(19)
(11)EP 3 626 841 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
17.11.2021 Bulletin 2021/46

(21)Application number: 18195795.2

(22)Date of filing:  20.09.2018
(51)International Patent Classification (IPC): 
C21D 8/10(2006.01)
C21D 1/25(2006.01)
C22C 38/16(2006.01)
C22C 38/50(2006.01)
C21D 9/08(2006.01)
C21D 1/63(2006.01)
C22C 38/46(2006.01)
C22C 38/58(2006.01)
(52)Cooperative Patent Classification (CPC):
C21D 1/25; C21D 9/085; C22C 38/58; C22C 38/46; C21D 8/105; C21D 1/63; C22C 38/50; C22C 38/16

(54)

HIGH STRENGTH MICRO ALLOYED STEEL SEAMLESS PIPE FOR SOUR SERVICE AND HIGH TOUGHNESS APPLICATIONS

NAHTLOSES ROHR AUS HOCHFESTEM MIKROLEGIERTEM STAHL FÜR SAUERGASBESTÄNDIGKEITS- UND HOCHZÄHIGKEITSANWENDUNGEN

TUYAU SANS SOUDURE EN ACIER MICRO ALLIÉ HAUTE RÉSISTANCE POUR SERVICE SULFUREUX ET DES APPLICATIONS DE HAUTE TÉNACITÉ


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(43)Date of publication of application:
25.03.2020 Bulletin 2020/13

(73)Proprietor: Vallourec Tubes France
92100 Boulogne-Billancourt (FR)

(72)Inventors:
  • DA TRINDADE FILHO Vicente Braz
    92100 BOULOGNE-BILLANCOURT (FR)
  • SILVEIRA E SILVA Julio Marcio
    92100 BOULOGNE-BILLANCOURT (FR)
  • CALDAS VILAS BÔAS Ana Carolina
    92100 BOULOGNE-BILLANCOURT (FR)
  • LINNE, Cédric
    92100 BOULOGNE-BILLANCOURT (FR)

(74)Representative: Casalonga 
Casalonga & Partners Bayerstraße 71/73
80335 München
80335 München (DE)


(56)References cited: : 
EP-A1- 1 876 254
EP-A1- 2 728 030
EP-A1- 3 006 585
CN-A- 102 154 593
EP-A1- 2 133 443
EP-A1- 2 843 072
EP-B1- 1 954 847
JP-A- H0 920 961
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description


    [0001] The present invention relates to micro alloyed steels with a yield strength of at least 485 MPa (70 ksi), and preferably of at least 555 MPa (80 ksi) with outstanding toughness behavior, good weldability and improved sulphide stress cracking resistance. Pipes of the invention comply with tensile requirements of grades X70 and X80 according with American Petroleum Institute standard API 5L, with sulfide stress corrosion (SSC) and hydrogen induced cracking (HIC) resistance.

    [0002] The challenges to develop high-strength seamless pipes starts with the premium quality of the steel, especially regarding the narrow chemistry variation of micro alloying elements and lower carbon content in order to achieve the necessary mechanical properties and excellent weldability characteristics.

    [0003] CN102154593 discloses an X80 steel grade anti-corrosion low-temperature seamless line pipe which comprises the following components in percentage by weight: 0.08 to 0.14 percent of C, 0.20 to 0.35 percent of Si, 1.10 to 1.40 percent of Mn, less than or equal to 0.015 percent of P, less than or equal to 0.005 percent of S, 0.10 to 0.20 percent of Mo, 0.020 to 0.060 percent of A1, 0.02 to 0.05 percent of Nb, 0.05 to 0.10 percent of V, 0.10 to 0.20 percent of Cu, 0.10 to 0.20 percent of Ni, less than or equal to 0.015 percent of Ti, less than or equal to 0.15 percent of Cr, 0.0015 to 0.0060 percent of Ca, less than or equal to 0.0005 percent of B, less than or equal to 0.012 percent of N, less than or equal to 0.43 percent of CEV, less than or equal to 0.23 percent of Pcm and Fe and impurity elements.

    [0004] Line pipes used for transporting oil & gas have increased in strength every year in order to improve the project efficiency and at the same time decreasing investment costs. Additionally, requirement for high deformability and enhanced weldability are continuous demanded.

    [0005] However, the strength and toughness trade-off, combined with the need for sulfide stress corrosion (SSC) and hydrogen induced cracking (HIC) resistance (e.g. sour resistance) is difficult to achieve. In particular, quenched and tempered (Q&T) seamless pipes of API 5L grade X70 typically exhibit maximum hardness values, measured at 1.5-2.0 mm depth from the pipe surfaces (according to API 5L-ISO 3183), below 250 HV10, whereas currently new projects require lower values to make the material weldable and resistant to SSC as per Region 3 in NACE MR-0175/ISO15156-2. This SSC resistance corresponds to high H2S combined with low pH conditions. But lower maximum hardness values cannot be consistently achieved with current steel chemical compositions and processes.

    [0006] An objective of the invention is to propose robust steel grades that fulfill the above requirements. The invention proposes steel grades according to DNV 555 SP ("X80QOS") for sour service application within Class 3 domain.

    [0007] The present invention also relates to tubular products, such as tubes or pipes, preferably seamless pipes, made from said steel, as well as a process for manufacturing such tubular products.

    [0008] In addition, the present invention concerns use of such tubular products as seamless pipes for line pipes for applications as process pipes, flowlines or risers in the oil and gas industry. Advantageously, seamless pipes according to the invention allow reduced pipe wall thickness without any disadvantage in terms of the overall material performance under severe applications.

    [0009] Harsher environment applications had encouraged a search for accessories made of steels having good and stable mechanical properties and a satisfying toughness behavior at low temperatures, especially where high imposed strains can take place at cryogenic service temperatures down to -60°C or even down to -80°C.

    [0010] The required increase in strength while maintaining adequate ductility of hot-processed seamless pipes for the afore-described applications also requires the development of new alloying concepts. In particular, adequate high ductility or toughness at low service temperatures is difficult to attain with conventional alloying concepts or conventional processes.

    [0011] Typically known methods for improvement of the tensile strength are increasing the carbon content or the carbon equivalent by using conventional alloying concepts and/or using micro alloying concepts, based on the mechanism of precipitation hardening.

    [0012] Micro-alloying elements, such as titanium, niobium and vanadium, are, generally speaking, employed to increase the strength. Depending on the alloying design, Titanium can already partially precipitate at high temperatures in the liquid phase forming very coarse titanium nitride. Niobium forms niobium (C, N) precipitates at lower temperatures. With further decreasing temperature, vanadium carbides and nitrides are also formed.

    [0013] Nevertheless exceedingly coarse precipitates of these micro-alloying elements frequently impair the ductility and toughness. Accordingly, the concentration of these alloying elements is generally limited. In addition, the concentration of carbon and nitrogen required for the proper formation of precipitates must be taken into account, making the whole chemical composition definition complex.

    [0014] In order to overcome these aforementioned drawbacks, new alloying concepts based on the addition of elements suitable to increase tensile strength by solution hardening in combination with micro-alloying techniques have been duly investigated.

    [0015] Some offshore applications are mainly performed in corrosive media, and particularly in presence of hydrogen sulphide (H2S), which is responsible for a dangerous form of cracking in low alloy steels with a high yield strength, known as sulphide stress cracking (SSC).

    [0016] Sulphide stress cracking resistance is thus of particular importance for oil companies since it is relevant to the safety of equipment.

    [0017] Furthermore, offshore pipeline installation can be performed by reel-laying. However, the process of reeling on and off the reel drum does lead to significant plastic deformation of the pipes. Indeed, during reel-laying, repeated plastic strain is generated into the pipeline, which may affect strength and ductility of the line pipe material and alters its corrosion resistance, especially in presence of hydrogen sulphide.

    [0018] Therefore there is a real need to provide steels suitable for harsh environment, and especially for ultra-deep offshore applications that conciliate both good and stable mechanical properties: high strength, high toughness and suitable sulphide stress cracking resistance.

    [0019] More particularly, the steel should allow the manufacture of seamless pipes that can be used as line pipes, for applications like process pipes, flowlines or risers in the oil and gas industry..

    [0020] The steel should also present excellent impact properties at service temperatures down to -60°C (in transversal directions) across the entire wall thickness of the pipe.

    [0021] The present invention is disclosed in the appended claims.

    [0022] The steel of the present invention may present a yield strength preferably greater than or equal to 485 MPa, and lower than or equal to 695 MPa, preferably between 495 and 675 MPa.

    [0023] According to a preferred embodiment of the present invention, steel's yield strength is greater than or equal to 555 MPa and lower than or equal to 705 MPa, in order to comply with grade X80 of API, and preferably steel's yield strength is lower than or equal to 675 MPa, in order to fulfill DNV GL ST-F101 standards.

    [0024] The yield strength is determined by tensile tests as defined in standards ASTM A370-17 and ASTM E8/E8M-13a.

