WO2023286338A1 - Alliage à base de ni-cr-mo pour tuyau soudé ayant une excellente aptitude au façonnage et une excellente résistance à la corrosion - Google Patents

Alliage à base de ni-cr-mo pour tuyau soudé ayant une excellente aptitude au façonnage et une excellente résistance à la corrosion Download PDF

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WO2023286338A1
WO2023286338A1 PCT/JP2022/009729 JP2022009729W WO2023286338A1 WO 2023286338 A1 WO2023286338 A1 WO 2023286338A1 JP 2022009729 W JP2022009729 W JP 2022009729W WO 2023286338 A1 WO2023286338 A1 WO 2023286338A1
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corrosion resistance
weld
less
ductility
cracks
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PCT/JP2022/009729
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English (en)
Japanese (ja)
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大樹 前田
富高 韋
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日本冶金工業株式会社
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Priority to CN202280049165.0A priority Critical patent/CN117651784A/zh
Priority to DE112022003529.3T priority patent/DE112022003529T5/de
Publication of WO2023286338A1 publication Critical patent/WO2023286338A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon

Definitions

  • the present invention relates to Ni--Cr--Mo alloys, and more particularly to Ni--Cr--Mo alloys that can maintain workability and corrosion resistance even after welding.
  • Ni-Cr-Mo alloys are widely used in harsh corrosive environments such as chemical plants, natural gas fields, and oil fields because they are materials with extremely high corrosion resistance. It is also used in the cladding of heaters, etc., and is also used in severe environments where it is prone to corrosion. For use in such fields, various welding and processing are required, and in many cases, processing is applied to the welded portion. Therefore, workability and corrosion resistance are required for the welded portion as well as for the base material portion. However, since the weld zone becomes a solidified structure, the workability is lowered due to the occurrence of cracks and the ductility deterioration of the weld zone as well as the deterioration of corrosion resistance. Therefore, improvement is required.
  • Patent Document 1 For such Ni--Cr--Mo alloys, a manufacturing method in which Mo segregation is reduced for the purpose of improving corrosion resistance (see, for example, Patent Document 1), and a technique for controlling carbides that affect corrosion resistance (for example, Patent Document 2) is shown.
  • Patent Document 2 a manufacturing method in which Mo segregation is reduced for the purpose of improving corrosion resistance
  • Patent Document 2 a technique for controlling carbides that affect corrosion resistance
  • an object of the present invention is to provide a Ni-Cr-Mo alloy that is excellent in weld workability and corrosion resistance.
  • the present invention was completed through experiments. : 0.02 to 1.00%, P: 0.030% or less, S: 0.005% or less, Cr: 18.0 to 24.0%, Mo: 7.5 to 9.0%, Cu: 0.01-0.20%, Al: 0.005-0.400%, Ti: 0.1-1.0%, Fe: 3.0-6.0%, Nb: 2.5-4. 0%, Co: 0.01-0.50%, V: 0.05-0.50%, N: 0.002-0.020%, Sn: 0.003-0.030%, W: 0 .05 to 0.50%, Nb+Ti+V: 2.5 to 4.5%, Cu+10Sn: 0.40 or less, and the balance being Ni and unavoidable impurities.
  • O 0.005% or less
  • Mg 0.001-0.010%
  • Ca 0.0001-0.0100%
  • FIG. 2 is a schematic diagram of sample collection in Examples.
  • the test piece had a plate thickness of 3 mm, a width of 30 mm and a length of 100 mm, and was sampled with the tensile direction parallel to the rolling direction.
  • the workability after welding was evaluated by the elongation ratio defined below.
  • Welds were made by non-filler plasma welding.
  • the welding conditions are a current of 100 A, a voltage of 30 V, a speed of 500 mm/min, a center gas and a back gas of 100% Ar gas, a shield gas of 93% Ar + 7% H2 gas, and a groove shape of I type.
  • the welded portion was made smooth by bead cutting. The test piece was taken so that the weld bead was perpendicular to the tensile direction and the welded part was in the center of the parallel part of the test piece.
