Proceedings of The Twelfth (2002) International Offshore and Polar Engineering Conference Kitakyushu, Japan, May 26 31, 2002

Copyright 2002 by The International Society of Offshore and Polar Engineers ISBN 1-880653-58-3 (Set); ISSN 1098-6189 (Set)

Development of Weldable Super 13Cr Martensitic Stainless Steel for Flowline

K.Kondo*), K.Ogawa*), H.Amaya*), M.Ueda**), and H.Ohtani*),
*)Corporate Research & Development Laboratories, Amagasaki Hyogo Japan **)Wakayama Steel Works Minato Wakayama Japan Sumitomo Metal Industries, Ltd.

ABSTRACT
Development of a weldable 13Cr martensitic stainless steel for flowline is introduced. Alloy design concept, weldability and corrosion resistance of newly developed 13Cr martensitic stainless steels for CO2 with a small amount of H2S environment are described. The concept of welding is also introduced including welding material and welding process. Super duplex stainless steel is recommended as a welding material for girth welding in order to meet even or overmatching in tensile properties, so that sulfide stress cracking (SSC) susceptibility is minimized and the enough impact toughness is secured even in the heat affected zone without the post weld heat treatment. The effect of environmental factors on SSC and localized corrosion of the weldable 13Cr martensitic stainless steel joint welded by gas tungsten arc welding (GTAW) and gas metal arc welding (GMAW) employing super duplex stainless steel as a welding material is discussed.

KEY WORDS:
duplex; SSC

Flowline; weldable; 13Cr; stainless; martensite;

Super 13Cr with the improved resistance to general corrosion, localized corrosion and sulfide stress cracking (SSC) have been proposed for OCTG usage[4-8]. The basic concept is the increase in effective Cr content by the reducing carbon content, the addition of nickel to maintain martensitic phase without ferrite and the addition of Mo to improve the resistance to localized corrosion and SSC. Since the lowering the carbon content causes the reduction of the hardenability of the steels, the possibility of improved weldability has been also expected. Moreover the substantial corrosion resistance and good toughness even in the heat affected zone (HAZ) has also been achieved by modifying the conventional chemistry to Ultra Low Carbon Steel because the increase in the hardness in HAZ is restrained sufficiently. Several modified Super 13Cr steels have been proposed for flow line application in CO2 or CO2/H2S environment[911]. Some of them have been already installed as the sub-sea flow line in the North Sea field[12]. In this paper the development of the weldable Super 13Cr line pipe for CO2+H2S environment is introduced from the viewpoint of the alloy design, weldability and corrosion resistance.

ALLOY DESIGN INTRODUCTION

13% Cr steel has been widely used over years as an OCTG material because of its excellent corrosion resistance. The use of 13% Cr steel OCTG is recognized as a standard countermeasure to contend with corrosion attack initiated by carbon dioxide in oil and gas wells[1-3]. However, conventional type of 12-13% Cr steel has not been utilized so much as line pipe because of its relatively poor weldability, which requires pre-heating prior to welding and post weld heat treatment (PWHT). Utilizing carbon steel with corrosion inhibitor system to handle the wet hydrocarbon products containing CO2 and or H2S is one solution, however it does not seem practical in a sub-sea completion system due to difficulty of controlling the inhibitor system and high cost for injection system. Therefore duplex stainless steel has been employed for flow line in sweet environment, because of its property of maintenance free and the superior weldability in spite of increasing the cost of materials. Recently a number of new 13Cr martensitic stainless steels, that is,

GENERAL CONCEPT ON PHASE BALANCE IN MARTENSITIC STAINLESS STEEL

Martensitic stainless steel has been qualified as not only good corrosion resistance due to high Cr content but also high strength due to martensitic structure. In order to create a new alloy design of improved steel with maintaining martensitic structure, it is helpful to understand the phase diagram because the critical content of composition could be estimated. One problem is whether it is possible to increase Cr content in order to obtain superior corrosion resistance. Effect of chromium content on equilibrium relationship in 0.2% C steel is described in Figure 1. In order to obtain martensitic phase without ferrite, a steel with chemical composition, that is inside of the austenite single phase region (called loop) at solution temperature is austenitized then cooled to room temperature to transform into martensite. Air quenching is normally applied because of the high susceptibility to quench crack or delayed fracture and a rapid cooling is not necessary due to good hardenability in high Cr steel. The finishing temperature