    [0025] The steel of the present invention exhibits outstanding hardness and toughness behavior, especially under stringent conditions, namely in presence of a corrosive media. Indeed, the steel of the invention presents excellent mechanical properties and a high toughness at temperatures even down to -80°C, as well as an improved sulphide stress cracking resistance.

    [0026] The steel of the present invention can particularly be used in tubular products, preferably seamless pipes, exhibiting uniform hardness throughout their wall thickness, even for thinner wall thickness.

    [0027] As a result, the steel of the present invention is able to lead to seamless pipes having high yield and tensile strengths, a high strain capacity, a low and uniform hardness, namely throughout their entire length and wall thickness, and exhibiting a high and steady toughness performance, while presenting an excellent SSC resistance.

    [0028] Furthermore, the steel of the present invention is able to lead to seamless pipes displaying high and steady toughness performance, even after being strained and aged, while still presenting an excellent SSC resistance. In other words, the seamless pipes made from the steel of the invention can still be used efficiently under harsh conditions even after undergoing a plastic deformation. In particular, seamless pipes made from the steel of the invention are able to display good and stable mechanical properties during reel-laying.

    [0029] Thus, another object of the present invention concerns a seamless pipe made from a steel as previously defined.

    [0030] The present invention also relates to a process for manufacturing a seamless pipe comprising the following successive steps:
    1. (a) providing a steel having a chemical composition as defined in appended claims, and hot forming a seamless pipe thereof
    2. (b) cooling down the seamless pipe obtained at (a) to room temperature,
    3. (c) heating up the cooled seamless pipe obtained at (b) to an austenitization temperature (AT) ranging from 890 to 970°C, preferably between 900 to 930°C to obtain an austenitized seamless pipe, and then quenching said austenitized seamless pipe down to room temperature to obtain a quenched seamless pipe,
    4. (d) heating up the quenched seamless pipe obtained at (c) to a tempering temperature (TT) ranging from 610 to 680°C, and preferably 630 to 670°C before keeping said seamless pipe at the temperature TT and then cooling said seamless pipe down to ambient temperature to obtain a quenched and tempered seamless pipe.


    [0031] The seamless pipe thus obtained from the steel of the invention presents an improved sulphide stress cracking resistance. As previously mentioned, the tubular product and notably the steel seamless pipes are particularly suitable for demanding environments. These demanding environments may incorporate a combination of very challenging factors including, for example, deep-water locations, increased pressure and temperature wells, more corrosive products, and lower design temperatures. These conditions, when added to stringent weldability and toughness criteria already associated with pipe specifications for offshore oil and gas exploration applications, place ever increasing demands on the materials and supply capability.

    [0032] This product presents the advantages of having good and stable mechanical properties throughout its length and wall thickness, which is the distinction of a substantially uniform microstructure, as well as an excellent SSC resistance.

    [0033] Thus, the present invention also relates to the use of such a seamless pipe for line pipes, for applications as process pipes,flowlines or risers in the oil and gas industry.

    [0034] Other subjects, characteristics, aspects and advantages of the invention will emerge even more clearly on reading the description and the examples that follow.

    [0035] In what follows and unless otherwise indicated, the limits of a range of values are included within this range, in particular in the expressions "of between" and "ranging from...to...".

    [0036] Moreover, the expressions "at least one" and "at least" used in the present description are respectively equivalent to the expressions "one or more" and "greater than or equal to".

    Carbon



    [0037] The chemical composition of the steel according to the present invention contains 0.05 ≤ C ≤ 0.10% by weight, relative to the total weight of said chemical composition. In other words, the chemical composition of the steel contains carbon (C) in a content ranging from 0.05 to 0.10% by weight, relative to the total weight of said chemical composition; it being understood that both lower (0.05% by weight) and higher (0.10% by weight) limits being included.

    [0038] Carbon significantly increases the tensile strength of the steel according to the present invention. However, it also increases the hardness, which is not desirable for sour-service applications. The objective is to achieve high strength and at the same time low hardness and high toughness. Below 0.05% by weight, the tensile strength decreases significantly and there is a risk to have yield strength below expectation. In other words, the content of carbon has to be higher than or equal to 0.05% by weight in order to ensure grade X70 and/or X80 strengths in case of quenched and tempered seamless pipes

    [0039] In addition, above 0.10% by weight, properties such as weldability, ductility and toughness are negatively affected. The steel is indeed more susceptible to peaks of hardness in the Heat Affected Zone, lower toughness at the weld joint and lower sour service resistance.

    [0040] The carbon content is preferably higher than or equal to 0.06% (0.06% ≤ C) by weight, relative to the total weight of the chemical composition.

    [0041] The carbon content is preferably lower than or equal 0.08% (C ≤ 0.08%) by weight, relative to the total weight of the chemical composition.

    [0042] The carbon content preferably ranges from 0.06 to 0.08% by weight, relative to the total weight of the chemical composition. In other words, the chemical composition of the steel according to the present invention preferably contains 0.06 ≤ C ≤ 0.08% by weight, relative to the total weight of said chemical composition.

    Silicon



    [0043] The chemical composition of the steel according to the present invention further contains 0.15 ≤ Si ≤ 0.35% by weight, relative to the total weight of said chemical composition. In other words, the chemical composition of the steel contains silicon (Si) in a content ranging from 0.15% to 0.35% by weight, relative to the total weight of said chemical composition; it being understood that both lower (0.15% by weight) and higher (0.35% by weight) limits being included.

    [0044] This element is used as deoxidizer in liquid state and this effect is more effectively obtained with contents above 0.15% by weight. Such contents also increase strength of the steel, especially the ultimate tensile strength, improving the yield ratio (YS/UTS). However, above 0.35% by weight, the toughness of the steel is negatively affected and decreases.

    [0045] Silicon is also needed to retard softening phenomenon during high temperature tempering and also the derating of the tensile properties of the steel. The silicon content is preferably higher than or equal to 0.23% (0.23% ≤ Si) by weight, and more preferably higher than or equal to 0.26% (0.26% ≤ Si) by weight relative to the total weight of the chemical composition.

    [0046] The silicon content is preferably lower than or equal to 0.31% (Si ≤ 0.31%) by weight, and more preferentially lower than or equal to 30% (Si ≤ 0.30%) by weight, relative to the total weight of the chemical composition.

    [0047] The silicon content preferably ranges from 0.23 to 0.31% by weight, and more preferentially from 0.26 to 0.30% by weight, relative to the total weight of the chemical composition. In other words, the chemical composition of the steel according to the present invention preferably contains 0.23 ≤ Si ≤ 0.31% by weight, and more preferentially 0.26 ≤ Si ≤ 0.30% by weight, relative to the total weight of said chemical composition.

    Manganese



    [0048] The chemical composition of the steel according to the present invention further contains 1.20 ≤ Mn ≤ 1.50% by weight, relative to the total weight of said chemical composition. In other words, the chemical composition of the steel contains manganese (Mn) in a content ranging from 1.20 to 1.50% by weight, relative to the total weight of said chemical composition; it being understood that both lower (1.20% by weight) and higher (1.50% by weight) limits being included.

    [0049] Manganese is beneficial to the hot workability of the steel. It also increases the hardenability of the steel. Furthermore, manganese increases the tensile strength of the steel by means of solid solution hardening. Properties such as weldability and toughness are negatively affected when the content of manganese exceeds 1.50% by weight, relative to the total weight of the steel.

    [0050] The manganese content is preferably higher than or equal to 1.35% (1.35% ≤ Mn) by weight, and more preferentially 1.40% (1.40% ≤ Mn) by weight relative to the total weight of the chemical composition.

    [0051] The manganese content is preferably lower than or equal to 1.45% (Mn ≤ 1.45%) by weight, relative to the total weight of the chemical composition.

    [0052] The manganese content preferably ranges from 1.35 to 1.45% by weight, and more preferentially from 1.40 to 1.45% by weight, relative to the total weight of the chemical composition. In other words, the chemical composition of the steel according to the present invention preferably contains 1.35 ≤ Mn ≤ 1.45% by weight, and more preferentially 1.40 ≤ Mn ≤ 1.45% by weight relative to the total weight of said chemical composition.

    Chromium



    [0053] The chemical composition of the steel according to the present invention further contains 0.02 ≤ Cr ≤ 0.10% by weight, relative to the total weight of said chemical composition. In other words, the chemical composition of the steel contains chromium (Cr) in a content ranging from 0.02 to 0.10% by weight, relative to the total weight of said chemical composition; it being understood that both lower (0.02% by weight) and higher (0.10% by weight) limits being included.

    [0054] Chromium improves the hardenability of the steel leading to enhancement of the tensile strengths. But higher content can be deleterious to the weldability of the steels due to increasing on hardness and decreasing the toughness.

    [0055] The content of chromium has to remain lower than or equal to 0.10% by weight in order to avoid any hard spots (high local hardness spots) during tempering and/or during welding caused by the formation and the precipitation of carbides. Such precipitates are indeed detrimental to SSC.

    [0056] The chromium content is preferably higher than or equal to 0.06% (0.06% ≤ Cr) by weight, relative to the total weight of the chemical composition.

    [0057] The chromium content is preferably lower than or equal to 0.08% (Cr ≤ 0.08%) by weight, relative to the total weight of the chemical composition.

