EP0178334B1 - Aciers inoxydables martensiques pour tubes d'acier sans soudure - Google Patents

Aciers inoxydables martensiques pour tubes d'acier sans soudure Download PDF

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Publication number
EP0178334B1
EP0178334B1 EP19840112233 EP84112233A EP0178334B1 EP 0178334 B1 EP0178334 B1 EP 0178334B1 EP 19840112233 EP19840112233 EP 19840112233 EP 84112233 A EP84112233 A EP 84112233A EP 0178334 B1 EP0178334 B1 EP 0178334B1
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Prior art keywords
weight
amount
steel
martensitic stainless
pipe
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Expired
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EP19840112233
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German (de)
English (en)
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EP0178334A1 (fr
Inventor
Hiroshi Ohtsubo
Tatsuo Kawasaki
Isao Takada
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JFE Steel Corp
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Kawasaki Steel Corp
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Application filed by Kawasaki Steel Corp filed Critical Kawasaki Steel Corp
Priority to EP19840112233 priority Critical patent/EP0178334B1/fr
Priority to DE8484112233T priority patent/DE3482772D1/de
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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
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • 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

Definitions

  • This invention relates to the use of martensitic stainless steels for the manufacture of seamless steel pipe such as oilwell pipe and pipeline tubing.
  • Martensitic stainless steels two representative grades of which are SUS 410 and SUS 420 (Japan Industrial Standard [JIS] designations), have excellent corrosion resistance in highly corrosive environments containing CO2, These materials are thus regarded as excellent candidates for use in oil-well pipe, geothermal well pipe, and pipeline tubing.
  • the strength of oil-well pipe is normally required to be least equivalent to that of American Petroleum Institute (API) standard L80 grade steel (yield strength ? 80 ksi).
  • Pipeline tubing should generally have a strength at least equivalent to that of API standard X60 grade steel (yield strength ? 60 ksi).
  • Martensitic stainless steels having a variety of strengths can be obtained by the application of specific types of heat treatment, such as quench-tempering, normalizing-tempering, or just tempering.
  • specific types of heat treatment such as quench-tempering, normalizing-tempering, or just tempering.
  • tempering is performed at a temperature of less than 600°C.
  • each of these steels developed stress-corrosion cracking when tempered at less than 600°C, but none demonstrated stress-corrosion cracking when tempered at 600°C or more (a cross "X” in Table 1 indicates the presence of stress-corrosion cracking; an open circle “0” indicates the absence of stress-corrosion cracking).
  • a cross "X” in Table 1 indicates the presence of stress-corrosion cracking; an open circle “0” indicates the absence of stress-corrosion cracking.
  • a martensitic stainless steel material for disc brake of motorcycle which consists of 0.04 to 0.10% by weight of C + N; 0 to 0.5% by weight of Si; 1.0 to 2.5% by weight of Mn; 10.0 to 14.5% by weight of Cr; 0 to 0.5% by weight of Ni; 0 to 0.5% by weight of Cu and the remainder thereof being Fe.
  • the fabricating of the disc brakes is performed by melting the steel and subjecting to hot rolling and annealing to prepare a hot rolled annealed sheet. The sheet is then hardened by applicating a temperature of 800 to 1050°C.
  • martensitic stainless steels decreases as the ferrite content of the steel structure increases.
  • the ferrite content at 1200°C exceeds 40%, the ferrite content in the normal quenching or normalizing temperature range of 900-1000°C rises to 20% or more, making it difficult to achieve the high strength required in pipeline tubing and oil-well pipe by temperature at 600°C or more.
  • martensitic stainless steels must be composed of not more than 40% ferrite at 1200°C.
  • compositions in which the austenite phase (which becomes martensite at room temperature) exists in combination with a ferrite phase comprising 20-30% of the composition have the worst hot workability.
  • the hot workability is about the same as that of austenitic single-phase steels (which become martensitic single-phase steels at room temperature or below the Ms point).
  • the hot workability rises sharply with increasing ferrite content above this point.
  • martensitic stainless steels with a ferrite content of 40% or less at 1200°C have inferior hot workability, their use in the production of high-strength seamless steel pipe by the processing described below tends to result in defects, complicating pipe manufacture.
  • Seamless stainless steel pipe is generally produced either by an inclined rolling method such as the plug mill or mandrel mill process, or by a hot extrusion method, of which the Ugine-Sejournet and Erhart pushbench processes are typical.
  • certain types of matensitic stainless steels namely, those with a ferrite content of 40% or less at 1200°C
  • seamless steel pipe is manufactured from these steels by a cross rolling process such as the plug mill process or the mandrel mill process, defects arise on both the outside and inside walls of the pipe during piercing of the billet on a piercing mill. For this reason, seamless pipe made of this type of steel is generally produced by a hot extrusion process, such as the Ugine-Sejournet process.