303

1600 1500 Temperature / C 1400 1300 1200 1100 1000 900 800 700
+M7 ++M7

0.2%C - Fe - Cr
L L+

0% 20 L++M23
(

Phase ratio

100%
)

L++ +

Cr / mass%

18

martensite + ferrite 0%Mo martensite + austenite

austenite

16

(-loop)
+M23 + M23 + +M23
M23 : M23C6 M7 : M7C3 M3 : M3C

1%Mo 2%Mo martensite

14

12

10

12

14

++M3 +M3

Ni / mass%

+M7+M23

+M7+M3

10

20
Cr / mass%

30

Fig.2 Martensite single phase in low C-Fe-Cr-Mo system

Fig.1. Section diagram at 0.2%C in Fe-Cr-C ternary system of martensitic transformation (Mf) is located at about 150C that is almost critical point not to retain austenite. Therefore the maximum Cr content for transformable steel without ferrite has been determined to be about 13% in 0.2% C steel. Increasing Cr content more than about 13%, the ferrite forms at the solution temperature and remains in the microstructure, then it detracts much from the strength, hot workability and resistance to SSC. Since carbon element has been known to stabilize and expand the austenite region in the phase diagram, Cr and C could be increased simultaneously to maintain the martensitic microstructure. However in that case the effective Cr content is scarcely increased because of decrease in solute Cr by increasing precipitation of M23C6 type carbide where the main constituent of M has been reported to be Cr. Moreover the deterioration of toughness due to the increase in Cr carbide is also reported[13]. Therefore it is meaningless to increase Cr content with increase in C content in order to prevent the formation of ferrite. From the discussions above, the reducing the C content should be adopted to increase effective Cr. In this case ferrite also forms at solution temperature due to a lack of austenite stabilizing element. In order to obtain austenite single phase at solution temperature, some austenite stabilizing element such as Ni, Co, Cu, and Mn should be added or raised in content. Ni is the most suitable element because it has the strongest effect on forming austenite phase compared with other elements[13]. Though some modification could be also available for these alloys, the basic idea for improved steel should be low C, about 13% Cr and addition of Ni. The martensitic phase region at room temperature without ferrite and retained austenite in 0.01%C-Fe-Cr-Mo system after austenitized at This was verified by the 1050C is indicated in Figure 2. microstructure observation of steels containing 12 to 19% Cr, 2 to 14% Ni, and 0 to 3% Mo. Though Ni addition is necessary to stabilize austenite phase and not to form ferrite at solution temperature, too much addition makes the austenite phase excessively stable, then retained austenite remains because the finishing temperature of martensitic transformation falls below room temperature. Too much addition of Cr forms ferrite, therefore only limited narrow region of martensitic single phase is shown. Since Mo has been known to be the ferrite-forming element and lowers the Ms temperature, the addition of Mo also narrows the martensitic single phase region remarkably.

Approach to improved resistance to SSC in low alloy steel (conventional approach) Improvement in susceptibility of hydrogen embrittlement of materials in itself Decrease in impurity element Refinement of grain size Homogenized microstructure Copernican change New approach to improved resistance to SSC in martensitic stainless steel Suppression of corrosion rate Decrease in generated hydrogen Decreased in hydrogen permeation rate Decrease in hydrogen content in steel

