World

1999 KCI Publishing BV

SSW99-042

PAGE 331

Development of weldable martensitic stainless steel line pipe by
HF- ERW process

Authors: Naoshi Ayukawa (Pipe & Tube Sales Dept, Nippon Steel Corporation, J apan), Hideyuki Nakamura (Nagoya R&D Lab-
oratories, Nippon Steel Corporation, J apan), Motofumi Koyuba (Pipe Dept, Nagoya Works, Nippon Steel Corporation, J apan),
Akihiro Miyasaka (Nagoya R&D Laboratories, Nippon Steel Corporation, J apan), Manabu Ueda (Pipe Dept, Nagoya Works, Nip-
pon Steel Corporation, J apan), Hitoshi Asahi (Steel Research Laboratories, Nippon Steel Corporation, J apan), Koichi Nose (Steel
Research Laboratories, Nippon Steel Corporation, J apan),

Abstract

A new type of martensitic stainless steel
line pipe having excellent weldability and
high corrosion resistance in wet CO

2


environments manufactured by the high-
frequency electric-resistance welding
(HF-ERW) process was developed on a
commercial scale. The newly developed
pipe is characterised by greater produc-
tivity compared with the conventional
martensitic stainless steel seamless
pipes, higher dimensional accuracy, in
respect of thickness and outside diame-
ter and capability of manufacturing thin-
ner-wall pipes.

1 Introduction

Recently, oil wells and natural gas wells
containing considerable amounts of carbon
dioxide (CO

2

) have been increasingly going
into service, and martensitic stainless steel
oil country tubular goods (OCTG) (ex. AISI
420) are used for such environments. As for
line pipe use, however, martensitic stainless
steel pipes have not been popular because
of its poor weldability. Although some new
types of seamless martensitic stainless
steel pipe with improved weldability have
been developed (refs 1, 2) and going into
service since a few years ago, no HF-ERW
martensitic stainless steel pipe has been
fully developed.
In this study, we have developed, on com-
mercial scale, a new HF-ERW martensitic
stainless steel line pipe with excellent eld
weldability and corrosion resistance in wet
CO

2

environment. The newly developed
steel contains 1113% Cr. It also contains
Ni and a little amount of Mo. Amounts of C
and N are extremely low. The well-control-
led chemical composition makes it possible
to obtain high corrosion resistance and
good weldability at the same time. As for
manufacturing process, we have developed
a new method for inert gas shielding in
seam welding process. This prevents Cr
oxide formation during seam welding, and
sound weld seam has been obtained.
The newly developed HF-ERW martensitic
stainless steel line pipe has higher produc-
tivity than seamless martensitic stainless
line pipes. In addition, it has higher dimen-
sional accuracy, and thinner wall thickness
is available.
In the following, the design concept for
material, the manufacturing process, and
the dimensional and mechanical properties
of the trial products are described. The
mechanical properties and corrosion resis-
tance of the HF-ERW portion and the
welded joint are also described.

2 Concept of materials design

2.1 Target properties

Figure 1 shows the service environment of
martensitic stainless steel line pipes. The
target of the development was to obtain a
martensitic stainless steel that has suf-
cient corrosion resistance in the wet CO

2


environment shown in gure 1. Table 1
shows the target properties including
mechanical ones. The target low-tempera-
ture toughness in the base metal, the ERW
portion and the welded joint was set at 40J
or above in terms of the absorbed energy at
20C in the Charpy V-notch impact test.
Girth welding was assumed to be carried
out without pre-heating and post weld heat
treatment (PWHT). Target strength grade
was set at American Petroleum Institute
(API) X80 considering the matching with
weld materials.

2.2 Basic concept

Figure 2 shows the basic concept to obtain
weldable martensitic stainless steel line
pipes having tough welded joint, excellent
weldability and high corrosion resistance.
To obtain good CO

2

corrosion resistance,

Development of weldable martensitic stainless steel line pipe by HF-ERW process

Stainless Steel World



1999 KCI Publishing BV

SSW99-042

PAGE 332

Cr content must be 11% or above. Lower C
and N contents are required to keep the
hardness in the heat-affected zone (HAZ)
from increasing. To prevent the formation of
coarse

-ferrite that impairs the toughness
of the HAZ, Ni, which is a

-phase stabilis-
ing element other than C and N, is added to
produce a fully martensitic structure in the
HAZ. Mo is added to increase the sulphide
stress cracking (SSC) resistance in the wet
CO

2

environments containing trace
amounts of H

2

S (0.001 bar or below).