  • Object of the invention is to enable the practical application of the plug mill and mandrel mill process in martensitic stainless steels having a ferrite content of 40% or less at 1200°C, for the manufacture of seamless steel pipe without formation of defects during pipe fabrication at high productivity and low cost.
  • the object is solved by the use of martensitic stainless steel consisting of not more than 0.30% by weight of C, not more than 1.0% by weight of Si, not more than 2.0% by weight of Mn, 11-14% by weight of Cr, 0.005 ⁇ 0.10% by weight of AI, and not more than 0.10% by weight of N, wherein the amount of P is held to no more than 0.02% by weight and the amount of S to no more than 0.003% by weight, the remainder thereof being Fe and unavoidable impurities, said steel having a ferrite content of not more than 40% by weight at 1200°C for manufacture of seamless steel pipe by the Mannesmann plug mill or mandrel mill process.
  • This invention also contemplates the use of martensitic stainless steel consisting of not more than 0.30% by weight of C, not more than 1.0% by weight of Si, not more than 2.0% by weight of Mn, 11-14% by weight of Cr, 0.005 ⁇ 0.10% by weight of Al, not more than 0.01% by weight of N, and one or more elements selected from the group consisting of up to 3.5% by weight of Ni, up to 2.0% by weight of Cu, up to 2.5% by weight of Mo, up to 0.10% by weight of Nb, and up to 0.10% by weight of V, the remainder thereof being Fe and unavoidable impurities, said steel having a ferrite content of not more than 40% by weight at 1200°C for manufacture of seamless steel pipe by the Mannesmann plug mill or mandrel mill process.
  • the present invention furthermore contemplates the use of martensitic stainless steel consisting of not more than 0.30% by weight of C, not more than 1.0% by weight of Si, not more than 2.0% by weight of Mn, 11-14% by weight of Cr, 0.005 ⁇ 0.10% by weight of Al, not more than 0.10% by weight of N, and one or more elements selected from the group consisting of rare earth elements, Ca, and B, the amount of the rare earth elements ranging from 4 x (% of S) to 20 x (% of S), that of Ca from 1 x (% of S) to 10 x (% of S), and that of B from 0.001 to 0.008% by weight, wherein the amount of P is held to no more than 0.02% by weight and the amount of S to no more than 0.003% by weight, the remainder thereof being Fe and unavoidable impurities, said steel having a ferrite content of not more than 40% by weight at 1200°C, for manufacture of seamless steel pipe by Mannesmann plug mill or mandrel mill process
  • the invention also contemplates the use of martensitic stainless steels consisting of not more then 0.30% by weight of C, not more than 1.0% by weight of Si, not more than 2.0% by weight of Mn, 11-14% by weight of Cr, 0.005 ⁇ 0.10% by weight of AI, not more than 0.10% by weight of N, and one or more elements selected from the group consisting of up to 3.5% by weight of Ni, up to 2.0% by weight of Cu, up to 2.5% by weight of Mo, up to 0.10% by weight of Nb, and up to 0.10% by weight or less of V, as well as one or more elements selected from the group consisting of the rare earth elements, Ca, and B, the amount of the rare earth elements ranging from 4 x (% of S) to 20 x (% of S), that of Ca from 1 x (% of S) to 10 x (% of S), and that of B from 0.001 to 0.008% by weight, wherein the amount of P is held to no more than 0.02% by weight and the amount
  • Carbon is necessary for strength. However, because corrosion resistance declines at a carbon content, in excess of 0.30%, the upper limit on carbon content has been set at 0.30%.
  • Chromium markedly increases corrosion resistance in CO 2 -containing environments.
  • the addition of at least 11% is intended to prevent pitting and crevice corrosion.
  • this element also is ferrite- forming.
  • the addition of more than 14% therefore increases the amount of ferrite, making it difficult to achieve the desired strength under the heat conditions (tempering temperature) necessary to preserve resistance of the steel to stress-corrosion cracking.
  • the range in the chromium content was thus set at 11-14%.
  • Silicon is effective as a deoxidizer and should preferably be included at a level of at least 0.2%.
  • a content of more than 1.0% reduces toughness, so we set an upper limit of 1.0%.
  • Aluminum acts as a deoxidizer, reducing the level of oxygen in the steel by oxygen fixation, enhancing the hot workability.
  • the stabilizing effects of AI addition are not observed at less than 0.005%; these effects reach a saturation level at 0.10%.
  • the content of AI was thus limited to a range of from 0.005% by 0.10%.
  • Nitrogen increases the strength and corrosion resistance of the steel up to a concentration of 0.10%, beyond which additional improvement is not observed. For this reason, the N content was set at not more than 0.10%.
  • Sulfur is present in the steel as an undesirable impurity that severely reduces the hot workability of the steels in the present invention. This adverse effect is particularly large during piercing of the billet on a piercing mill when the seamless pipe is fabricated by the plug mill process or the mandrel mill process. A sulfur level in excess of 0.003% makes if difficult to produce scratch-free seamless pipe, which is why the S content must be held to no more than 0.003%.
  • P is another impurity unavoidably present in steels. It produces a marked deterioration in the hot workability of the steel at high temperatures of 1200°C and above. This element causes scratch formation on the inside wall of the tube during piercing of the billet on a piercing mill. Piercing without scratch formation is difficult at a P level about 0.02%, and so this must be held to 0.02% or less.