Fig.3 A new approarch to improve the resistance to SSC

RESISTANCE TO SULFIDE STRESS CRACKING

A lot of work for improved resistance to SSC in low alloy steel which is caused by hydrogen embrittlement has been reported. It has been well recognised that microstructure control such as refinement of grain size, homogenizing structure, and decrease in segregation of impurity element along grain boundary, is the most effective factor to improve the resistance to SSC[14]. While a typical martensitic stainless steel API13Cr has been known that critical limit to H2S partial pressure for SSC is quite inferior to low alloy steels in spite of high Cr content. Though the microstructure control could be applied to improve the resistance to SSC, successful improvement has not reported however. Kushida et al. tried to understand this problem, then clarified the effect of Cr, Mo, Ni on the hydrogen embrittlement in martensitic steels[15]. According to their result, as the content of alloying elements such as Cr, Mo and Ni increased, the apparent hydrogen diffusion coefficient decreased. Since hydrogen content in steel is proportional to the inverse of the hydrogen diffusion coefficient, the hydrogen content in high Cr steel becomes quite large compared with low alloy steels. Consequently the high Cr steel with quite smaller diffusion coefficient has a much higher susceptibility to hydrogen embrittlement. Since threshold hydrogen content in these steels were proved to be almost

304

1.0 Corrosion rate / mm/y

0.1

Maximun Hardness / Hv

: No crack : Pitting : Crack

400 Mother Metal Heat Affected Zone 350

0.01

0.001

0.001MPa H2S +3.0MPaCO2, 5%NaCl, 25C, constant load, 1y

300

250

1 2 Mo / mass%

200

Fig.4 Effect of Mo content on corrosion rate and SSC susceptibility

0.005

0.01 C / mass%

0.015

Corrosion rate / mm/y

1.6 25%NaCl,
150C

3.0MPaCO2,

Decrease in effective Cr content due to precipitation of Cr carbide

Fig.6 Effect of carbon content on the maximum hardness in mother metal and the heat affected zone by welding

1.2 0.8 0.4 0

13Cr-0.2C
Improvement of corrosion resistance by addition of Mo

0.1%V 13Cr-5Ni-2Mo 900 YS TS / MPa TS YS V-free

800

0.01C-4.5Ni-2Mo
8 9 10 11 12 13 14 Effective Cr content / mass% 15

700 850CX30min WQ +630X1hr AC 0 0.05 Carbon Content / mass%

Fig.5.Effect of Cr content on the corrosion rate in CO2 environment

600

constant, it should be concluded that the conventional approach to improving the resistance to SSC by controlling the microstructure is not suitable for the high Cr steels and then the hydrogen permeation rate should be decreased. As shown in Figure 3, the most favourable solution to decrease in hydrogen content in high Cr steels is lowering the hydrogen permeation rate by means of the suppression of the hydrogen generated on the surface by corrosion, which corresponds to lowering the corrosion rate. The SSC resistance of the various low C martensitic stainless steel has been investigated in 5% NaCl solution with 3.0MPa CO2 and 0.001MPa H2S at 25C. The test results of the corrosion rate and SSC susceptibility are shown in Figure 4. The corrosion rate was remarkably reduced with the increase in Mo content. The steel with 2% Mo or higher content did not suffer SSC, while steels with 1% Mo or no addition suffered SSC or pitting in exposed environment.

Fig.7 Effect of V and C contents on tensile strength

reduced due to Cr carbide precipitation, however they still showed superior corrosion resistance. Therefore the general corrosion property is improved not only by the increase in effective Cr but also by the increase in Mo and/or Ni content in the improved martensitic stainless steel.

SUPPRESSION OF HARDENING IN HEAT AFFECTED ZONE

The effect of C content on the maximum hardness in the HAZ is shown in Figure 6. The maximum hardness in the base metal consisting of the tempered martensite was about 280 in Vickers Hardness and did not show so much relation with the C content. However the maximum hardness in HAZ was increasing with the C content. It is reasonable to think that the portion heated just below melting point in the HAZ transforms into harder martensite due to super-saturation by increasing C solution, because most of the carbide dissolves at that temperature. Lowering of C below 0.015% is favorable to the corrosion resistance in the HAZ without PWHT since the increase in maximum hardness bring about the higher susceptibility to SSC.

