US3915697A - Bainitic steel resistant to hydrogen embrittlement - Google Patents

Bainitic steel resistant to hydrogen embrittlement Download PDF

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US3915697A
US3915697A US545897*A US54589775A US3915697A US 3915697 A US3915697 A US 3915697A US 54589775 A US54589775 A US 54589775A US 3915697 A US3915697 A US 3915697A
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steel
hydrogen embrittlement
resistant
ratio
bainitic
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Lucio Giuliani
Mario Sarracino
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Centro Sperimentale Metallurgico SpA
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Centro Sperimentale Metallurgico SpA
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/002—Bainite

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  • ABSTRACT A bainitic steel resistant to hydrogen embrittlement, and therefore resistant to sulphide stress corrosion cracking and highly useful in the oil industry, consists essentially of 0.15-0.35 C; up to 0.8 Mn; 0.8-1.0 Si; 1.0-2.0 Cr; 0.l-0.5 Mo; 0.2-0.6 Al; up to 0.03 P; up to 0.03 S; up to 0.05 Cu; 0002-0004 B; up to 01 Ta, balance essentially iron.
  • the ratio SizMn is l?. and the ratio Mo-Al is 1-3.
  • the sum of 0.5 X 7cCr 7cMO 100 X %B is l-2. preferably ll.5.
  • the bainitic structure is obtained directly in the as-rolled condition by air cooling any of a wide range of plate thicknesses.
  • N 80 A steel widely used in the oil industry is known as N 80 and has the weight composition of 0.35-0.40 C, 1.5 Mn, 0.3 Si, 0.3 Mo, up to 0.03 S, up to 0.03 P, 0.12 Cu. balance essentially iron. Although this steel complies with API LX, its average lifetime in oil industry applications is not very satisfactory.
  • Another object of the present invention is the provision of a high strength steel having a bainitic structure in the as-rolled condition for a wide range of plate thicknesses.
  • the steel of the present invention has the following per cent composition by weight: 0.15-0.35 C, up to 0.8 Mn, 0.8-1.0 Si, 1.0-2.0 Cr, 0.1-0.5 Mo, 0.2-0.6 Al, up to 0.03 P, up to 0.03 S, up to 0.05 Cu, 0002-0004 B, up to 0.1 Ta, balance essentially iron.
  • the SizMn ratio is l-2, and the Mo:Al ratio is 1-3.
  • Cr, Mo and B satisfy the relation 0.5 X %Cr %Mo 100 X %B 1-2, preferably l-] .5.
  • the chromium helps to make the structure more uniform and suppresses surface anodic activity of the steel facilitating oxidation of the sulphur from S to S". This latter action is also performed by silicon. although to a lesser extent.
  • Copper must be held to a low limit, because it raises the electrode potential in the presence of sulphur and favors the release of hydrogen, thus increasing the hydrogen concentration at the surface and hence its gradient inside the metal. It is to be noted that low copper is in contrast to the prior art in which it is higher.
  • the silicon performs the function of promoting diffusion of hydrogen, thereby tending to eliminate sharp gradients of hydrogen concentration.
  • the aluminum and chromium are synergetic at low stress; while the silicon and molybdenumare synergetic at high stress. This improves the behavior of the steel in contact with hydrogen.
  • the steel according to the present invention has longer life in a hydrogenating environment. and this life is less subject to variation according to applied load, than is true of the prior art.
  • the steel of the present invention also has good mechanical properties. including a tensile strength of. for example, kg/mm'-, a yield strength of, for example. 65 kg/mm'-, in the normalized condition. good creep resistance, and improved wear resistance.
  • a very important characteristic of the present invention is that the bainitic structure is obtained directly in the as-rolled condition for a wide range of plate thicknesses.
  • the preferred range of plate thickness is 10-30 mm; although thicknesses up to 60 mm can be rolled if a decrease of about 10 kg/mm in the values of the ultimate tensile strength and the yield strength can be accepted.
  • No special heat treatment is needed: the hainitic structure may be obtained directly by. for example, air cooling from a rolling temperature of. say. 850C. However, an increase in ultimate tensile strength and yield strength can be achieved by tempering at about 650C. for a time of about 90 minutes.
  • test specimens were machined from 20 mm. plate rolled at 850C and air cooled, with tempering for 90 minutes at 650C, and having the weight per cent composition 0.22 C, 0.65 Mn, 0.8 Si, 1.0 Cr. 0.41 Mo, 0.20 Al, 0.012 S, 0.011 P. 0.02 Cu. 0.002 B and 0.03 Ta. balance essentially iron.
  • the test specimens were similar in shape to standard round test specimens according to A.S.A. specifications, but with special characteristics for stress-corrosion testing.
  • a bainitic steel resistant to hydrogen embrittlement having the weight per cent composition 0.15-0.35 C. up to 0.8 Mn. 0.8l.0 Si. 1.0-2.0 Cr. 0. l0.5 Mo. 0. l0.6 Al. up to 0.03 P. up to 0.03 S. up to 0.05 Cu. 0002-0004 B. up to 01 Ta. balance essentiall v iron. the ratio SizMn being l2. the ratio MozAl being l-3. and the sum of 0.5 X 'fiCr 92 Mo 100 X /(B being l2.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)