  • Table 1 shows the above test results.
  • the total amount of Nb + Ti + V is low even if any one of Ti, Nb, and V is not added (Nos. 8, 9, and 10) and Ti, Nb, and V are all included.
  • the elongation was significantly reduced in sample (#11).
  • the C content and N content were high (Nos. 12 and 13), the elongation was remarkably lowered.
  • Fig. 1 shows the relationship between the amount of Co and the elongation ratio of samples Nos. 1 to 7
  • Fig. 2 shows the relationship between the amount of Cu and the elongation ratio for Nos. 1 to 6. Improvement in elongation was confirmed when Cu or Co was added compared to no addition of Cu or Co (Nos. 6 and 7), and improvement in elongation of the weld zone was observed as the amount of Cu and the amount of Co increased.
  • a test piece with a length of 500 mm was taken in the pipe-making direction of the pipe, and a steel cylinder of 135R (mm) was subjected to a bending test based on the press bending method.
  • the bead was placed on the lower side of the pipe, and the cylinder was pushed in from above.
  • FIG. 3 plots the bending test results at 135R, with the horizontal axis representing the Sn content and the vertical axis representing the Cu content. A sample with no defect was indicated by ⁇ , and a sample with a defect was indicated by ⁇ . In the figure, cracking was not observed in the region where Cu+10 ⁇ Sn was 0.40 or less, but cracking was observed when Cu and Sn exceeded 0.40 and were high. Therefore, it is necessary to limit the amount of Cu and the amount of Sn and to set Cu+10 ⁇ Sn to 0.40 or less.
  • C 0.002-0.020%
  • C is an element that affects workability and corrosion resistance.
  • C combines with Nb, Ti and V in the Ni--Cr--Mo alloy to form carbides. Excess carbide in the weld reduces ductility and initiates cracks during welding. Furthermore, in the heat affected zone due to heat treatment and welding, it combines with Cr and Mo, which are effective for maintaining corrosion resistance, and M6C (M is mainly Mo, Ni, Cr, Si), M23C6 (M is mainly Cr, Mo, Fe) tends to form carbides.
  • C is defined as 0.002 to 0.020%. It is preferably 0.003 to 0.015%. Most preferably, it is between 0.003 and 0.010%.
  • Si 0.02-1.00% Si is an element effective for deoxidation and also needs to be 0.02% or more in order to improve fluidity during welding. However, if the fluidity of molten metal becomes too good, a convex bead cannot be secured in the shape of the welded portion, so it must be suppressed to 1.00% or less. In addition, it is an element that promotes the formation of M6C and M23C6 and lowers intergranular corrosion resistance. Therefore, Si is defined as 0.02 to 1.00%. It is preferably 0.03 to 0.80%, more preferably 0.05 to 0.50%.
  • Mn 0.02-1.00% 0.02% or more is necessary because Mn segregates at grain boundaries and fixes P and S that cause weld cracks and suppresses weld cracks. However, it is an element that promotes the formation of MnS and lowers the pitting corrosion resistance, so the content should be 1.00% or less. Therefore, Mn is defined as 0.02 to 1.00%. It is preferably 0.03 to 0.80%, more preferably 0.05 to 0.50%.
  • P 0.030% or less
  • P is an element that segregates at grain boundaries and deteriorates hot workability and corrosion resistance.
  • the susceptibility to weld cracking is increased by forming a eutectic with a low melting point with Ni. Therefore, it is desirable to reduce P. Therefore, P is set to 0.030% or less. It is preferably 0.028% or less, more preferably 0.020% or less.
  • S 0.005% or less
  • S is an element that segregates at grain boundaries and degrades hot workability, and forms MnS to degrade corrosion resistance.
  • S is defined as 0.005% or less. It is preferably 0.002% or less, more preferably 0.0015% or less.