GENERAL CORROSION RESISTANCE

Low C martensitic stainless steel is expected to have good corrosion resistance to CO2 environment compared with conventional API13Cr OCTG Steel. Figure 5 demonstrates that the corrosion rate of low C martensitic stainless steel in the CO2 environment at 150C decreased enormously, while conventional API13Cr steel showed high corrosion rate in spite of the nominal Cr content is about 13%. The 10 or 11% Cr, Ni and Mo bearing steel is considered to be almost equivalent in effective Cr with API13Cr because that in the API13Cr steel should be

305

EFFECT OF CARBON STABILIZING ELEMENT

In order to realise a mass-production of a new generation alloy, a stability of mechanical property is required. Figure 7 shows the effect of carbon and vanadium which is a common impurity element in high Cr steels, on the tensile strength after tempering. Even in the low carbon martensitic steels secondary hardening was observed and the strongest hardening was obtained with the specific carbon content range around 0.01%. A reduction of vanadium content by refining costs much and even in the vanadium free steels other slight secondary hardening alloy such as molybdenum and chromium are thought to scatter the mechanical properties. Therefore the addition of carbon stabilizing element to prevent precipitation of secondary carbide was carried out. The addition of a small amount of Ti reduced the secondary hardening remarkably. However the secondary hardening was observed again in the alloy with too much addition of Ti. Since the strength as quenched condition was also reduced remarkably by titanium addition, free carbon that can cause precipitation hardening, should be suppressed quite low. In the case of too much titanium addition intermetallic compound such as TiNi is considered to precipitate and showed secondary hardening again. Moreover it has been clarified that Ti addition is effective to maintain finer microstructure in the HAZ due to the pinning effect by TiN precipitate, because the solubility of TiN is sufficiently low even at the temperature just below melting point. As a result a superior corrosion resistance is expected due to the low and stable tensile strength and fine microstructure in the HAZ by the addition of a suitable amount of Ti.
Mo content / mass%

4 3 2

Resistant to CO2 6% Ni general corrosion Resistant to SSC

Weldle Super 13Cr

1

Martensite single phase

0 10 11 12 13 14 Cr content / mass% 15

Fig.8 The role of alloying element in weldable super 13Cr for CO2/H2S environment
700

Yield strength / MPa

600

500

DEVELOPED ALLOY AND TYPICAL MECHANICAL PROPERTIES ALLOY COMPOSITION

From the result discussed above, the region of suitable chemical composition of weldable Super 13Cr are indicated in Figures 8. The nominal chemical composition is ultra low-C (less than 0.015%) 12Cr6Ni-2.5Mo steel. The chemical composition ranges of these developed alloys are arranged in Table 1. Table 1. Chemical compositions of Weldable Super 13Cr (mass%) (UNS No.S41426) C Cr Ni Mo Ti 13Cr-S Max. 0.03 11.5 -13.5 4.5 -6.5 1.5 -3.0 0.01 -0.5
400 0 50 100 150 200 250 300

Temperature / C
Fig.9 Typical yield strength change at elevated temperatures

400

Absorbed Energy / J/cm2

300

MECHANICAL PROPERTIES
Figures 9 shows the typical yield strength change of steel from a room temperature to elevated temperatures. These steels show high strength within API X80 grade at a room temperature. Moreover the drop of the yield strength with increase in temperature seems smaller compered with other steels especially with duplex stainless steel. The high yield strength around 100C is favourable to employ these steels for a flowline. The typical impact properties of 13Cr-S is shown in figures 10. Sufficient absorbed energy is shown much below 46C that correspond to the severest specification for the impact properties for flowlines.

200

100

0 -120 -100 -80 -60 -40 -20

20

Temperature / C
Fig.10 Typical impact properties in 13Cr-S

306

WELDABILITY PERFORMANCE OF HEAT AFFECTED ZONE

The HAZ properties of the super 13Cr martensitic stainless steel line pipe was investigated using simulated HAZ test to clarify the properties distribution in the zones affected at various temperatures. The pipe employed was 550Mpa (80ksi) grade in 0.2% yield strength and 253 mm in diameter and 12.3 mm in wall thickness and consists of Steel 13Cr-S of which typical chemical compositions are shown in Table 2. The test specimens were treated with simulated weld thermal cycles heated up to the peak temperature of 600 to 1400C and cooled in the average cooling rate of 3 to 30 C /s. The simulated HAZ treated specimens were evaluated in terms of the Vickers hardness test and Charpy impact test at -30C using 5mm thick V notched specimens. Table 2 Chemical composition of material tested (mass%) C 13Cr-S 0.008 Si 0.15 Mn 0.43 Cr 12.0 Ni 6.5 Mo 2.5 Ti 0.1