  • the martensitic stainless steels used in the present invention may also contain one or more elements selected from the group consisting of Ni, Cu, Mo, Nb, and V, and one or more elements chosen from the group consisting of rare earth metals, Ca, and B. The reasons for the limits set to the contents for each of these are given below.
  • Nickel increases corrosion resistance. The addition of more than 3.5%, however, produces no further improvement in corrosion resistance. Because Ni is expensive, the upper limit of addition was set at 3.5%.
  • Molybdenum Mo enhances the strength and corrosion resistance of the steel. At levels of under 0.01 %, this effect is not fully exhibited, while the addition of more than 2.5% produces no corresponding increase in effect. Because Mo too is a high-priced metal, Mo addition was limited to a range of from 0.01 % to 2.5%.
  • Niobium increases steel strength, but is ineffective at levels of under 0.01 %. The addition of over 0.10% fails to produce additional improvement. The range of Nb addition was thus set at 0.01-0.10%.
  • Vanadium increases the strength of the steel, but is not effective at levels below 0.1%. Further improvement does not result from the addition of more than 0.10%. The range in the content of V was thus set at 0.01-0.10%.
  • Copper improves the strength and corrosion resistance of the steel. However, because the addition of more than 2.0% reduces hot workability, the upper limit on copper addition was set at 2.0%.
  • Rare earth metals (REM), calcium The rare earth metals and calcium are powerful sulfide-forming elements. The formation of the sulfides of rare earth metals or calcium reduces the amount of sulfur in solid solution within the steel, thereby improving the hot workability of the steel. However, when the amount of rare earth elements is four times as great as the sulfur content (wt%) or the amount of calcium less than equivalent to the amount of sulfur, this effect is minor. On the other hand, when the level of rare earth elements is greater than 20 times, or the level of calcium greater than 10 times, the amount of sulfur, this effect reaches a saturation point and the oxides and sulfides of these elements may even have the opposite effect of increasing surface defects. For these reasons, we limited the amount of rare earth metals to a range of from 4 x (%S) to 20 x (%S), and the amount of calcium to a range of from 1 x (%S) to 10 x (%S).
  • ferrite content for the steels of the present invention of 40% or less at 1200°C. This is because, as we have seen above, even the plug mill and mandrel mill processes can be used to manufacture seamless pipe without hindrance or defects from steels having a ferrite content of more than 40% at 1200°C.
  • the ferrite content (%) at 1200°C is defined by Eq. (1) below:
  • a bloom obtained by continuous casting or blooming is rolled into a round billet.
  • This billet is then heated to a given temperature, preferably from 1200 to 1250°C, and pierced and rolled by means of the Mannesmann plug mill process or the Mannesmann mandrel mill process.
  • the billet is first pierced on a piercer, then rolled by an elongator, a plug mill, a reeler and a sizer, in that order.
  • the Mannesmann mandrel mill process is used, the billet is first pierced on a piercer then rolled respectively on a mandrel mill and hot-stretch reducer.
  • the pipe is heat-treated either in a batch-type furnace or by induction heating.
  • This heat treatment may consist of quench-tempering, normalize-tempering, or simply tempering. This gives steel pipe of the desired strength.
  • Table 2 shows the chemical constituents and whether or not defects were formed for a number of examples illustrating the present invention and several comparative examples.
  • a billet having a diameter of 175 mm was heated to 1230°C and pierced on a piercer to form a tube with an outside diameter of 185 mm and a wall thickness of 19.76 mm.
  • the inside and outside walls of the tube were examined.
  • An "X" in the table denotes that defects such as scratches or cracks were found on the tube wall.
  • An open circle 0 indicates that no defects were observed, or only minor faults of no practical consequence noted.
  • the ferrite (%) shown in Table 1 shows the ferrite contents (%) at 1200° which was calculated using Eq. (1). If the computed value was negative, this was indicated in the table as 0.
  • the rare earth metals used in the examples shown in Table 2 consisted primarily of cesium (approx. 50%).
  • the martensitic stainless steels used in seamless steel tube in accordance with the present invention raises the hot workability, and especially the hot piercability, of steels having ferrite contents of 40% or less at 1200°C, despite the difficulty previously encountered in manufacturing seamless pipe from such steels by a plug mill or a mandrel mill process. This is achieved by holding down the P and the S contents of the steel. As a result, seamless steel pipe need no longer be manufactured by a hot extrusion process, and can now be manufactured free of defects by a plug mill or a mandrel mill process. Because this permits the use of plug mill and mandrel mill processes in the production of seamless pipe from this type of steel, higher productivity can be achieved, along with increased yield and reduced costs.
  • This invention also provides the use of martensitic stainless steels for manufacturing seamless steel pipe wherein, in addition to restricting the levels of P and S, one or more elements selected from the rare earth metals, calcium, and boron are added, further increasing the hot piercability of the steel. This permits the manufacture of defect-free seamless steel pipe by means of a mandrel mill or plug mill process.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Claims (4)