    [0058] The chromium content preferably ranges from 0.06 to 0.08% by weight, relative to the total weight of the chemical composition. In other words, the chemical composition of the steel according to the present invention preferably contains 0.06 ≤ Cr ≤ 0.08% by weight, relative to the total weight of said chemical composition.

    Molybdenum



    [0059] The chemical composition of the steel according to the present invention further contains 0.10 ≤ Mo ≤ 0.30% by weight, relative to the total weight of said chemical composition. In other words, the chemical composition of the steel contains molybdenum (Mo) in a content ranging from 0.10 to 0.30% by weight, relative to the total weight of said chemical composition; it being understood that both lower (0.10% by weight) and higher (0.30% by weight) limits being included.

    [0060] Molybdenum increases both yield and tensile strengths and supports the homogeneity of the mechanical properties, the microstructure and the toughness of the steel along the whole length and thickness of the seamless pipe. The presence of molybdenum also makes possible to increase the tempering temperature and to provide thicker seamless pipes, without changing other process parameters, improving thus the hardness of said seamless pipe, as well as its SSC resistance. Molybdenum also increases the hardenability of the steel.

    [0061] The molybdenum content is preferably higher than or equal to 0.16% (0.16% ≤ Mo) by weight, and more preferentially higher than or equal to 0.20% (0.20% ≤ Mo) by weight, relative to the total weight of the chemical composition.

    [0062] The molybdenum content is preferably lower than or equal to 0.26% (Mo ≤ 0.26%) by weight, and more preferably lower than or equal to 0.24% (Mo ≤ 0.24%) by weight relative to the total weight of the chemical composition.

    [0063] The molybdenum content preferably ranges from 0.16 to 0.26% by weight, more preferentially from 0.20 to 0.24% by weight relative to the total weight of the steel. In other words, the chemical composition of the steel according to the present invention preferably contains 0.16 ≤ Mo ≤ 0.26% by weight, more preferentially 0.20 ≤ Mo ≤ 0.24% by weight relative to the total weight of said chemical composition.

    [0064] The chemical composition of the steel according to the present invention preferably satisfies the following formula (2) between Cr and Mo, the contents of which are expressed in weight%,



    [0065] In other words, the sum of Cr and Mo contents is preferably lower than or equal to 0.35% by weight, relative to the total weight of the steel. Higher value of these elements combination can cause very high strength combined with undesirable high hardness. Therefore, a very high tempering temperature might be necessary causing recrystallization of the martensite laths formed near to the pipe surfaces during the quenching process. On the other hand, too lower tempering temperature can drive to undesirable too high values for hardness and/or tensile strength.

    Aluminum



    [0066] The chemical composition of the steel according to the present invention further contains 0.015 ≤ Al ≤ 0.040% by weight, relative to the total weight of said chemical composition. In other words, the chemical composition of the steel contains aluminum (Al) in a content ranging from 0.015 to 0.040% by weight, relative to the total weight of said chemical composition; it being understood that both lower (0.015% by weight) and higher (0.040% by weight) limits being included.

    [0067] Aluminum is a powerful steel deoxidizer and grain refiner. The content of aluminum should not exceed 0.040% by weight because the cleanliness of the steel can be negatively affected by a potential stronger formation of aluminum oxides. However, too low value of Al is also not desirable due to the necessary deoxidation of the steel as well as because of the necessity of a reasonable amount of AlN in order to inhibit the grain growth during rolling, heat treatment and welding operations.

    [0068] The aluminum content is preferably higher than or equal to 0.20% (0.20% ≤ Al) by weight, relative to the total weight of the chemical composition.

    [0069] The aluminum content is preferably lower than or equal to 0.35% (Al ≤ 0.35%) by weight, relative to the total weight of the chemical composition.

    [0070] The aluminum content preferably ranges from 0.20 to 0.35% by weight, relative to the total weight of the steel. In other words, the chemical composition of the steel according to the present invention preferably contains 0.20 ≤ Al ≤ 0.35% by weight, relative to the total weight of said chemical composition.

    Nitrogen



    [0071] The chemical composition of the steel according to the present invention further contains 0.002 ≤ N ≤ 0.012% by weight, relative to the total weight of said chemical composition. In other words, the chemical composition of the steel contains nitrogen (N) in a content ranging from 0.002 to 0.012% by weight, relative to the total weight of said chemical composition; it being understood that both lower (0.002% by weight) and higher (0.012% by weight) limits being included.

    [0072] Above 0.012% by weight, nitrogen forms coarse carbo-nitrides that negatively affect the toughness and it is also deleterious to SSC resistance. Additionally, too high nitrogen can also accelerate the strain ageing of steel pipes that are undertaken to plastic deformation during reel laying process. On the other hand, too lower content of nitrogen is also deleterious due to the reduction of the precipitation of the carbonitrides and/or aluminum nitrides that are necessary for grain growth inhibition, and to increase the tensile properties.

    [0073] The nitrogen content is preferably higher than or equal to 0.005% (0.005% ≤ N) by weight, relative to the total weight of the chemical composition.

    [0074] The nitrogen content is preferably lower than or equal to 0.10% (N ≤ 0.10%) by weight, relative to the total weight of the chemical composition.

    [0075] The nitrogen content preferably ranges from 0.005 to 0.10% by weight, relative to the total weight of the steel. In other words, the chemical composition of the steel according to the present invention preferably contains 0.005 ≤ N ≤ 0.10% by weight, relative to the total weight of said chemical composition.

    Nickel



    [0076] The chemical composition of the steel according to the present invention further contains 0.10 ≤ Ni ≤ 0.30% by weight, relative to the total weight of said chemical composition. In other words, the chemical composition of the steel contains nickel (Ni) in a content ranging from 0.10 to 0.30% by weight, relative to the total weight of said chemical composition; it being understood that both lower (0.10% by weight) and higher (0.30% by weight) limits being included.

    [0077] Nickel improves the steel hardness. It increases yield strength, as well as tensile strength. Nickel is a very important element to improve the toughness, especially at very low temperatures.

    [0078] The nickel content is preferably higher than or equal to 0.12% (0.12% ≤ Ni) by weight, relative to the total weight of the chemical composition.

    [0079] The nickel content is preferably lower than or equal to 0.20% (Ni ≤ 0.20%) by weight, relative to the total weight of the chemical composition.

    [0080] The nickel content preferably ranges from 0.12 to 0.20% by weight, relative to the total weight of the steel. In other words, the chemical composition of the steel according to the present invention preferably contains 0.12 ≤ Ni ≤ 0.20% by weight, relative to the total weight of said chemical composition.

    Vanadium



    [0081] The chemical composition of the steel according to the present invention further contains 0.02 ≤ V ≤ 0.06% by weight, relative to the total weight of said chemical composition. In other words, the chemical composition of the steel contains vanadium (V) in a content ranging from 0.02 to 0.06% by weight, relative to the total weight of said chemical composition; it being understood that both lower (0.02% by weight) and higher (0.06% by weight) limits being included.

    [0082] Vanadium increases the tensile properties due to precipitation hardening phenomenon. Above 0.06% by weight, vanadium precipitates (nitrides and/or carbides) increase the risk of having peaks of hardness at Heat Affected Zone as well as a scattering in toughness values at low temperatures and/or a shift of transition temperatures to higher temperatures. Consequently, the toughness properties are negatively impacted by such contents. On the other hand, too lower content of vanadium does not increase the strength of the steels. Vanadium also has a minor effect on the hardenability of steels.

    [0083] The vanadium content is preferably higher than or equal to 0.03% (0.03% ≤ V) by weight, relative to the total weight of the chemical composition.

    [0084] The vanadium content is preferably lower than or equal to 0.05% (V ≤ 0.05%) by weight relative to the total weight of the chemical composition.

    [0085] The vanadium content preferably ranges from 0.03 to 0.05% by weight relative to the total weight of the chemical composition. In other words, the chemical composition of the steel according to the present invention preferably contains 0.03 ≤ V ≤ 0.05% by weight relative to the total weight of said chemical composition.

    Niobium



    [0086] The chemical composition of the steel according to the present invention further contains 0.01 ≤ Nb ≤ 0.03% by weight, relative to the total weight of said chemical composition. In other words, the chemical composition of the steel contains niobium (Nb) in a content ranging from 0.01 to 0.03% by weight, relative to the total weight of said chemical composition; it being understood that both lower (0.01% by weight) and higher (0.03% by weight) limits being included.

    [0087] Niobium leads to carbide and/or nitride precipitates resulting into a fine grain size microstructure by grain boundary pinning effects and improved tensile strength. However, above 0.03% by weight, niobium can have a negative impact in the hardness, especially at the Heat Affected Zone. And then it can also have a negative impact on the toughness through the formation of coarse precipitates.

    [0088] The niobium content is preferably higher than or equal to 0.02% (0.02% ≤ Nb) by weight, relative to the total weight of the chemical composition.

    [0089] The niobium content is preferably lower than or equal to 0.028% (Nb ≤ 0.028%) by weight relative to the total weight of the chemical composition.