Abstract

A bainitic steel resistant to hydrogen embrittlement, and therefore resistant to sulphide stress corrosion cracking and highly useful in the oil industry, consists essentially of 0.150.35 C; up to 0.8 Mn; 0.8-1.0 Si; 1.0-2.0 Cr; 0.1-0.5 Mo; 0.2-0.6 Al; up to 0.03 P; up to 0.03 S; up to 0.05 Cu; 0.002-0.004 B; up to 0.1 Ta, balance essentially iron. The ratio Si:Mn is 1-2 and the ratio Mo-Al is 1-3. The sum of 0.5 X %Cr + %MO + 100 X %B is 1-2, preferably 1-1.5. The bainitic structure is obtained directly in the as-rolled condition by air cooling any of a wide range of plate thicknesses.

Description

United States Patent Giuliani et a1. Oct. 28, 1975 BAINITIC STEEL RESISTANT T0 3,348,981 10/1967 Goda et a1. 75/124 x HYDROGEN EMBRITTLEMENT 3,600.161 8/1971 Inouye et a1. 4. 75/124 X Inventors: Lucio Giuliani; Mario Sarracino,
both of Rome, Italy Assignee: Centro Sperimentale Metallurgico S.p.A., Rome, Italy Filed: Jan. 31, 1975 Appl. No.: 545,897
US. Cl. 75/124; 75/126 C; 75/126 P; 148/37 Int. Cl. ..C22C 38/06; C22C 38/22; C22C 38/32 Field of Search 75/124, 126 P, 126 C; 148/37 References Cited UNITED STATES PATENTS 11/1956 Herzog 75/124 X 5/1966 Wada et a1 75/124 8/1972 Kubota et al. 75/124 Primary E.\'aminerL. Dewayne Rutledge Assistant Examiner-Arthur J. Steiner Attorney, Agent, or Firm-Young & Thompson [57] ABSTRACT A bainitic steel resistant to hydrogen embrittlement, and therefore resistant to sulphide stress corrosion cracking and highly useful in the oil industry, consists essentially of 0.15-0.35 C; up to 0.8 Mn; 0.8-1.0 Si; 1.0-2.0 Cr; 0.l-0.5 Mo; 0.2-0.6 Al; up to 0.03 P; up to 0.03 S; up to 0.05 Cu; 0002-0004 B; up to 01 Ta, balance essentially iron. The ratio SizMn is l?. and the ratio Mo-Al is 1-3. The sum of 0.5 X 7cCr 7cMO 100 X %B is l-2. preferably ll.5. The bainitic structure is obtained directly in the as-rolled condition by air cooling any of a wide range of plate thicknesses.
2 Claims, N0 Drawings BAINITIC STEEL RESISTANT TO HYDROGEN EMBRITTLEMENT rig rods and for pipes through which crude oil is pumped. ln oil well practice, the hydrogen sulphide and other sulphur compounds in the oil liberate hydrogen in contact with the steel, which gives rise to hydrogen embrittlement; and the steel of the present invention is particularly resistant to this.
Steels used in the oil industry are subjected to enormous stresses, especially during drilling operations. These steels accordingly have an ultimate tensile strength of 600-100 kg/mm or higher. However, such steels have a marked tendency to crack due to hydrogen embrittlement, and thus have a shorter life than lower strength steels.
It is believed that the cracking of high strength steels used in the oil industry results from microscopic structural inhomogeneities. It is believed that inclusions provide points of stress concentration: the larger the inclusion and the higher the strength of the matrix, the greater will be the stress concentration. Diffusion of hydrogen in steel seems to berelated to the local stress concentration; and so the hydrogen tends to concentrate at the larger inclusions in the matrix. This results in sharp localized hydrogen concentration gradients, which in turn promotes fracture. Therefore, high strength steels for use in the oil industry should ideally be as resistant as possible to hydrogen embrittlement.
A steel widely used in the oil industry is known as N 80 and has the weight composition of 0.35-0.40 C, 1.5 Mn, 0.3 Si, 0.3 Mo, up to 0.03 S, up to 0.03 P, 0.12 Cu. balance essentially iron. Although this steel complies with API LX, its average lifetime in oil industry applications is not very satisfactory.
Accordingly, it is an object of the present invention to provide a high strength steel particularly durable under conditions of the oil industry.
Another object of the present invention is the provision of a high strength steel having a bainitic structure in the as-rolled condition for a wide range of plate thicknesses.
Finally, it is an object of the present invention to provide a high strength steel which will be relatively simple and inexpensive to produce and rugged and durable in use.
Other objects, features and advantages of the present invention will become apparent from a consideration of the following more particular disclosure.
The steel of the present invention has the following per cent composition by weight: 0.15-0.35 C, up to 0.8 Mn, 0.8-1.0 Si, 1.0-2.0 Cr, 0.1-0.5 Mo, 0.2-0.6 Al, up to 0.03 P, up to 0.03 S, up to 0.05 Cu, 0002-0004 B, up to 0.1 Ta, balance essentially iron. The SizMn ratio is l-2, and the Mo:Al ratio is 1-3. Cr, Mo and B satisfy the relation 0.5 X %Cr %Mo 100 X %B 1-2, preferably l-] .5.