300

Impact value (J/cm2)

200

100

RT

(( ))

1000

1500

Peak temperature / C
Fig.12 Effects of peak temperature and cooling rate on impact properties of simulated HAZ

The Vickers hardness in the simulated HAZ of this steel are shown in Figure 11. The hardness did not increase so much and the effect of peak temperature was not so remarkable. The maximum hardness was about 300 in Vickers number which was observed in the simulated HAZ heated to 1000-1200C. The impact toughness of simulated HAZ of this steel are shown in Figure 12. Enough high impact value over 200 kJ/cm at -30C was obtained in all the HAZ heated up 600 to 1400C and cooled with the cooling rate of 10C /s. Since this steel is alloyed with Titanium, Ti(C,N) precipitation remains as a stabilizer for C and N atom to prevent hardening after martensitic transformation, moreover keeps microstructure fine so that good toughness can be obtained at wide temperature range of the weld thermal cycles.

SELECTION OF WELD METAL

The weld metal in the weldment of super 13Cr martensitic steel line pipe was designed from a point of view to obtain as high mechanical and corrosion properties in the weldment as in the base metal. The base metal of this steel is designed as enough low hardness in the HAZ even without post weld heat treatment to have sufficient resistance to sulfide stress corrosion cracking[9]. Therefore the weld metal is also to be designed to have sufficient SSC resistance even without PWHT. The weld metal consisting of ferrite and austenite duplex stainless steel is expected to have even or higher SSC resistance than this 13Cr base metal. However conventional duplex stainless steel weld such as 22Cr is under-matching to the base metal of which strength is X-80 grade. In addition by using under-matching weld metal, the SSC can easily occur because high stress distributes at the HAZ[16]. So the weld metal should be designed by even or over matching materials so called super duplex stainless steel which strengthened by the addition of tungsten and the increase of nitrogen[17]. Table 3. shows typical example of corrosion test result of welded joints of 13Cr-S employing 22Cr duplex stainless steel (22.1Cr-8.4Ni-3.3Mo0.1N) or Super duplex stainless steel (25.7Cr-9.3Ni-3.1Mo-2.3W0.26N) as a welding consumable. Constant load method was carried out under the condition shown in Table 3. Table 3. Corrosion test result of welded joints of 13Cr-S using two types of duplex stainless steels as welding consumables Test condition Weld metal SSC test result 25oC, 0.004MPa H2S 22Cr Failure(230h) +0.096MPa CO2, duplex Failure(609h) 68,000ppm Cl-, pH 4.5 Super No Failure duplex No Failure Applied stress: 1y of base metal Welded joints with 22Cr duplex as a welding consumable suffered SSC while those with Super duplex did not suffer SSC. It is considered that much stress concentration exists in the HAZ near fusion line employing under-matching welding material such as 22Cr duplex stainless steel, as a result SSC arised. In practical fabrication the welding consumable already developed for a super duplex stainless steel is employable to obtain the matching weld metal.