  • Cr 18.0-24.0% Cr is a very important element for forming a passive film on the surface of the alloy to maintain corrosion resistance. However, the addition of excessive Cr promotes precipitation of M23C6, resulting in deterioration of corrosion resistance. Therefore, Cr is defined as 18.0 to 24.0%. It is preferably 20.0 to 24.0%, more preferably 21.0 to 23.0%.
  • Mo 7.5-9.0% Mo, like Cr, is an important element for forming a passive film and maintaining corrosion resistance. However, excessive addition of Mo promotes precipitation of M6C, resulting in deterioration of corrosion resistance. Also, excessive addition of Mo increases strength but decreases ductility. Therefore, Mo is defined as 7.5-9.0%. Preferably, it is 8.0-9.0%, more preferably 8.0-8.5%.
  • Cu 0.01-0.20%
  • Cu is an important element for improving the ductility of the base material and the weld zone, so 0.01% is necessary. However, excessive addition reduces hot workability and causes weld cracks.
  • Cu is defined as 0.01 to 0.20%. Preferably, it is 0.02-0.15%, more preferably 0.02-0.10%.
  • Al 0.005-0.400% Since Al is an element effective for deoxidation, 0.005% is required. By making Al 0.005% or more, O can be made 0.005% or less. However, excessive addition reduces hot workability. In addition, it forms alumina clusters, resulting in linear defects on the surface of the alloy plate. Therefore, Al is set to 0.005 to 0.400%. It is preferably 0.020 to 0.300%, more preferably 0.050 to 0.300%.
  • Ti 0.1-1.0% Ti combines with C and N to form carbides (TiC) and nitrides (TiN), which refines the solidification structure of the weld zone and improves ductility, while suppressing the formation of M6C and M23C6, which cause a decrease in corrosion resistance. do.
  • TiC carbides
  • TiN nitrides
  • TiO 2 oxides
  • Fe 3.0-6.0% Fe is added to reduce the production cost and at the same time has the effect of reducing the amount of O in the alloy. However, since excessive addition causes deterioration of corrosion resistance, it is defined as 3.0 to 6.0% or less. It is preferably 3.0 to 5.0%, more preferably 3.0 to 4.5%.
  • Nb 2.5-4.5%
  • Nb combines with C and N to form carbides (NbC) and nitrides (NbN), thereby refining the solidified structure of the weld zone and improving ductility. Also, it suppresses the formation of M6C and M23C6, which cause deterioration of corrosion resistance. On the other hand, it dissolves and increases the strength, but reduces the ductility. Moreover, excessive addition of Nb causes a decrease in hot workability due to a decrease in ductility development temperature. Therefore, Nb is defined as 2.5 to 4.5%. Preferably, it is 2.8-4.0%, more preferably 2.8-3.8%.
  • Co 0.01-0.50% Since Co is an important element for improving the ductility of the base material and weld zone, 0.01% is necessary. However, excessive addition reduces hot workability and causes weld cracks. Therefore, Co is defined as 0.01 to 0.50%. Preferably, it is 0.01 to 0.30%. More preferably 0.01 to 0.20%.
  • V 0.05-0.50% Like Nb and Ti, V combines with C and N to form carbides (VC) and nitrides, thereby refining the solidified structure of the weld zone and improving ductility. Also, it suppresses the formation of M6C and M23C6, which cause deterioration of corrosion resistance. On the other hand, it dissolves and increases the strength, but reduces the ductility. V was defined as 0.05-0.50%. Preferably, it is 0.10 to 0.50%. More preferably 0.10 to 0.30%.
  • N 0.002-0.020%
  • N combines with Nb, Ti and V to form nitrides and carbonitrides.
  • An optimum amount of nitrides and carbonitrides improves ductility by refining the solidified structure of the weld zone.
  • excessive nitrides and carbonitrides in the weld zone reduce ductility and become starting points for cracks during welding.
  • N is defined as 0.002 to 0.020%.
  • it is 0.002 to 0.016%. More preferably, it is 0.002 to 0.010%.
  • Sn 0.003-0.030%
  • Sn is an element that improves corrosion resistance when added in a very small amount.