In the steel of the present invention, the chromium helps to make the structure more uniform and suppresses surface anodic activity of the steel facilitating oxidation of the sulphur from S to S". This latter action is also performed by silicon. although to a lesser extent.
Manganese must be held to a low limit, because of its high bonding with S and because it locks the austenite in a metastable form which, upon further transformation, gives rise to martensite that is very sensitive to hydrogen embrittlement.
Copper must be held to a low limit, because it raises the electrode potential in the presence of sulphur and favors the release of hydrogen, thus increasing the hydrogen concentration at the surface and hence its gradient inside the metal. It is to be noted that low copper is in contrast to the prior art in which it is higher.
The silicon performs the function of promoting diffusion of hydrogen, thereby tending to eliminate sharp gradients of hydrogen concentration.
The aluminum and chromium are synergetic at low stress; while the silicon and molybdenumare synergetic at high stress. This improves the behavior of the steel in contact with hydrogen.
As a result, the steel according to the present invention has longer life in a hydrogenating environment. and this life is less subject to variation according to applied load, than is true of the prior art.
The steel of the present invention also has good mechanical properties. including a tensile strength of. for example, kg/mm'-, a yield strength of, for example. 65 kg/mm'-, in the normalized condition. good creep resistance, and improved wear resistance.
A very important characteristic of the present invention is that the bainitic structure is obtained directly in the as-rolled condition for a wide range of plate thicknesses. The preferred range of plate thickness is 10-30 mm; although thicknesses up to 60 mm can be rolled if a decrease of about 10 kg/mm in the values of the ultimate tensile strength and the yield strength can be accepted. No special heat treatment is needed: the hainitic structure may be obtained directly by. for example, air cooling from a rolling temperature of. say. 850C. However, an increase in ultimate tensile strength and yield strength can be achieved by tempering at about 650C. for a time of about 90 minutes.
EXAMPLE A large number of test specimens were machined from 20 mm. plate rolled at 850C and air cooled, with tempering for 90 minutes at 650C, and having the weight per cent composition 0.22 C, 0.65 Mn, 0.8 Si, 1.0 Cr. 0.41 Mo, 0.20 Al, 0.012 S, 0.011 P. 0.02 Cu. 0.002 B and 0.03 Ta. balance essentially iron. The test specimens were similar in shape to standard round test specimens according to A.S.A. specifications, but with special characteristics for stress-corrosion testing. namely, overall length: mm.; length of end section: 64 mm.; length of reduced cylindrical section: 7 mm.; radius of fillet: 14 mm.; diameter of end section: 10 mm.; diameter of reduced section: 4 mm.; both ends threaded for a length of 18 mm. A like number of specimens of the same size and shape were cut from N 80 steel. These specimens were immersed in a solution of 0.03 M sodium sulphide in 0.5 M acetic acid. This solution is a known test solution that accelerates the effects of oil well environment on steel.
The specimens were subjected to various static tensile loads while immersed in the above solution, and the life of the specimens to failure was noted. Fifty specimens of each steel for each load were tested. and the results, both in terms of the absolute tensile load. and in terms of the percentage of the tensile strength that that load amounts to, are set forth in the following tables.
TABLE I life of the steel in hours From a consideration of the foregoing disclosure. therefore. it will be evident that all of the initially recited objects of the present invention have been achieved.
Although the present invention has been described and illustrated in connection with preferred embodiments. it is to be understood that modifications and variations may be resorted to without departing from the spirit of the invention. as those skilled in this art will readily understand. Such modifications and variations are considered to be within the purview and scope of the present invention as defined by the appended claims.
Having described our invention. we claim:
1. A bainitic steel resistant to hydrogen embrittlement. having the weight per cent composition 0.15-0.35 C. up to 0.8 Mn. 0.8l.0 Si. 1.0-2.0 Cr. 0. l0.5 Mo. 0. l0.6 Al. up to 0.03 P. up to 0.03 S. up to 0.05 Cu. 0002-0004 B. up to 01 Ta. balance essentiall v iron. the ratio SizMn being l2. the ratio MozAl being l-3. and the sum of 0.5 X 'fiCr 92 Mo 100 X /(B being l2.
2. A bainitic steel as claimed in claim 1. said sum being ll.5.