3 Trial products of HF- ERW pipe

3.1 Chemical composition and manufacturing
process

Table 2 shows the chemical composition of
the ultra-low C, ultra-low N, 11% Cr, 3.5%
Ni and 1% Mo steel developed. Figure 3
shows the manufacturing process. Air cool-
ing after hot rolling forms a homogeneous
martensitic structure in the base metal. The
obtained strip was annealed below the Ac

1


temperature to reduce the strength to
desired level. This strip was formed into a
pipe by HF-ERW process with a diameter of
10

3

/

4

in. in a most advanced ERW pipe mill
at Nagoya Works. Welding was done in an
inert-gas atmosphere so as to prevent the
formation of chromium oxide and in-line
seam heat treatment was applied to reduce
the ERW portion hardness.

3.2 Mechanical properties and microstructure

3.2.1 St rengt h

Table 3 shows the results of tensile tests for
the base metal and HF-ERW portion.
Because of the proper heat treatment
applied to the hot-rolled strip, strength of
the X80 grade was stably obtained. The
tensile test specimen containing the HF-
ERW portion ruptured in the base metal
after tensile test. This showed that good
welding was done. Strength at elevated
temperatures are illustrated in gure 4.
A decline in yield strength with increasing
temperature was small. The yield strengths
at temperatures from 100 to 150C, which
are expected service temperatures, were as
high as those at a room temperature.

3.2.2 Toughness

Figure 5 shows the results of the Charpy
impact test on the base metal and the HF-
ERW portion. Table 4 shows the results of a
V-notched impact test conducted on the
HAZ of the seam heat treatment with vari-
ous positions of the notch. Figure 6 sche-
matically shows the HAZ of the seam heat
treatment. Both the base metal and the HF-
ERW portion proved to have enough
absorbed energy at 20C.

3.2.3 Crack t i p openi ng di spl acement (CTOD)

Table 6 shows the results of the CTOD test.
The target CTOD value of 0.15 (

= 0.15mm)
was satised in all areas including the HF-
ERW portion.

3.2.4 Hardness

Table 5 shows the Vickers hardness of the
base metal and the HF-ERW portion. The
actual Vickers hardness was under 300 (Hv
< 300), which meets the target hardness of
not higher than 350.

3.2.5 Mi crost ruct ure

Figure 7 shows the microstructure of the
base metal and the HF-ERW portion. Both
the base metal and the HF-ERW portion
proved to have homogeneous tempered
martensite structures.

3.3 Pipe dimensions

Table 7 shows the roundness and the
eccentricity of the trial pipes. The round-
ness and the eccentricity averaged 0.15%
and 0.9%, respectively. The dimensional
accuracy was much better than that of ordi-
nary seamless pipes and comparable to
that of ordinary HF-ERW pipes.

3.4 Welded joints

Table 8 shows the gas tungsten-arc welding
(GTAW) conditions. Figure 8 shows the
hardness prole and macrostructure in the
welded joint. Table 9 shows the results of
the tensile tests on the welded joints. All
tensile specimens ruptured in the base
metal. As is evident from table 10, the
welded joint have enough absorbed energy.
Table 11 shows the results of the CTOD
test. The welded joint, like the base metal,
has sufcient property.

4 Corrosion properties

4.1 General corrosion properties

Corrosion tests at 100C in 25 mass% NaCl
aqueous solution were conducted for base

Stainless Steel World 99 Conference

Stainless Steel World



1999 KCI Publishing BV

SSW99-042

PAGE 333

metal, HF-ERW portion and girth weld por-
tion. The test conditions are listed in
table 12. The results are tabulated in
table 13. In any conditions, the corrosion
rates were lower than 0.01mm/y and no
crevice corrosion was observed.

4.2 Sulphide stress cracking (SSC) properties

An SSC test were carried out under condi-
tions which are listed in table 14. The results
are listed in table 15. The critical H

2

S partial
pressure for this line pipe is estimated to be
0.001 bar in 5% NaCl solution.

4.3 Cathodic protection properties

Resistance to hydrogen embrittlement
under cathodic protection was tested under
conditions listed in table 16. Even at
1194mV vs SCE, which corresponds to an
over cathodic protection, no crack was
observed. The steel was immune from
hydrogen embrittlement even under
cathodic protection.