  • Sn is defined as 0.003 to 0.030%. It is preferably 0.004 to 0.020%, more preferably 0.006 to 0.010%.
  • W 0.05-0.50% Like Mo, W has the effect of improving corrosion resistance, but excessive addition forms carbides and lowers corrosion resistance. Therefore, W is defined as 0.05 to 0.50%. Preferably, it is 0.10 to 0.40%. More preferably, it is 0.10 to 0.30%.
  • Nb+Ti+V 2.5-4.5%
  • Nb, Ti and V combine with C and N to form carbides, nitrides and carbonitrides.
  • An optimum amount of nitrides and carbonitrides improves the ductility of the weld zone by refining the solidified structure of the weld zone.
  • excessive nitrides and carbonitrides in the weld zone reduce ductility and become starting points for cracks during welding.
  • Nb+Ti+V 2.5 to 4.5%.
  • it is 2.8-4.5%, more preferably 3.0-4.0%.
  • Cu+10Sn 0.40 or less
  • the amount of Sn added to Cu increases, a compound with a low melting point is formed, which causes cracks in the weld zone. Therefore, it is set to 0.40 or less. It is preferably 0.35 or less, more preferably 0.30 or less.
  • O 0.005% or less
  • O forms oxides and deteriorates weldability and hot workability. It also forms blow holes during welding and improves melt flow during welding. Therefore, it is desirable to reduce it.
  • the formation of Al 2 O 3 clusters and Ti oxides lowers the hot workability and causes linear defects. Therefore, O is set to 0.005% or less. Preferably, it is 0.004% or less, more preferably 0.003% or less.
  • Mg 0.001-0.010% Like Mn, Mg segregates at grain boundaries and fixes P and S, which cause weld cracks, to suppress weld cracks. On the other hand, when Mg is contained in a certain amount or more, inclusions aggregate on the weld bead, causing deterioration of workability and deterioration of corrosion resistance due to starting points of corrosion. In addition, MgO inclusions are formed and clustered, which causes surface defects in the product. Therefore, Mg was defined as 0.001 to 0.010%. Preferably, it is 0.002 to 0.008%. More preferably, it is 0.002 to 0.005%.
  • Ca 0.0010 to 0.0100%
  • Ca like Mn, segregates at grain boundaries and fixes P and S, which cause weld cracks, to suppress weld cracks.
  • Ca when Ca is contained in a certain amount or more, inclusions aggregate on the weld bead, causing deterioration of workability and deterioration of corrosion resistance due to starting points of corrosion.
  • CaO inclusions are formed and clustered, which causes surface defects in products. Therefore, Ca is defined as 0.0010 to 0.0100%. Preferably, it is 0.0020 to 0.0070%. More preferably, it is 0.0020 to 0.0050%.
  • the Vickers hardness of the base metal, welded zone, and heat-affected zone after welding is 280HV or less.
  • the above balance consists of Ni and unavoidable impurities.
  • the unavoidable impurities are components that are mixed due to various factors during the industrial production of the Ni-based alloy, and those that are allowed to be contained within a range that does not adversely affect the effects of the present invention. means.
  • heat treatment it is more desirable to apply heat treatment to the entire processed part and the part including the welded part.
  • a heat treatment of about 1000° C. ⁇ 1 min in an air atmosphere is sufficient. That is, it is possible to avoid heat treatment at a high temperature, for example, up to 1160° C. for a long time, for example, up to about 1 hour.
  • oxide scale is generated in an air atmosphere, and it is necessary to remove this by pickling or mechanical polishing, but there is an advantage that this can be avoided.
  • Ni--Cr--Mo alloy a method for producing a Ni--Cr--Mo alloy according to the present invention.
  • the method for producing the Ni--Cr--Mo alloy of the present invention is not particularly limited, it is desirable to produce it by the following method.
  • raw materials such as scrap, Ni, Cr, and Mo are melted in an electric furnace and decarburized by oxygen blowing in AOD (Argon Oxygen Decarburization) and/or VOD (Vacuum Oxygen Decarburization).