Claims (2)

1. A BAINITIC STEEL RESISTANT TO HYDROGEN EMBRITTLEMENT, HAVING THE WEIGHT PER CENT COMPOSITION 0.15-0.35C,UP TO 0.8 MN, 0.8-1.0 SI, 1.0-2.0 CR 0.1-0.5 MO, 0.1-0.6 AL, UP TO 0.03 P, UP TO 0.03 S, UP TO 0.35 CU, 0.002-0.004 B, UP TO 0.1 TA, BALANCE ESSENTIALLY IRON, THE RATIO SI:MN BEING 1-2, THE RATIO MO:AL BEING 1-3, AND THE SUM OF 0.5X%CR+%MO+100X %B BEING 1-2.
2. A bainitic steel as claimed in claim 1, said sum being 1-1.5.
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Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4453986A (en) * 1982-10-07 1984-06-12 Amax Inc. Tubular high strength low alloy steel for oil and gas wells
US4533405A (en) * 1982-10-07 1985-08-06 Amax Inc. Tubular high strength low alloy steel for oil and gas wells
US5523540A (en) * 1992-05-27 1996-06-04 Alloy Rods Global, Inc. Welding electrodes for producing low carbon bainitic ferrite weld deposits
WO1996022396A1 (en) * 1995-01-20 1996-07-25 British Steel Plc Improvements in and relating to carbide-free bainitic steels and methods of producing such steels
FR2740476A1 (en) * 1995-10-27 1997-04-30 Kobe Steel Ltd SPRING STEEL WITH EXCELLENT FRAGILIZATION RESISTANCE TO HYDROGEN AND FATIGUE
US6149862A (en) * 1999-05-18 2000-11-21 The Atri Group Ltd. Iron-silicon alloy and alloy product, exhibiting improved resistance to hydrogen embrittlement and method of making the same
US6506266B1 (en) * 1999-11-05 2003-01-14 Fag Oem Und Handel Ag Tire or solid wheel for wheelsets of rail vehicles
US6632301B2 (en) 2000-12-01 2003-10-14 Benton Graphics, Inc. Method and apparatus for bainite blades
US20100068549A1 (en) * 2006-06-29 2010-03-18 Tenaris Connections Ag Seamless precision steel tubes with improved isotropic toughness at low temperature for hydraulic cylinders and process for obtaining the same
US20100193085A1 (en) * 2007-04-17 2010-08-05 Alfonso Izquierdo Garcia Seamless steel pipe for use as vertical work-over sections
US20100294401A1 (en) * 2007-11-19 2010-11-25 Tenaris Connections Limited High strength bainitic steel for octg applications
US20100319814A1 (en) * 2009-06-17 2010-12-23 Teresa Estela Perez Bainitic steels with boron
US20110097235A1 (en) * 2007-07-06 2011-04-28 Gustavo Lopez Turconi Steels for sour service environments
US8414715B2 (en) 2011-02-18 2013-04-09 Siderca S.A.I.C. Method of making ultra high strength steel having good toughness
US8636856B2 (en) 2011-02-18 2014-01-28 Siderca S.A.I.C. High strength steel having good toughness
US8821653B2 (en) 2011-02-07 2014-09-02 Dalmine S.P.A. Heavy wall steel pipes with excellent toughness at low temperature and sulfide stress corrosion cracking resistance
US9187811B2 (en) 2013-03-11 2015-11-17 Tenaris Connections Limited Low-carbon chromium steel having reduced vanadium and high corrosion resistance, and methods of manufacturing
US9340847B2 (en) 2012-04-10 2016-05-17 Tenaris Connections Limited Methods of manufacturing steel tubes for drilling rods with improved mechanical properties, and rods made by the same
US9598746B2 (en) 2011-02-07 2017-03-21 Dalmine S.P.A. High strength steel pipes with excellent toughness at low temperature and sulfide stress corrosion cracking resistance
US9644248B2 (en) 2013-04-08 2017-05-09 Dalmine S.P.A. Heavy wall quenched and tempered seamless steel pipes and related method for manufacturing said steel pipes
US9657365B2 (en) 2013-04-08 2017-05-23 Dalmine S.P.A. High strength medium wall quenched and tempered seamless steel pipes and related method for manufacturing said steel pipes
US9803256B2 (en) 2013-03-14 2017-10-31 Tenaris Coiled Tubes, Llc High performance material for coiled tubing applications and the method of producing the same
US9970242B2 (en) 2013-01-11 2018-05-15 Tenaris Connections B.V. Galling resistant drill pipe tool joint and corresponding drill pipe
US10844669B2 (en) 2009-11-24 2020-11-24 Tenaris Connections B.V. Threaded joint sealed to internal and external pressures
US11105501B2 (en) 2013-06-25 2021-08-31 Tenaris Connections B.V. High-chromium heat-resistant steel
US11124852B2 (en) 2016-08-12 2021-09-21 Tenaris Coiled Tubes, Llc Method and system for manufacturing coiled tubing
US11833561B2 (en) 2017-01-17 2023-12-05 Forum Us, Inc. Method of manufacturing a coiled tubing string
US11952648B2 (en) 2011-01-25 2024-04-09 Tenaris Coiled Tubes, Llc Method of forming and heat treating coiled tubing
US12129533B2 (en) 2015-04-14 2024-10-29 Tenaris Connections B.V. Ultra-fine grained steels having corrosion- fatigue resistance