400

Vickers hardness

300

200

RT

(( ))

1000

1500

Peak temperature / C
Fig.11 Effects of peak temperature and cooling rate on hardness of simulated HAZ

307

Table 4 Tensile and bending properties of Steel 13Cr-S welded joints

Welding process Welding condition Weld heat Inter-pass input temperature (kJ/mm) (C) 1.1 1.6 2.2 GTAW 1.6 1.6 1.6 GMAW 1.6 150-200 400 <50 <50 None None 650C, 5min None <50 <50 <50 Tensile properties Tensile Fractured strength portion (MPa) 871 Base metal 874 Base metal 874 Base metal 873 Base metal 873 Base metal 872 Base metal 884 Base metal 883 Base metal 881 Base metal 884 Base metal 868 Base metal 862 Base metal 871 Base metal 876 Base metal Bending properties Results (Bending radius:2xT) No defects No defects No defects No defects No defects No defects No defects No defects No defects No defects No defects No defects No defects No defects

PWHT None None None

PROPERTIES OF WELDED JOINTS

The weld joining test was conducted to confirm the applicability of the

300

Impact value (J/cm2)

gas tungsten arc welding(GTAW) process and gas metal arc welding(GMAW) process. Pipe consisting of Steel 13Cr-S used for
the simulated HAZ test was employed. The welding consumable of X80 grade super duplex stainless steel with the diameter of 1.2 mm was employed for the both of GTAW and GMAW. The weld joining test with GTAW in the whole joint was conducted to clarify the allowable range of welding variable of weld heat input and inter-pass temperature. The welding was done with the various conditions of weld heat input of 1.1 to 2.2 kJ/mm and inter-pass temperature of 50 to 400C using the U shape bevel. The joint consisted of 6, 8, 14 passes for the heat input of 2.2, 1.6 and 1.1 respectively. The post weld heat treatment was not done except for one joint. Just one joint of those was PWHT treated at 650C for 5min to confirm the allowance of short duration PWHT. The welded joints obtained were evaluated in terms of mechanical properties by tensile, bending, Charpy impact and hardness test and corrosion property by SSC test. The mechanical tests were done according to the ASME Sec. IX. The SSC test was carried out using the four points bending test specimen with a notch at the fusion boundary of weldment. The test was conducted in the 5%NaCl solution with 0.001MPa H2S and 0.3MPa CO2 in partial pressure at 25C and applying stress of 100% yield stress of base metal for 336 hours. The weld joining test using GMAW accompanied with GTAW in just root pass was conducted to clarify the applicability of this welding process. The welding consisted of four layers and was done with the GMA welding condition of 140A in welding current, 27V in welding voltage and welding speed in 140mm/min using V shape bevel. In order to achieve prevention of porosity the shielding gas consisting 20% nitrogen and 80% argon was employed. The welded joints were evaluated without PWHT in the same terms as the above GTAW. The tensile and bending test results of the GTAW joints in the various welding conditions were summarized in Table 4. In tensile test the fractured portions of all the joints were at the base metal with sufficient high tensile strength. And any of the joints had no defects in the bending test. The effects of weld heat input and inter-pass temperature on the fracture toughness, which are Charpy impact test at -30C, are shown in Figures 13 and 14. The fracture toughness of weld metal and fusion line was sufficiently high in all the test conditions. All the Charpy impact values were higher than 150kJ/cm2 at the fusion line as well as at the weld metal. The impact value was slightly lowered by

200

100

Fusion line Weld metal open : As weld solid : PWHT(650C,5min)

Weld heat input (J/mm)

Fig.13 Effects of weld heat input on impact value

300

Impact value (J/cm2)

200

100
: Weld metal : Fusion line

100

200

300

400

Interpass temperature / C
Fig.14 Effects of inter-pass temperature on impact value

308

Table 5. SSC resistance of Steel 13Cr-S welded joints

Welding process GTAW GMAW Welding condition Weld heat Inter-pass input temperature (kJ/mm) (C) 1.6 <50 1.6 <50 1.6 <50 Resistance to SSC Results ( Four points bend test ) No SSC No SSC No SSC No SSC No SSC No SSC

PWHT(C) None 650C,5min None

PWHT but the value remained over 130 kJ/cm2. The results of SSC test of 13Cr-S GTAW joints in the various welding conditions were summarized in Table 5. SSC were not observed in any joints as results of inspection in the cross section using the microscope in the magnification of 500. The tensile and bending test results of the GMAW joints have already been summarized in Table 4 together with GTAW. In tensile test the fractured occurred at the base metal with sufficient high tensile strength. And any of the joints had no defects in the bending test. Finally the joints had no SSC in the same condition as GTAW joints shown in Table 5. From these results it was clarified that 13Cr-S line pipe has superior mechanical properties and SSC resistance in the weldment in all the welding condition range tested