5 Conclusions

1 A new type of weldable martensitic stain-
less steel line pipe, with thin wall thick-
ness and high dimensional accuracy, has
been developed by applying improved
inert-gas shielding technology in HF-
ERW process.
2 The developed pipes were weldable
without pre-heating and PWHT. All inves-
tigated properties, including those of HF-
ERW portion and welded joint, proved to
satisfy the target mechanical properties
and corrosion resistance requirements.

Ref erences

1 H. Asahi, K. Nose, H. Inoue, H. Tamehiro, T. Teras-
awa, M. Koyuba and N. Ayukawa: Corrosion and
Mechanical Properties of Weldable Martensitic
Stainless Line pipes, Super martensitic Stainless
Steels 99, 2728 May 1999.
2 K. Nose, H. Asahi, H. Tamehiro and H. Inoue: The
Material Design and Properties of Martensitic Stain-
less Steel for Flowline Line Pipes, 16th Interna-
tional Conference on Offshore Mechanics and
Arctic Engineering, The Offshore Mechanics and
Arctic Engineering Division of the American Society
of Mechanical Engineers, ISBN 0-7918-1801-2, 13
18 April 1997.

Development of weldable martensitic stainless steel line pipe by HF-ERW process

Stainless Steel World



1999 KCI Publishing BV

SSW99-042

PAGE 334
Figure 1. Application image of develop-
ment.
Figure 2. Basic concept of alloy design for new weldable martensitic stainless line pipe.
Figure 3. Manufacturing process.

Stainless Steel World 99 Conference

Stainless Steel World



1999 KCI Publishing BV

SSW99-042

PAGE 335
Figure 4. Strength at elevated tempera-
tures.
Figure 5. Charpy impact test results of base metal and ERW portion (transverse direction,
1/2 sub-size)

Development of weldable martensitic stainless steel line pipe by HF-ERW process

Stainless Steel World



1999 KCI Publishing BV

SSW99-042

PAGE 336
Figure 6. Schematic diagram of ERW portion and seam heat treatment zone.
Figure 7. Microstructure of ERW portion and
base metal.
Figure 8. Macrograph and hardness prole of weld cross- section.
|-------|
25m

Stainless Steel World 99 Conference

Stainless Steel World



1999 KCI Publishing BV

SSW99-042

PAGE 337

Process HF-ERW
Grade X80 equivalent (YS

550 MPa, TS

620 MPa)
CO

2

corrosion Corrosion rate < 0.1 mm/y (100C, 10 bar, CO

2

, sweet)
Toughness* vE

-20

40J (full size, transverse)
Hardness* Hv

350
Weldability no cold crack (without pre-heating and PWHT)

Table 1. Target performance of development.
* including weld joint HAZ

C Si Mn P S Cr Ni Mo Ti N
Aiming < 0.015 0.2 0.5 < 0.03 < 0.003 11.0 3.5 1.0 0.03 < 0.015
Actual 0.003 0.19 0.43 0.026 0.0013 11.0 3.5 1.0 0.027 0.0067

Table 2. Chemical composition of tested steel (wt.%).

Location Orientation YS (MPa) TS (MPa) El. (%)
Base metal Transverse 611 766 27
ERW portion Transverse 635 795 24
Aiming

550

620

20

Table 3. Tensile test results.

Notch position Temp (C) Energy (J ), average Shear area (%), average
ERW portion (weld centre) 20 142 100
WC + 1mm 20 131 100
WC + 2mm 20 116 100
WC + 5mm 20 120 100
WC + 12mm* 20 123 100

Table 4. Charpy impact test results of ERW portion and seam heat treatment zone (transverse direction 1/ 2 sub- size).
* WC + 12mm: boundary of the visible seam heat treatment zone

Average Max.
Base metal 245 257
ERW portion 280 294
Seam heat treatment zone 246 261

Table 5. Hardness of base metal and HF- ERW HAZ.

Location Spec. Orientation/size Temp. (C) CTOD (

/mm),
average
Base metal BS7448 Part 1 Transverse/B

2B
(B=5mm)
20 0.35
ERW portion (weld cen-
tre)
BS7448 Part 1 Transverse/B

2B
(B=5mm)
20 0.52
WC + 5mm BS7448 Part 1 Transverse/B

2B
(B=5mm)
20 0.46
Criteria 20

0.15

Table 6. CTOD test results.