1. Utilisation d'acier inoxydable martensitique comprenant au plus 0,30% en poids de C, au plus 1,0% en poids de Si, au plus 2,0% en poids de Mn, 11 à 14% en poids de Cr, 0,005 à 0,10% en poids de AI, et au plus 0,10 en poids de N, la proportion de P étant maintenue à au plus 0,02% en poids et la proportion de S à au plus 0,003% en poids, le complément consistant en Fe et des impuretés inévitables, ledit acier ayant une teneur en ferrite de 40% en poids au plus à 1.200°C pour la fabrication de tube d'acier sans soudure par le procédé Mannesmann avec fraise à queue ou fraise à mandrin.
2. Utilisation d'acier inoxydable martensitique comprenant au plus 0,30% en poids de C, au plus 1,0% en poids de Si, au plus 2,0% en poids de Mn, 11 à 14% en poids de Cr, 0,005 à 0,10% en poids de AI, et au plus 0,10 en poids de N, et un ou plusieurs éléments choisis dans le groupe comprenant jusqu'à 3,5% en poids de Ni, jusqu'à 2% en poids de Cu, jusqu'à 2,5% en poids de Mo, jusqu'à 0,10% en poids de Nb, et jusqu'à 0,10% en poids de V, la proportion de P étant maintenue à au plus 0,02% en poids et la proportion de S à au plus de 0,003% en poids, le complément étant constitué par Fe et des impuretés inévitables, ledit acier ayant une teneur en ferrite de 40% en poids au plus à 1.200°C pour la fabrication de tuyau d'acier sans soudure par le procédé Mannesmann avec fraise à queue ou fraise à mandrin.
3. Utilisation d'acier inoxydable martensitique comprenant au plus 0,30% en poids de C, au plus 1,0% en poids de Si, au plus 2,0% en poids de Mn, 11 à 14% en poids de Cr, 0,005 à 0,10% en poids de AI, et au plus 0,10 en poids de N, et un ou plusieurs éléments choisis dans le groupe comprenant des éléments des terres rares allant de 4 x (% de S) à 20 x (% de S), celle de Ca de 1 x (% de S) à 10 x (% de S), et celle de B de 0,001 à 0,008% en poids, la proportion de P étant maintenue à 0,02% en poids au plus et la proportion de S à 0,003% en poids au plus, le complément étant constitué par Fe et des impuretés inévitables, ledit acier ayant une teneur en ferrite de 40% en poids au plus à 1.200°C, pour la fabrication de tuyaux d'acier inoxydable par le procédé Mannesmann avec fraise à queue ou fraise à mandrin.
4. Utilisation d'acier inoxydable martensitique comprenant au plus 0,30% en poids de C, au plus 1,0% en poids de Si, au plus 2,0% en poids de Mn, 11 à 14% en poids de Cr, 0,005 à 0,10% en poids de AI, et au plus 0,10 en poids de N, et un ou plusieurs éléments choisis dans le groupe comprenant jusqu'à 3,5% en poids de Ni, jusqu'à 2% en poids de Cu, jusqu'à 2,5% en poids de Mo, jusqu'à 0,10% en poids de Nb, et jusqu'à 0,10% en poids ou moins de V, ainsi qu'un ou plusieurs éléments choisis dans le groupe comprenant les éléments des terres rares, Ca et B, la proportion des éléments des terres rares allant de 4 x (% de S) à 20 x (% de S), celle de Ca de 1 x (% de S) à 10 x (% de S), et celle de B de 0,001 à 0,008% en poids, la proportion de P étant maintenue à 0,02% en poids au plus et à la proportion de S à 0,003% en poids au plus, le complément étant constitué par Fe et des impuretés inévitables, ledit acier ayant une teneur en ferrite de 40% en plus à 1.200°C, pour la fabrication de tube d'acier sans soudure par le procédé Mannesmann avec fraise à queue ou fraise à mandrin.
EP19840112233 1984-10-11 1984-10-11 Aciers inoxydables martensiques pour tubes d'acier sans soudure Expired EP0178334B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP19840112233 EP0178334B1 (fr) 1984-10-11 1984-10-11 Aciers inoxydables martensiques pour tubes d'acier sans soudure
DE8484112233T DE3482772D1 (de) 1984-10-11 1984-10-11 Rostfreie martensitische staehle fuer nahtlose rohre.