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US3600161A (en) * 1965-07-09 1971-08-17 Nippon Steel Corp Low-alloyed high strength steel having resistance to the sulfide corrosion cracking
US3684493A (en) * 1969-03-20 1972-08-15 Nippon Kokan Kk Sea-water corrosion resisting steel containing aluminum for welding structures

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US2770563A (en) * 1953-03-07 1956-11-13 Acieries De Pompey Low alloy steel tubing
US3251682A (en) * 1961-11-29 1966-05-17 Yawata Iron & Steel Co Low-alloy tough steel
US3348981A (en) * 1964-02-21 1967-10-24 Yawata Iron & Steel Co High tension low temperature tough steel
US3600161A (en) * 1965-07-09 1971-08-17 Nippon Steel Corp Low-alloyed high strength steel having resistance to the sulfide corrosion cracking
US3684493A (en) * 1969-03-20 1972-08-15 Nippon Kokan Kk Sea-water corrosion resisting steel containing aluminum for welding structures

Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4453986A (en) * 1982-10-07 1984-06-12 Amax Inc. Tubular high strength low alloy steel for oil and gas wells
US4533405A (en) * 1982-10-07 1985-08-06 Amax Inc. Tubular high strength low alloy steel for oil and gas wells
US5523540A (en) * 1992-05-27 1996-06-04 Alloy Rods Global, Inc. Welding electrodes for producing low carbon bainitic ferrite weld deposits
WO1996022396A1 (en) * 1995-01-20 1996-07-25 British Steel Plc Improvements in and relating to carbide-free bainitic steels and methods of producing such steels
US5879474A (en) * 1995-01-20 1999-03-09 British Steel Plc Relating to carbide-free bainitic steels and method of producing such steels
FR2740476A1 (en) * 1995-10-27 1997-04-30 Kobe Steel Ltd SPRING STEEL WITH EXCELLENT FRAGILIZATION RESISTANCE TO HYDROGEN AND FATIGUE
US6149862A (en) * 1999-05-18 2000-11-21 The Atri Group Ltd. Iron-silicon alloy and alloy product, exhibiting improved resistance to hydrogen embrittlement and method of making the same
US6506266B1 (en) * 1999-11-05 2003-01-14 Fag Oem Und Handel Ag Tire or solid wheel for wheelsets of rail vehicles
US6632301B2 (en) 2000-12-01 2003-10-14 Benton Graphics, Inc. Method and apparatus for bainite blades
US20100068549A1 (en) * 2006-06-29 2010-03-18 Tenaris Connections Ag Seamless precision steel tubes with improved isotropic toughness at low temperature for hydraulic cylinders and process for obtaining the same
US8926771B2 (en) 2006-06-29 2015-01-06 Tenaris Connections Limited Seamless precision steel tubes with improved isotropic toughness at low temperature for hydraulic cylinders and process for obtaining the same
US20100193085A1 (en) * 2007-04-17 2010-08-05 Alfonso Izquierdo Garcia Seamless steel pipe for use as vertical work-over sections
US20110097235A1 (en) * 2007-07-06 2011-04-28 Gustavo Lopez Turconi Steels for sour service environments
US8328958B2 (en) 2007-07-06 2012-12-11 Tenaris Connections Limited Steels for sour service environments