    [0090] The niobium content preferably to the total weight of the chemical composition. In other words, the chemical composition of the steel according to the present invention preferably contains 0.02% ≤ Nb ≤ 0.028% by weight relative to the total weight of said chemical composition.

    [0091] The chemical composition of the steel according to the present invention preferably satisfies the following formula (3) between Nb and V, the contents of which are expressed in weight%,



    [0092] In other words, the sum of Nb and V contents is preferably lower than or equal to 0.07% by weight, relative to the total weight of the steel in order to avoid any hardness peak in the heat affected zone (HAZ) and to improve the SSC resistance in this region.

    Titanium



    [0093] The chemical composition of the steel according to the present invention further contains 0.001% ≤Ti ≤ 0,025%; by weight, relative to the total weight of said chemical composition. In other words, the chemical composition of the steel contains titanium (Ti) in a content up to 0.025% by weight, relative to the total weight of said chemical composition; it being understood that upper limit is included (0.025% by weight).

    [0094] Above 0.025% by weight, titanium can lead to the coarse carbide and/or nitride precipitates, which drive to a poorer grain refinement control as well as to a higher susceptibility to secondary cracking on SSC tests. In addition, at such contents, titanium negatively affects the yield strength and the toughness of the steel.

    [0095] The titanium content is preferably in the range of 0.005≤Ti≤ 0.020% by weight, relative to the total weight of the chemical composition.

    [0096] The chemical composition of the steel according to the present invention preferably satisfies the following formula (4) between Nb, V and Ti, the contents of which are expressed in weight%,



    [0097] In other words, the sum of Nb, V and Ti contents is preferably lower than or equal to 0.095% by weight, relative to the total weight of the steel. This element combination is important to avoid hardness spot in the heat affected zone of girth welds, improving the SSC resistance and the toughness in this region.

    Balance and residual elements



    [0098] The balance of the chemical composition of the steel according to the present invention is made of Fe and residual elements resulting from the steel production and casting processes, including P, S, B, Ca, Cu and mixtures thereof.

    [0099] In some embodiments, the chemical composition contains residual elements chosen from P, S, B, Ca, Cu and mixtures thereof.

    [0100] The term "residual elements" refers to inevitable elements resulting from the steel production and casting processes.

    [0101] The contents of the residual, expressed in weight%, relative to the total weight of said chemical composition, are preferably as follows:










    Boron



    [0102] The boron (B) content is preferably lower than or equal to 0.0005% by weight, relative to the total weight of the chemical composition of the steel. Above this content, boron can negatively impact the weldability due to hard spots formation at the Heat Affected Zone. More preferably, the steel composition is boron free. Boron free composition contains Boron less than 0.0005% by weight, relative to the total weight of the chemical composition of the steel.

    Copper



    [0103] The chemical composition of the steel according to the present invention may further contain Cu ≤ 0.12% by weight, relative to the total weight of said chemical composition. In other words, the chemical composition of the steel may further contain copper (Cu) in a content lower than or equal to 0.12% by weight, relative to the total weight of said chemical composition. Above 0.12% by weight, copper may lead to the surface defects due to the hot shortness phenomenon.

    [0104] Other elements such as Ca and REM (rare earth metals) can also be present as unavoidable residual elements. P and S decrease SSC resistance and the toughness.

    [0105] Carbon Equivalent and Pcm are calculated parameters in weight percent, relating the combined effects of different alloying elements in steels to an equivalent amount of carbon.

    [0106] The desire tensile strength can be varied by changing the amount of carbon and other alloying elements by means of a proper heat treatment. These parameters are very important to enable a better weldability, toughness and tensile strength. The lower Carbon Equivalent and Pcm, the better will be the weldability and toughness. But it cannot be too low, since the minimum tensile strength will not be reached.

    [0107] The present invention also relates to a seamless pipe, made from a steel as previously defined.

    [0108] According to one embodiment of the invention, seamless pipe are of the X80 grade, with a steel yield strength between 555 MPa and 740 MPa, a pipe wall thickness between à 15.1 and 35 mm, and such that the steel chemical composition contains in weight%, relative to the total weight of said chemical composition: 0.16 ≤ Mo ≤ 0.26, and preferably 0.20 ≤ Mo ≤ 0.24.

    [0109] According to another embodiment of the invention, seamless pipe are of the X70 grade, with a steel yield strength between 485 MPa and 635 MPa, a pipe wall thickness between 9,3 and 40 mm, and such that the steel chemical composition contains in weight%, relative to the total weight of said chemical composition: 0.10 ≤ Mo ≤ 0.21.

    [0110] Another object of the present invention concerns a process for manufacturing a seamless pipe as previously defined.

    [0111] More particularly, a seamless pipe made from steel according to the present invention is obtained according to conventional hot forming methods.

    [0112] For example, the steel according to the present invention may be melted by commonly-used melting practices and commonly-used casting process such as the continuous casting or the ingot casting-blooming methods.

    [0113] The steel is then heated to a temperature ranging from 1100 °C and 1300°C, so that at all points the temperature reached is favorable to the high rates of deformation the steel will undergo during hot forming.

    [0114] Preferably the maximum temperature is lower than 1300°C to avoid burning. Below 1100°C, the hot ductility of the steel is negatively impacted. The steel is advantageously hot formed in at least one step by rolling.

    [0115] A seamless pipe having the desired dimensions is thus obtained. This tubular product presents preferably a wall thickness ranging from 9.3 to 50 mm, and more preferably from 15 to 35 mm.

    [0116] The seamless pipe is then austenitized, i.e. heated up to an austenitization temperature (AT) to achieve a homogeneous microstructure along its length and across the wall section.

    [0117] The seamless pipe made of steel according to the present invention is then kept at the austenitization temperature AT for an austenitization time At of at least 2 minutes, the objective being that at all points of the tube, the temperature reached is at least equal to the austenitization temperature. The temperature should be homogeneous throughout the tube. The austenitization time At shall not be above 60 minutes because above such duration, the austenite grains grow undesirably large and lead to a coarser final structure. This would be detrimental to toughness and SSC resistance.

    [0118] The austenitized seamless pipe made of steel according to the present invention is then cooled to the ambient temperature, for example in water (water quench).

    [0119] The quenched seamless pipe made of steel according to the present invention is then tempered, i.e. heated up at a tempering temperature (TT) ranging from 630 to 670°C, preferably from 630 to 665°C, and more preferentially from 635 to 660°C.

    [0120] The tempering temperature has to remain below 670°C in order to avoid any recrystallization of martensite underneath the outer and inner pipe surfaces, that would be deleterious to the SSC resistance as well as the tensile properties and fatigue resistance, but higher than 630°C to keep the homogeneous microstructure all along the seamless pipe. The tempering temperature has to remain above 630°C, in order to avoid peaks of hardness at ID and OD surfaces

    [0121] Such tempering step is done during a tempering time Tt, preferably between 20 and 60 minutes. This leads to a quenched and tempered steel seamless pipe.

    [0122] The quenched and tempered steel seamless pipe according to the invention is then cooled down to the ambient temperature using either water or air cooling.

    [0123] At the end of the process of the present invention, the seamless pipe thus obtained may further undergo additional finishing steps, such as sizing, coating or straightening.

    [0124] The quenched and tempered steel seamless pipe is then useful for for line pipes, for applications as process pipes, flowlines or risers in the oil and gas industry.

    [0125] Thus the present invention also concerns use of a seamless pipe as previously defined for line pipes.

    [0126] Other characteristics and advantages of the invention are given in the following experimental section, which should be regarded as illustrative and not limiting the scope of the present application.

    EXAMPLES


    I. Example 1 - X80


    1. Tested steels



    [0127] The following compositions of seamless pipe's steels according to the present invention (A1), (A2) and (A3) have been prepared from the elements indicated in the table 1 below, the amounts of which are expressed as percent by weight, relative to the total weight of the chemical composition.
    Table 1
    Chemical composition (Unit: mass%, Balance: Fe and residual elements) C 0.075 0.062 0.075
    Si 0.273 0.277 0.298
    Cr 0.062 0.065 0.078
    Al 0.027 0.025 0.025
    N 0.005 0.0072 0.0088
    Nb 0.0215 0.0209 0.0236
    Ti 0.0055 0.0052 0.0055
    P 0.006 0.009 0.01
    s 0.0017 0.0023 0.0019
    B 0.0004 0.0004 0.0004
    Ca 0.0009 0.0012 0.0015
    Cu 0.029 0.05 0.04
    Pcm 0.181 0.173 0.190
    Ceq 0.381 0.381 0.404
    Steel A1 A2 A3
    C+Cr+Mo+Nb+V+Ti 0.372 0.410 0.4988
    Nb+V 0.060 0.065 0.065
    Nb+V+Ti 0.065 0.071 0.070
    Cr + Mo 0.234 0.280 0,319

    2. Protocol



    [0128] The steels (A1), (A2) and (A3) having the chemical compositions described in the table 1 above have been heated and then hot formed into seamless steel pipes of the desired dimensions by hot working using a rolling mill at 1250°C.