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Application Number Priority Date Filing Date Title
EP19840112233 EP0178334B1 (fr) 1984-10-11 1984-10-11 Aciers inoxydables martensiques pour tubes d'acier sans soudure

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EP0178334A1 EP0178334A1 (fr) 1986-04-23
EP0178334B1 true EP0178334B1 (fr) 1990-07-18

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US8211247B2 (en) 2006-02-09 2012-07-03 Schlumberger Technology Corporation Degradable compositions, apparatus comprising same, and method of use
US8220554B2 (en) 2006-02-09 2012-07-17 Schlumberger Technology Corporation Degradable whipstock apparatus and method of use
US9789544B2 (en) 2006-02-09 2017-10-17 Schlumberger Technology Corporation Methods of manufacturing oilfield degradable alloys and related products
US9982505B2 (en) 2005-08-31 2018-05-29 Schlumberger Technology Corporation Well operating elements comprising a soluble component and methods of use
US10316616B2 (en) 2004-05-28 2019-06-11 Schlumberger Technology Corporation Dissolvable bridge plug

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US8231947B2 (en) * 2005-11-16 2012-07-31 Schlumberger Technology Corporation Oilfield elements having controlled solubility and methods of use
US8211248B2 (en) 2009-02-16 2012-07-03 Schlumberger Technology Corporation Aged-hardenable aluminum alloy with environmental degradability, methods of use and making
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US9982505B2 (en) 2005-08-31 2018-05-29 Schlumberger Technology Corporation Well operating elements comprising a soluble component and methods of use
US8211247B2 (en) 2006-02-09 2012-07-03 Schlumberger Technology Corporation Degradable compositions, apparatus comprising same, and method of use
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EP0178334A1 (fr) 1986-04-23

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