400

Weld metal

Vickers hardness

300

200

Outer Middle Inner

CONCLUSION
The Alloy design of newly developed weldable Super 13Cr martensitic stainless steels for CO2+H2S environment was discussed. The results are summarised as follows: (1) The lowering C content less than 0.015% improves the toughness and the resistance to SSC by reducing the maximum hardness in the HAZ. (2) The suitable addition of Ti stabilizes and lowers the tensile strength, moreover it refines the microstructure in the HAZ. (3)Mo was clarified to be the very important element to improve. both the resistance to SSC and localised corrosion. (4) Weldable super 13Cr stainless steels 13Cr-S: ultra low-C (less than 0.015%) -12Cr-6Ni-2.5Mo-Ti for CO2 environment with a little amount of H2S was developed. (5)The welded joints of 13Cr-S by GTAW or GMAW using a super duplex welding material have stable performance such as tensile strength, fracture toughness and SSC resistance in the sufficiently wide range of welding conditions of 1.1 to 2.2 in heat input and up to 400C in inter-pass temperature.

10mm

100

distance

Fig.15 Hardness distribution in welded joint with 1.6kJ/mm in heat input and 50C in inter-pass temperature [5] Hashizume,S., Takaoka,T., Minami,Y., Ishizawa,Y. and Yamada,T., Corrosion/91, Paper No.28, NACE International, Houston, Texas, 1991 [6] Ueda,M., Kushida,T., Kondo,K. and Kudo,T., Corrosion/92, Paper No.55, NACE International, Houston, Texas, 1992 [7] Asahi,A., Hara,T., Kawakami,A. and Takahashi,T., Corrosion/95, Paper No.79, NACE International, Houston, Texas, 1995 [8] Barteri,M., DeCristofaro,N., Scoppio,L., Cumino,G. and Della Pina,G., Corrosion/95, Paper No.76, NACE International, Houston, Texas, 1995 [9] Ueda,M., Amaya,H., Kondo,K., Ogawa,K. and Mori,T., Corrosion/96, Paper No.58, NACE International, Houston, Texas, 1996 [10] Miyata,Y., Kimura,M., Koseki,T., Toyooka,T. and Murase,F., Corrosion/97, Paper No.19, NACE International, Houston, Texas, 1997 [11] Popperling,R., Niederhoff,K.A., Fliethman,J. and Keller,M., Corrosion/97, Paper No.38, NACE International, Houston, Texas, 1997 [12] Enerhang,J., Eliassen,S.L. and Kvaale,P.E., Corrosion/97, Paper No.38, NACE International, Houston, Texas, 1997 [13] Irvine,K.J., Crowe,D.J. and Pickering,F.B., Journal of The Iron and Steel Institute, August, 1960, pp386 [14] Gibala,R. and Hehemann,R.F., Hydrogen Embrittlement and Stress Corrosion Cracking, American Society for Metals 1984 [15] Kushida,T. and Kudo,T., Corrosion Engineering 41,799-809(1992) [16] Hirata,H., Amaya,H. and Komizo,Y., Proc. of OMAE 1997, Vol 3, p101 [17] Okamoto,H., Ueda,M. and Ogawa,K., Sumitomo Search, No54, October, 1993,p1

REFERENCES [1] Biagiotti,S.F.Jr.,P.E. and Reichman,J.S., Corrosion/95, Paper No.81, NACE International, Houston, Texas, 1995 [2] Kermani,M.B., Weighhill,G., Pendlington,T. and Elliot,G., Corrosion/95, Paper No.96, NACE International, Houston, Texas, 1995 [3] Baudoin,D.A., Barbin,D.K. and Skogsberg,J., Corrosion/95, Paper No.639, NACE International, Houston, Texas, 1995 [4] Tamaki,A., Corrosion/89, Paper No.469, NACE International, Houston, Texas, 1989

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