    [0129] The seamless steel pipes thus obtained have a wall thickness (WT) equal to 15.9mm or 25.4mm.

    [0130] After hot forming, the seamless steel pipes have undergone the following process conditions summarized in the table 2, with:

    AT: Austenitization temperature in °C

    At: Austenitization time in seconds

    TT: Tempering temperature in °C

    Tt: Tempering time in seconds



    [0131] The following steps, defined in table 2 and correspond to steps (c) and (d) of the process of the present invention.
    Table 2
    Steel (WT)AT (°C)At (s)TT (°C)Tt (s)
    A1 (25.4mm) 920 900 640 2400
    A2 (25.4mm) 920 900 644 2400
    A3 (25.4mm) 920 900 664 2400
    A1 (15.9mm) 920 900 644 2400
    A2 (15.9mm) 920 900 653 2400


    [0132] The mechanical properties, fracture mechanics and SSC behavior have then been evaluated for each steel (A1), (A2) (A3) according to the following methods.

    3. Hardness behavior



    [0133] The hardness behavior has been evaluated according to the standard ISO 6507-1.

    [0134] Each pipe (A1, 25.4mm), (A2, 25.4mm), (A3, 25.4mm), (A1, 15.9mm) and (A2, 15.9mm) has been cut in its transversal direction and divided in four quadrants. Four indentations on its outer wall, mid wall and inner wall have been performed on both bottom and head ends of the pipe. In other words, 16 measurements have been performed for each wall at the bottom end of the pipe and 16 others have been performed at the head end.

    [0135] The results are shown on figures 1a (representing the results obtained for pipes (A1, 25.4mm), (A2, 25.4mm) and (A3, 25.4mm)) and 1b (representing the results obtained for pipes (A1, 15.9mm) and (A2, 15.9mm)).

    [0136] Each graph represents all individual values of hardness measurements performed on different positions (bottom and head ends of the pipe), as well as on cross section (outer wall, mid wall and inner wall) for each pipe (A1, 25.4mm), (A2, 25.4mm), (A3, 25.4mm), (A1, 15.9mm) and (A2, 15.9mm).

    [0137] The results thus obtained clearly show that pipes made of steel according to the present invention comply with the requirements of DNVGL-ST-F101. Indeed, for both thicker (Figure 1a) and thinner (Figure 1b) walls, all hardness values are well below 250 HV10. This good level is even improved for the thinner walls (Figure 1b) since these values are mostly below 230 HV10.

    4. Tensile properties



    [0138] The tensile properties have been evaluated according to the standard ASTM A370.

    [0139] The tensile properties, represented by the yield strength, are shown on figures 2a (representing the results obtained for pipes (A1, 25.4mm), (A2, 25.4mm) and (A3, 25.4mm)) and 2b (representing the results obtained for pipes (A1, 15.9mm) and (A2, 15.9mm)).

    [0140] Each graph represents the yield strength values measured for each pipe (A1, 25.4mm), (A2, 25.4mm), (A3, 25.4mm), (A1, 15.9mm) and (A2, 15.9mm).

    [0141] The results thus obtained clearly show that pipes made of steel according to the present invention present a yield strength greater than or equal to 555 MPa (80 ksi). In other words, the steel according to the present invention corresponds to the grade X80.

    5. HIC resistance



    [0142] The HIC test, corresponding to the test according to NACE TM 0284 method, consists in immersing the test pipes in a solution (solution A) of 100% H2S. The testing duration is 96 hours. All specimens (A1, 25.4mm), (A2, 25.4mm), (A3, 25.4mm), (A1, 15.9mm) and (A2, 15.9mm) passed with no cracks, namely, crack sensitivity ratio (CSR), crack length ratio (CLR) and crack thickness ratio (CTR) are all zero.

    6. SSC resistance



    [0143] The SSC resistance corresponds to the sulphide stress corrosion cracking resistance. This SSC resistance has been evaluated for each pipe (A1, 25.4mm), (A2, 25.4mm) (A3, 25.4mm), (A1, 15.9mm) and (A2, 15.9mm) according to the three following methods:
    • the first SSC test, corresponding to standard NACE TM0177-2016 Method A, consists in immersing the pipes under axial load in an aqueous solution (Solution A), which consists of 5.0 wt.% of sodium chloride and 0.5 wt.% glacial acetic acid dissolved in distilled water. The pH of the solution before or after H2S saturation was in the range of 2.6 and 2.8. The solution temperature is 24°C. The testing duration is 720 hours, and the applied stress is 90% of the actual yield strength.
    • the second SSC test, corresponding to Four point bend test - ASTM G-39 standard, consists in immersing the pipes under load in an aqueous solution (Solution A), which consists of 5.0 wt.% of sodium chloride and 0.5 wt.% glacial acetic acid dissolved in distilled water. The pH of the solution before or after H2S saturation was in the range of 2.6 and 2.8. The solution temperature is 24°C. The testing duration is 720 hours, and the applied stress is 90% of the actual yield strength.


    [0144] The absence of failure was then determined.

    [0145] After 720 hours, the pipes according to the present invention presented no failures and no secondary cracks across the section. All the pipes show an excellent sulphide stress cracking resistance and can therefore be used in severe sour conditions.

    7. Test after straining and ageing



    [0146] The steel composition (A1) according to the present invention has been prepared from the elements indicated in the table 1 above. The steel (A1) thus obtained has then been hot formed according to the protocol previously mentioned in example 1 and the two following pipes (Ala) and (A1b) have been produced.

    [0147] After quenching and tempering, the pipe (A1b) has been aged and deformed according to the following protocol:
    The full wall strip specimen (A1b) has been submitted to uniaxial tensile stress causing a plastic deformation of 2% (A1b-2%) or of 5% (A1b-5%). The pipes have then been aged at 250°C for 1 hour. This protocol is intended to simulate the impact of reeling on the mechanical properties of the pipe at low temperatures.

    [0148] The mechanical properties, fracture mechanics and SSC behavior of the pipe (Ala) and of the aged and deformed pipes (A1b-2%) and (A1b-5%) have then been evaluated according to the following methods.

    7.1. Hardness behavior



    [0149] The hardness behavior has been evaluated according to the standard ISO 6507-1, as previously mentioned in example 1.

    [0150] The results obtained with (A1b-2%), having a wall thickness of 15.9mm, are mentioned in the table 3 here below. The following values correspond to the means of the four measurements of two of the four quadrants for each ends.
    Hardness (HV10) ― Table 3
    A1b-2%Outer wallMid wallInner wall
    Pipe trailing end Quadrant 1 215 220 237
    Quadrant 2 223 224 240
    Pipe leading end Quadrant 1 245 219 229
    Quadrant 2 219 224 246


    [0151] The results thus obtained clearly show that even after straining and ageing, pipes made of steel according to the present invention comply with the requirements of DNVGL-ST-F101. Indeed, all hardness values are below 250 HV10.

    7.2. Impact energy test



    [0152] For each pipe (Ala) and (A1b-5%), impact energy values have been determined according to the Charpy impact test ASTM E23 - Type A.

    [0153] Three notches located on different positions across the wall thickness (outer wall, mid wall and inner wall) were performed on pipes (Ala) and (A1b-5%). The pipes were then placed at different temperatures ranging from -10°C to -80°C.

    [0154] The absorbed energy (Joule) and the shear area (%) were then measured after impact Charpy tests at different temperatures.

    [0155] The results are given in the table 4 below for pipe (Ala) and pipe (A1b-5%). The results shown in the table correspond to the mean values of the three measurements using full size specimens.
    Charpy Impact Test ― table 4
    Test T (°C)Absorbed energy (J)Shear area (%)
    A1aA1b-5%A1aA1b-5%
    -80 348 166 100 60
    -60 343 251 100 100
    -30 377 272 100 100
    -10 385 280 100 100


    [0156] The results thus obtained show that pipes made of steel according to the present invention present no brittle fracture even at -80°C for the as-quenched and tempered conditions (A1a).

    [0157] In addition, even after a severe uniaxial deformation of 5% followed by ageing at 250°C for 1h, this good ductile behavior is kept for temperatures down to -60°C (A1b-5%).

    7.3. Crack tip opening displacement (CTOD)



    [0158] This method is used to determine when the crack starts to propagate.

    [0159] Three specimen were cut on each pipes (Ala), (A1b-2%) and (A1b-5%) using an electrical discharging machine (EDM) in order to guarantee narrow notches from which fatigue pre-cracks can extend by fatigue. The tests and results evaluations followed the standard BS 7448-1. The tested pipes had a wall thickness of 25.4 mm.

    [0160] DNVGL-ST-F101 specification establishes a minimum CTOD value of 0.150 mm for the design temperature.

    [0161] The CTOD values are given in the table 5 here below.
    CTOD ― Table 5
    SteelT(°C)CTOD values (mm)
    notch 1notch 2notch 3mean
    A1a -20°C 1.24 1.32 1.30 1.29
    A1a -60°C 1.28 1.27 1.20 1.25
    A1b-2% -60°C 1.19 1.28 1.20 1.23
    A1b-5% -60°C 1.08 1.13 1.10 1.10


    [0162] The results thus obtained show that the CTOD values of the steel according to the present invention are much higher than 0.150 mm. Indeed, even at -60°C, the CTOD values are higher than 1.10 mm.