US20100294401A1 (en) * 2007-11-19 2010-11-25 Tenaris Connections Limited High strength bainitic steel for octg applications
US8328960B2 (en) * 2007-11-19 2012-12-11 Tenaris Connections Limited High strength bainitic steel for OCTG applications
US20100319814A1 (en) * 2009-06-17 2010-12-23 Teresa Estela Perez Bainitic steels with boron
US10844669B2 (en) 2009-11-24 2020-11-24 Tenaris Connections B.V. Threaded joint sealed to internal and external pressures
US11952648B2 (en) 2011-01-25 2024-04-09 Tenaris Coiled Tubes, Llc Method of forming and heat treating coiled tubing
US8821653B2 (en) 2011-02-07 2014-09-02 Dalmine S.P.A. Heavy wall steel pipes with excellent toughness at low temperature and sulfide stress corrosion cracking resistance
US9598746B2 (en) 2011-02-07 2017-03-21 Dalmine S.P.A. High strength steel pipes with excellent toughness at low temperature and sulfide stress corrosion cracking resistance
US9188252B2 (en) 2011-02-18 2015-11-17 Siderca S.A.I.C. Ultra high strength steel having good toughness
US8414715B2 (en) 2011-02-18 2013-04-09 Siderca S.A.I.C. Method of making ultra high strength steel having good toughness
US9222156B2 (en) 2011-02-18 2015-12-29 Siderca S.A.I.C. High strength steel having good toughness
US8636856B2 (en) 2011-02-18 2014-01-28 Siderca S.A.I.C. High strength steel having good toughness
US9340847B2 (en) 2012-04-10 2016-05-17 Tenaris Connections Limited Methods of manufacturing steel tubes for drilling rods with improved mechanical properties, and rods made by the same
US9970242B2 (en) 2013-01-11 2018-05-15 Tenaris Connections B.V. Galling resistant drill pipe tool joint and corresponding drill pipe
US9187811B2 (en) 2013-03-11 2015-11-17 Tenaris Connections Limited Low-carbon chromium steel having reduced vanadium and high corrosion resistance, and methods of manufacturing
US9803256B2 (en) 2013-03-14 2017-10-31 Tenaris Coiled Tubes, Llc High performance material for coiled tubing applications and the method of producing the same
US10378074B2 (en) 2013-03-14 2019-08-13 Tenaris Coiled Tubes, Llc High performance material for coiled tubing applications and the method of producing the same
US10378075B2 (en) 2013-03-14 2019-08-13 Tenaris Coiled Tubes, Llc High performance material for coiled tubing applications and the method of producing the same
US11377704B2 (en) 2013-03-14 2022-07-05 Tenaris Coiled Tubes, Llc High performance material for coiled tubing applications and the method of producing the same
US9657365B2 (en) 2013-04-08 2017-05-23 Dalmine S.P.A. High strength medium wall quenched and tempered seamless steel pipes and related method for manufacturing said steel pipes
US9644248B2 (en) 2013-04-08 2017-05-09 Dalmine S.P.A. Heavy wall quenched and tempered seamless steel pipes and related method for manufacturing said steel pipes
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