Development of weldable martensitic stainless steel line pipe by HF-ERW process

Stainless Steel World



1999 KCI Publishing BV

SSW99-042

PAGE 338

Pipe no. Roundness Eccentricity
1 0.11% 1.03%
2 0.22% 0.90%
3 0.15% 0.90%
4 0.15% 0.64%
5 0.11% 1.03%
Average 0.15% 0.15%

Table 7. Roundness and eccentricity of pipes.
Roundness = (max. OD min. OD) / nominal OD

100% Eccentricity = (max. WT min. WT) / nominal WT

100%
OD = outer diameter WT = wall thickness

Welding method 15 pass GTAW
Filler superduplex (25% Cr)
Diameter 2.4mm
Groove V
Preheat not applied
Shield gas Ar
Heat input 0.81.2 kJ /mm
cap. 1.7 kJ /mm
Interpass max. 150C
PWHT not applied

Table 8. Girth welding condition.

Orientation TS (MPa) Failure position
Transverse 770 Base metal
781 Base metal
776 Base metal

Table 9. Results of weld tensile tests.

Notch position Temp. (C) Energy (J ), average Shear area (%), average
Weld metal 20 100 76
FL (fusion line) 20 105 78
FL + 2mm 20 122 78
FL + 5mm 20 109 76
Boundary of the visible HAZ 20 117 77

Table 10. Charpy impact test results of girth- welded joints (transverse orientation, 1/ 2 sub- size).

Location Spec. Orientation/size Temp. (C) CTOD ((/mm), average
Weld metal BS7448 Part 1 transverse/B

2B (B=5mm) 20 0.52
Fusion line BS7448 Part 1 transverse/B

2B (B=5mm) 20 0.41
Criteria 20

0.15

Table 11. CTOD test results of girth- welded joints.

Sweet Sweet (H

2

S)
Temperature 100C 100C
H

2

S partial pressure 0 0.001 bar
CO

2

partial pressure 10 bar 10 bar
NaCl contents 25 mass% 25 mass%
Test duration 91 days 91 days

Table 12. Conditions of general corrosion tests.

Stainless Steel World 99 Conference

Stainless Steel World



1999 KCI Publishing BV

SSW99-042

PAGE 339

As-welded + shot-blasted Machined
Base + ERW Girth Base + ERW Girth
Sweet < 0.01 mm/y < 0.01 mm/y < 0.01 mm/y < 0.01 mm/y
Sweet (H

2

S) < 0.01 mm/y < 0.01 mm/y < 0.01 mm/y < 0.01 mm/y

Table 13. Results of general corrosion tests.

Temperature 25C
H

2

S partial pressure 0.001 bar
CO

2

partial pressure 1 bar
NaCl contents 5 mass%
pH 4
Stress 100% YS
Test duration 30 days

Table 14. Conditions of SSC test (4- point bend beam test).

NaCl (%) Test conditions Results
H

2

S (bar) Girth, machined Girth, as-welded + shot-blasted ERW, machined
5 0.001 NC, NC NC, NC NC, NC

Table 15. Results of SSC test.
NC = no crack

Specimen location/orientation Girt weld cap/transverse weld
ERW weld cap/seam weld (not attened)
Specimen surface nish Girth weld cap surface was:
As-welded specimen: left intact
Machined specimen: machined at + nished (320 grid)
ERW seam weld was left intact
Stress 100% YS
Test solutions 3.5% NaCl
pH 5.4 (measured before test)
5.8 (for 1194mV) ~ 6.3 (for 894mV (measured after test)
Cathodic potential 1194mV vs SCE (1150mV vs Ag/AgCl)
894mV vs SCE (850mV vs Ag/AgCl)
Duration 90 days
Temperature 25C
Gas environment Open air

Table 16. Conditions for cathodic protection tests (4- point bend beam test).

Cathodic potential Girth weld ERW seam weld
As-pipe specimens
As-welded specimens Machined specimens
1194mV vs SCE No crack No crack No crack
894mV vs SCE No crack No crack No crack

Table 17. Cathodic protection test results.

Development of weldable martensitic stainless steel line pipe by HF-ERW process

Stainless Steel World



1999 KCI Publishing BV

SSW99-042

PAGE 340