    [0163] In addition, all the pipes (Ala), (A1b-2%) and (A1b-5%) present a ductile fracture mode.

    [0164] Both impact energy and CTOD tests show that the steel of the present invention present an excellent resistance to stress. Even after deformation and ageing, the pipes remain tough for temperatures down to -60°C.

    7.4. SSC resistance



    [0165] The SSC resistance has been evaluated for each pipes (A1a, 25.4mm), (A1a, 15.9mm) and (A1b-5%) according to the methods previously mentioned in example 1.

    [0166] After 720 hours, none of the pipes presented neither failures nor secondary cracks. All the pipes show an excellent sulphide stress cracking resistance, even after straining and ageing, and can therefore be used in severe sour conditions.

    II. Example 2 ― X70


    1. Tested steels



    [0167] The following compositions of seamless pipe's steels according to the present invention (A4) and (A5) have been prepared from the elements indicated in the table 1 below, the amounts of which are expressed as percent by weight, relative to the total weight of the chemical composition.
    Table 6
    SteelA4A5
    Chemical composition (Unit: mass%, Balance: Fe and residual elements) c 0.071 0.062
    Si 0.272 0.277
    Mn 1.419 1.432
    Cr 0.072 0.065
    Mo 0.107 0.120
    A1 0.029 0.025
    N 0.0051 0.0072
    Ni 0.168 0.18
    V 0.040 0.045
    Nb 0.0213 0.0209
    Ti 0.0023 0.0052
    P 0.007 0.009
    s 0.0016 0.0023
    B 0.0005 0.0004
    Ca 0.0013 0.0012
    Cu 0.029 0.05
    Pcm 0.172 0.173
    Ceq 0.364 0.381
    C+Cr+Mo+Nb+V+Ti 0.2962 0.3136
    Nb+V 0.0552 0.0613
    Nb+V+Ti 0.0572 0.0636
    Cr + Mo 0,179 0,185

    2. Protocol



    [0168] The steels (A4) and (A5) having the chemical compositions described in the table 6 above have been heated and then hot formed into seamless steel pipes of the desired dimensions by hot working using a rolling mill at 1250°C.

    [0169] The seamless steel pipes thus obtained have a wall thickness (WT) equal to 25.4mm.

    [0170] After hot forming, the seamless steel pipes have undergone the following process conditions:

    AT: Austenitization temperature at 920 °C

    At: Austenitization time during 900 seconds

    TT: Tempering temperature at 650°C

    Tt: Tempering time during 2400 seconds



    [0171] The mechanical properties, fracture mechanics, HIC and SSC behavior have then been evaluated for each steel (A4) and (A5) according to the following methods.

    3. Hardness behavior



    [0172] The hardness behavior has been evaluated according to the standard ISO 6507-1, according the method described for Example 1.

    [0173] The results are shown on figure 3.

    [0174] The results thus obtained clearly show that pipes made of steel according to the present invention comply with the requirements of DNVGL-ST-F101. All hardness values are below 240 HV10.

    4. Tensile properties



    [0175] The tensile properties have been evaluated according to the standard ASTM A370.

    [0176] The tensile properties, represented by the yield strength, are shown on figures 4. Each graph represents the yield strength values measured for each pipes (A4, 25.4mm) and (A5, 25.4mm).

    [0177] The results thus obtained clearly show that pipes made of steel according to the present invention present a yield strength greater than or equal to 485 MPa (70 ksi).

    5. HIC resistance



    [0178] Pipes (A4, 25.4mm) and (A5, 25.4mm) passed the HIC test, corresponding to the test according to NACE TM 0284 method, with no cracks after 96 hours, namely, crack sensitivity ratio (CSR), crack length ration (CLR) and crack thickness ratio (CTR) are all zero.

    6. SSC resistance



    [0179] Pipes (A4, 25.4mm) and (A5, 25.4mm) passed the SSC test, corresponding to the test according to NACE TM0177-2016 Method A, with no failures and no secondary cracks after 720 hours. All the pipes showed an excellent sulphide stress cracking resistance and can therefore be used in severe sour conditions.

    7. Test after straining and ageing



    [0180] The steel composition (A4) and (A5) according to the present invention has been prepared from the elements indicated in the table 6 above. The steel thus obtained has then been hot formed according to the protocol previously mentioned in example 2. After quenching and tempering, the pipe has been aged and deformed according to the following protocol: an uniaxial tensile stress causing a plastic deformation of 5% was applied to the full wall pipe, and then the pipes have then been aged at 250°C for 1 hour.

    7.1. Hardness behavior



    [0181] The hardness behavior has been evaluated according to the standard ISO 6507-1, as previously mentioned in example 1.

    [0182] The maximum hardness measurement obtained was 240HV10. The results thus obtained clearly show that even after straining and ageing, pipes made of steel according to the present invention comply with the requirements of DNVGL-ST-F101. Indeed, all hardness values are well below 250 HV10.

    7.2. Impact energy test



    [0183] For pipes according to Steel (A4), impact energy values have been determined according to the Charpy impact test ASTM E23 - Type A, using full size specimen.

    [0184] The results are given in the table 7 below for pipe (A4) without straining and ageing, and pipe (A4-5%) after straining and ageing. The results shown in the table correspond to the mean values of the three measurements using full size specimens.
    Charpy Impact Test ― table 7
    Test T (°C)Absorbed energy (J)Shear area (%)
    A4A4-5%A4A4-5%
    -80 390 175 100 70
    -60 405 287 100 100
    -30 400 298 100 100
    -10 403 297 100 100


    [0185] The results thus obtained show that pipes made of steel according to the present invention present no brittle fracture even at -80°C for the as-quenched and tempered conditions.

    [0186] In addition, even after a severe uniaxial deformation of 5% followed by ageing at 250°C for 1h, this good ductile behavior is kept for temperatures down to -60°C.

    7.3. Crack tip opening displacement (CTOD)



    [0187] Three specimen were cut on each pipes (A4) and (A4-5%), and respectively (A5). The tests and results evaluations followed the standard BS 7448-1. The tested pipes had a wall thickness of 25.4 mm.

    [0188] The CTOD values are given in the table 8 here below.
    CTOD ― Table 8
    SteelT(°C)CTOD values (mm)
    notch 1notch 2notch 3mean
    A4 -20°C 1.35 1.36 1.34 1.35
    A4 -60°C 1.23 1.20 1.27 1.23
    A5 -60°C 1.31 1.38 1.32 1.33
    A5 -60°C 1.24 1.18 1.21 1.21
    A4-5% -20°C 1.22 1.18 1.15 1.18
    A4-5% -60°C 1.02 1.08 1.11 1.07


    [0189] The results thus obtained show that the CTOD values of the steel according to the present invention are much higher than 0.150 mm as established by DNVGL-ST-F101 specification. Indeed, even at -60°C, the CTOD values are higher than 1 mm.

    [0190] In addition, all the pipes (Ala), (A1b-2%) and (A1b-5%) present a ductile fracture mode.

    [0191] Both impact energy and CTOD tests show that the steel of the present invention present an excellent resistance to stress. Even after deformation and ageing, the pipes remain tough for temperatures down to -60°C.

    7.4. SSC resistance



    [0192] After 720 hours, none of the pipes (A4) and (A4-5%) presents a failure nor secondary cracks. All the pipes show an excellent sulphide stress cracking resistance, even after straining and ageing, and can therefore be used in severe sour conditions.


    Claims

    1. Steel presenting a yield strength greater than or equal to 485 MPa and having a chemical composition consisting of, in weight%, relative to the total weight of said chemical composition,

    0.05 ≤ C ≤ 0.10

    0.15 ≤ Si ≤ 0.35

    1.20 ≤ Mn ≤ 1.50

    0.02 ≤ Cr ≤ 0.10

    0.10 < Mo ≤ 0.30

    0.015 ≤ Al ≤ 0.040

    0.002 ≤ N ≤ 0.012

    0.10 ≤ Ni ≤ 0.30

    0.02 ≤ V ≤ 0.06;

    0.01 ≤ Nb ≤ 0.03

    0.001 ≤ Ti ≤ 0,025

    the balance of the chemical composition of said steel being constituted by Fe and optionally one or more residual elements, chosen from P, S, B, Ca, Cu and mixtures thereof; the amounts of said residual elements, expressed in weight%, relative to the total weight of said chemical composition being as follows:

    P ≤ 0.012

    S ≤ 0.003

    B ≤ 0.0005

    Ca ≤ 0.004

    Cu ≤ 0.12;

    and the chemical composition of said steel satisfying the following formula (1) between C, Cr, Mo, Nb, V and Ti, the contents of which are expressed in weight%,


     
    2. Steel according to claim 1, wherein it presents a yield strength greater than or equal to 485 MPa, and below 695 MPa, preferably between 495 and 675 MPa.
     
    3. Steel according to claim 1 or 2, wherein it presents a yield strength greater than or equal to 555 MPa, and below 705 MPa, preferably below 675 MPa.
     
    4. Steel according to any of the preceding claims, wherein its chemical composition contains in weight%, relative to the total weight of said chemical composition: 0.06 ≤ C ≤ 0.08.
     
    5. Steel according to any of the preceding claims, wherein its chemical composition contains in weight%, relative to the total weight of said chemical composition: 0.23 ≤ Si ≤ 0.31, and preferably 0.26 ≤ Si ≤ 0.30.
     
    6. Steel according to any of the preceding claims, wherein its chemical composition contains in weight%, relative to the total weight of said chemical composition: 1.35 ≤ Mn ≤ 1.45, and preferably 1.40 ≤ Mn ≤ 1.45.
     
    7. Steel according to any of the preceding claims, wherein its chemical composition contains in weight%, relative to the total weight of said chemical composition: 0.06 ≤ Cr ≤ 0.08.
     
    8. Steel according to any of the preceding claims, wherein its chemical composition contains in weight%, relative to the total weight of said chemical composition: 0.16 ≤ Mo ≤ 0.26, and preferably 0.20 ≤ Mo ≤ 0.24.
     
    9. Steel according to any of the preceding claims, wherein its chemical composition contains in weight%, relative to the total weight of said chemical composition: 0,03 ≤ V ≤ 0,05
     
    10. Steel according to any of the preceding claims, wherein its chemical composition contains in weight%, relative to the total weight of said chemical composition: 0.02 ≤ Nb ≤ 0.028.
     
    11. Steel according to any of the preceding claims, wherein its chemical composition contains in weight%, relative to the total weight of said chemical composition: 0.005 ≤ Ti ≤ 0.020.
     
    12. Steel according to any of the preceding claims, wherein its chemical composition satisfies the following formula (2) between Cr and Mo, the contents of which are expressed in weight%,


     
    13. Steel according to any of the preceding claims, wherein its chemical composition satisfies the following formula (3) between Nb and V, the contents of which are expressed in weight%,


     
    14. Seamless pipe, made from a steel according to any one of the preceding claims.
     
    15. Seamless pipe according to claim 14, wherein steel yield strength is between 555 MPa and 740 MPa, pipe wall thickness is between à 15,1 and 35 mm, and the steel chemical composition contains in weight%, relative to the total weight of said chemical composition: 0.16 ≤ Mo ≤ 0.26, and preferably 0.20 ≤ Mo ≤ 0.24.
     
    16. Seamless pipe according to claim 14, wherein steel yield strength is between 485 MPa and 635 MPa, pipe wall thickness is between 9.3 and 40 mm, and steel chemical composition contains in weight%, relative to the total weight of said chemical composition: 0.10 ≤ Mo ≤ 0.21.
     
    17. Process for manufacturing a seamless pipe comprising the following successive steps:

    (a) providing a steel having a chemical composition as defined in any of claims 1 to 13, and hot forming a seamless pipe thereof

    (b) cooling down the seamless pipe obtained at (a) to room temperature,

    (c) heating up the cooled seamless pipe obtained at (b) to an austenitization temperature (AT) ranging from 890 to 970°C, preferably 900 to 930°C to obtain an austenitized seamless pipe, and then quenching said austenitized seamless pipe down to ambient temperature to obtain a quenched seamless pipe,

    (d) heating up the quenched seamless pipe obtained at (c) to a tempering temperature (TT) ranging from 610 to 680°C, and preferably 630 to 670°C before keeping said seamless pipe at the temperature TT and then cooling said seamless pipe down to ambient temperature to obtain a quenched and tempered seamless pipe.


     
    18. Process according to the preceding claim, wherein the tempering temperature (TT) ranges from 630 to 665°C, and preferably from 635 to 660°C.
     
    19. Use of a seamless pipe as defined in claims 14 to 16 for line pipes, for applications as process pipes, flowlines or risers in the oil and gas industry.
     


    Ansprüche

    1. Stahl mit einer Streckgrenze von höher als oder gleich 485 MPa und einer chemischen Zusammensetzung bestehend aus, in Gew.-% bezogen auf das Gesamtgewicht der chemischen Zusammensetzung:

    0,05 ≤ C ≤ 0,10

    0,15 ≤ Si ≤ 0,35

    1,20 ≤ Mn ≤ 1,50

    0,02 ≤ Cr ≤ 0,10

    0,10 < Mo ≤ 0,30

    0,015 ≤ Al ≤ 0,040

    0,002 ≤ N ≤ 0,012

    0,10 ≤ Ni ≤ 0,30

    0,02 ≤ V ≤ 0,06

    0,01 ≤ Nb ≤ 0,03

    0,001 ≤ Ti ≤ 0,025

    wobei der Rest der chemischen Zusammensetzung des Stahls von Fe und gegebenenfalls einem oder mehreren restlichen Elementen ausgewählt aus P, S, B, Ca, Cu und Gemischen davon gebildet wird; wobei die Mengen der restlichen Elemente, ausgedrückt in Gew.-% bezogen auf das Gesamtgewicht der chemischen Zusammensetzung, folgendermaßen sind:

    P ≤ 0,012

    S ≤ 0,003

    B ≤ 0,0005

    Ca ≤ 0,004

    Cu ≤ 0,12;

    und die chemische Zusammensetzung des Stahls der nachstehenden Formel (1) zwischen C, Cr, Mo, Nb, V und Ti, deren Gehalte in Gew.-% ausgedrückt werden, entspricht,


     
    2. Stahl gemäß Anspruch 1, der eine Streckgrenze von höher als oder gleich 485 MPa und unter 695 MPa, vorzugsweise zwischen 495 und 675 MPa, aufweist.
     
    3. Stahl gemäß Anspruch 1 oder 2, der eine Streckgrenze von höher als oder gleich 555 MPa und unter 705 MPa, vorzugsweise unter 675 MPa, aufweist.
     
    4. Stahl gemäß einem der vorstehenden Ansprüche, dessen chemische Zusammensetzung in Gew.-%, bezogen auf das Gesamtgewicht der chemischen Zusammensetzung, enthält: 0,06 ≤ C ≤ 0,08.
     
    5. Stahl gemäß einem der vorstehenden Ansprüche, dessen chemische Zusammensetzung in Gew.-%, bezogen auf das Gesamtgewicht der chemischen Zusammensetzung, enthält: 0,23 ≤ Si ≤ 0,31 und vorzugsweise 0,26 ≤ Si ≤ 0,30.
     
    6. Stahl gemäß einem der vorstehenden Ansprüche, dessen chemische Zusammensetzung in Gew.-%, bezogen auf das Gesamtgewicht der chemischen Zusammensetzung, enthält: 1,35 ≤ Mn ≤ 1,45 und vorzugsweise 1,40 ≤ Mn ≤ 1,45.
     
    7. Stahl gemäß einem der vorstehenden Ansprüche, dessen chemische Zusammensetzung in Gew.-%, bezogen auf das Gesamtgewicht der chemischen Zusammensetzung, enthält: 0,06 ≤ Cr ≤ 0,08.
     
    8. Stahl gemäß einem der vorstehenden Ansprüche, dessen chemische Zusammensetzung in Gew.-%, bezogen auf das Gesamtgewicht der chemischen Zusammensetzung, enthält: 0,16 ≤ Mo ≤ 0,26 und vorzugsweise 0,20 ≤ Mo ≤ 0,24.
     
    9. Stahl gemäß einem der vorstehenden Ansprüche, dessen chemische Zusammensetzung in Gew.-%, bezogen auf das Gesamtgewicht der chemischen Zusammensetzung, enthält: 0,03 ≤ V ≤ 0,05.
     
    10. Stahl gemäß einem der vorstehenden Ansprüche, dessen chemische Zusammensetzung in Gew.-%, bezogen auf das Gesamtgewicht der chemischen Zusammensetzung, enthält: 0,02 ≤ Nb ≤ 0,028.
     
    11. Stahl gemäß einem der vorstehenden Ansprüche, dessen chemische Zusammensetzung in Gew.-%, bezogen auf das Gesamtgewicht der chemischen Zusammensetzung, enthält: 0,005 ≤ Ti ≤ 0,020.
     
    12. Stahl gemäß einem der vorstehenden Ansprüche, dessen chemische Zusammensetzung der nachstehenden Formel (2) zwischen Cr und Mo, deren Gehalte in Gew.-% ausgedrückt werden, entspricht,


     
    13. Stahl gemäß einem der vorstehenden Ansprüche, dessen chemische Zusammensetzung der nachstehenden Formel (3) zwischen Nb und V, deren Gehalte in Gew.-% ausgedrückt werden, entspricht,


     
    14. Nahtloses Rohr, hergestellt aus einem Stahl gemäß einem der vorstehenden Ansprüche.
     
    15. Nahtloses Rohr gemäß Anspruch 14, wobei die Streckgrenze des Stahls zwischen 555 MPa und 740 MPa beträgt, die Wanddicke des Rohrs zwischen 15,1 und 35 mm beträgt und die chemischen Zusammensetzung des Stahls in Gew.-%, bezogen auf das Gesamtgewicht der chemischen Zusammensetzung, enthält: 0,16 ≤ Mo ≤ 0,26 und vorzugsweise 0,20 ≤ Mo ≤ 0,24.
     
    16. Nahtloses Rohr gemäß Anspruch 14, wobei die Streckgrenze des Stahls zwischen 485 MPa und 635 MPa beträgt, die Wanddicke des Rohrs zwischen 9,3 und 40 mm beträgt und die chemischen Zusammensetzung des Stahls in Gew.-%, bezogen auf das Gesamtgewicht der chemischen Zusammensetzung, enthält: 0,10 ≤ Mo ≤ 0,21.
     
    17. Verfahren zur Herstellung eines nahtlosen Rohrs, umfassend die folgenden aufeinanderfolgenden Schritte:

    (a) Bereitstellen eines Stahls mit einer chemischen Zusammensetzung gemäß einem der Ansprüche 1 bis 13 und Warmformen eines nahtlosen Rohrs daraus,

    (b) Abkühlen des bei (a) erhaltenen nahtlosen Rohrs auf Raumtemperatur,

    (c) Erhitzen des bei (b) erhaltenen abgekühlten nahtlosen Rohrs auf eine Austenitisierungstemperatur (AT) in dem Bereich von 890 bis 970 °C, vorzugsweise 900 bis 930 °C, um ein austenitisiertes nahtloses Rohr zu erhalten, und dann Abschrecken des austenitisierten nahtlosen Rohrs auf Umgebungstemperatur, um ein abgeschrecktes nahtloses Rohr zu erhalten,

    (d) Erhitzen des bei (c) erhaltenen abgeschreckten nahtlosen Rohrs auf eine Tempertemperatur (TT) in dem Bereich von 610 bis 680 °C und vorzugsweise 630 bis 670 °C, bevor das nahtlose Rohr bei der Temperatur TT gehalten wird, und dann Abkühlen des nahtlosen Rohrs auf Umgebungstemperatur, um ein abgeschrecktes und getempertes nahtloses Rohr zu erhalten.


     
    18. Verfahren gemäß dem vorstehenden Anspruch, wobei die Tempertemperatur (TT) in dem Bereich von 630 bis 665 °C und vorzugsweise von 635 bis 660 °C liegt.
     
    19. Verwendung eines nahtlosen Rohrs gemäß Ansprüchen 14 bis 16 für Leitungsrohre, für Anwendungen als Prozessrohre, Flussleitungen oder Steigrohre in der Öl- und Gasindustrie.
     


    Revendications

    1. Acier présentant une limite d'élasticité supérieure ou égale à 485 MPa et possédant une composition chimique constituée de, en % en poids, par rapport au poids total de ladite composition chimique,

    0,05 ≤ C ≤ 0,10

    0,15 ≤ Si ≤ 0,35

    1,20 ≤ Mn ≤ 1,50

    0,02 ≤ Cr ≤ 0,10

    0,10 < Mo ≤ 0,30

    0,015 ≤ Al ≤ 0,040

    0,002 ≤ N ≤ 0,012

    0,10 ≤ Ni ≤ 0,30

    0,02 ≤ V ≤ 0,06;

    0,01 ≤ Nb ≤ 0,03

    0,001 ≤ Ti ≤ 0,025

    le reste de la composition chimique dudit acier étant constituée par Fe et éventuellement un ou plusieurs éléments résiduels, choisis parmi P, S, B, Ca, Cu et des mélanges correspondants ; les quantités desdits éléments résiduels, exprimées en % en poids, par rapport au poids total de ladite composition chimique étant comme suit :

    P ≤ 0,012

    S ≤ 0,003

    B ≤ 0,0005

    Ca ≤ 0,004

    Cu ≤ 0,12;

    et la composition chimique dudit acier satisfaisant la formule suivante (1) entre C, Cr, Mo, Nb, V et Ti, les teneurs desquels étant exprimées en % en poids,


     
    2. Acier selon la revendication 1, qui présente une limite d'élasticité supérieure ou égale à 485 MPa, et inférieure à 695 MPa, préférablement entre 495 et 675 MPa.
     
    3. Acier selon la revendication 1 ou 2, qui présente une limite d'élasticité supérieure ou égale à 555 MPa, et inférieure à 705 MPa, préférablement inférieure à 675 MPa.
     
    4. Acier selon l'une quelconque des revendications précédentes, sa composition chimique contenant en % en poids, par rapport au poids total de ladite composition chimique : 0,06 ≤ C ≤ 0,08.
     
    5. Acier selon l'une quelconque des revendications précédentes, sa composition chimique contenant en % en poids, par rapport au poids total de ladite composition chimique : 0,23 ≤ Si ≤ 0,31, et préférablement 0,26 ≤ Si ≤ 0,30.
     
    6. Acier selon l'une quelconque des revendications précédentes, sa composition chimique contenant en % en poids, par rapport au poids total de ladite composition chimique : 1,35 ≤ Mn ≤ 1,45, et préférablement 1,40 ≤ Mn ≤ 1,45.
     
    7. Acier selon l'une quelconque des revendications précédentes, sa composition chimique contenant en % en poids, par rapport au poids total de ladite composition chimique : 0,06 ≤ Cr ≤ 0,08.
     
    8. Acier selon l'une quelconque des revendications précédentes, sa composition chimique contenant en % en poids, par rapport au poids total de ladite composition chimique : 0,16 ≤ Mo ≤ 0,26, et préférablement 0,20 ≤ Mo ≤ 0,24.
     
    9. Acier selon l'une quelconque des revendications précédentes, sa composition chimique contenant en % en poids, par rapport au poids total de ladite composition chimique : 0,03 ≤ V ≤ 0,05.
     
    10. Acier selon l'une quelconque des revendications précédentes, sa composition chimique contenant en % en poids, par rapport au poids total de ladite composition chimique : 0,02 ≤ Nb ≤ 0,028.
     
    11. Acier selon l'une quelconque des revendications précédentes, sa composition chimique contenant en % en poids, par rapport au poids total de ladite composition chimique : 0,005 ≤ Ti ≤ 0,020.
     
    12. Acier selon l'une quelconque des revendications précédentes, sa composition chimique satisfaisant la formule suivante (2) entre Cr et Mo, les teneurs desquels étant exprimées en % en poids,


     
    13. Acier selon l'une quelconque des revendications précédentes, sa composition chimique satisfaisant la formule suivante (3) entre Nb et V, les teneurs desquels étant exprimées en % en poids,


     
    14. Tuyau sans soudure, fait d'un acier selon l'une quelconque des revendications précédentes.
     
    15. Tuyau sans soudure selon la revendication 14, la limite d'élasticité de l'acier étant comprise entre 555 MPa et 740 MPa, l'épaisseur de paroi de tuyaux étant comprise entre 15,1 et 35 mm, et la composition chimique de l'acier contenant en % en poids, par rapport au poids total de ladite composition chimique : 0,16 ≤ Mo ≤ 0,26, et préférablement 0,20 ≤ Mo ≤ 0,24.
     
    16. Tuyau sans soudure selon la revendication 14, la limite d'élasticité de l'acier étant comprise entre 485 MPa et 635 MPa, l'épaisseur de paroi de tuyaux étant comprise entre 9,3 et 40 mm, et la composition chimique de l'acier contenant en % en poids, par rapport au poids total de ladite composition chimique : 0,10 ≤ Mo ≤ 0,21.
     
    17. Procédé pour la fabrication d'un tuyau sans soudure comprenant les étapes successives suivantes :

    (a) mise à disposition d'un acier possédant une composition chimique telle que définie dans l'une quelconque des revendications 1 à 13, et le formage à chaud d'un tuyau sans soudure avec celui-ci

    (b) refroidissement du tuyau sans soudure obtenu en (a) à température ambiante,

    (c) chauffage du tuyau sans soudure refroidi obtenu en (b) à une température d'austénisation (TA) dans la plage de 890 à 970 °C, préférablement 900 à 930 °C pour obtenir un tuyau sans soudure austénisé, et ensuite trempe dudit tuyau sans soudure austénisé jusqu'à la température ambiante pour obtenir un tuyau sans soudure trempé,

    (d) chauffage du tuyau sans soudure trempé obtenu en (c) à une température de revenu (TR) dans la plage de 610 à 680 °C, et préférablement 630 à 670 °C avant de maintenir ledit tuyau sans soudure à la température TR et ensuite refroidissement dudit tuyau sans soudure jusqu'à la température ambiante pour obtenir un tuyau sans soudure trempé et revenu.


     
    18. Procédé selon la revendication précédente, la température de revenu (TR) se situant dans la plage de 630 à 665 °C, et préférablement de 635 à 660 °C.
     
    19. Utilisation d'un tuyau sans soudure tel que défini dans les revendications 14 à 16 pour des pipelines, pour des applications comme tuyaux de procédé, conduites d'écoulement ou colonnes montantes dans l'industrie du pétrole et du gaz.
     




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    Cited references

    REFERENCES CITED IN THE DESCRIPTION



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    Patent documents cited in the description