  • FIG. 4 shows a schematic diagram of sampling of the test piece.
  • a cold-rolled sheet 1 includes a weld bead 2 .
  • a test piece 3 containing only the base material portion and a test piece 4 containing the base material portion and the welded portion were prepared and subjected to a tensile test.
  • Welds were made by non-filler plasma welding.
  • the welding conditions are a current of 100 A, a voltage of 30 V, a speed of 500 mm/min, a center gas and a back gas of 100% Ar gas, a shield gas of 93% Ar + 7% H2 gas, and a groove shape of I type.
  • the welded portion was made smooth by bead cutting.
  • the test piece 4 was sampled so that the weld bead was perpendicular to the tensile direction and the welded portion was in the center of the parallel portion of the test piece.
  • Both test pieces 3 and 4 had a plate thickness of 3 mm, a width of 30 mm and a length of 100 mm, and were sampled with the tensile direction parallel to the rolling direction.
  • Elongation ratio (% of elongation of test piece including weld zone) / (% of elongation of test piece of base metal part only)
  • test piece having a length of 500 mm was taken in the pipe-making direction of the pipe, and bending tests of 135R, 115R, and 95R were performed using a steel cylinder based on the press bending method.
  • the bead was placed on the lower side of the pipe, and the cylinder was pushed in from above.
  • Defects (cracks) in the bending part were confirmed by using an optical microscope and magnifying them 20 to 400 times to confirm the presence or absence of defects. In addition, when the crack exceeded 0.1 mm, it was regarded as defective. D indicates that cracks occurred at 135R, no cracks occurred at 135R, C indicates that cracks occurred at 115R, no cracks occurred at 115R, and cracks occurred at 95R. A was rated as B, and a rated as A was that no cracks occurred even in 95R.
  • Hardness of Weld Zone Vickers hardness was measured in the base metal, weld zone, and heat-affected zone to evaluate the hardness of the weld zone.
  • a 3 mm material was used for the test piece, and the cross section was finished by polishing with #120 emery paper.
  • a load of 1 kgf during measurement was applied to each of the base material, the weld zone, and the heat-affected zone, and the average hardness was evaluated by performing three-point measurements.
  • Numbers 1 to 20 have only one C among the judgments and are within the allowable range, and are examples of the invention.
  • Nos. 21 to 38 contain D or have two or more Cs even if they do not contain D, are outside the allowable range, and are comparative examples. Comparative examples Nos. 21 to 38 will be described below.
  • No. 21 has no Co added, so the ductility is D, which is out of range.
  • No. 22 has a high C content, the ductility, cracking, and corrosion resistance are C, and the hardness of the weld zone is also high, which is out of the range.
  • Nb+Ti+V is high and out of range, so the crack is D, and the hardness at the weld is also high and out of range.
  • Number 31 has no V added, so the ductility is D, which is out of range.
  • Number 32 is out of range with high N and D in ductility and cracking.
  • the Cu+10Sn was high, so the crack was D, which is out of range.
  • Number 35 is out of range with a low W and a D in corrosion resistance, which is out of range.
  • Number 36 is out of range with a high W and a D in corrosion resistance, which is out of range.
  • Cu+10Sn is high, so the crack is D, which is out of range.
  • C and N are low, so the ductility is D, which is out of range.

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Abstract

Le problème décrit par la présente invention est de fournir un alliage à base de Ni-Cr-Mo présentant une excellente aptitude au façonnage et une excellente résistance à la corrosion au niveau d'une partie soudée. La solution selon l'invention porte sur un alliage à base de Ni-Cr-Mo comprenant, en pourcentage en masse, de 0,002 à 0,020 % de C, de 0,02 à 1,00 % de Si, de 0,02 à 1,00 % de Mn, 0,030 % ou moins de P, 0,005 % ou moins de S, de 18,0 à 24,0 % de Cr, de 7,5 à 9,0 % de Mo, de 0,01 à 0,20 % de Cu, de 0,005 à 0,400 % d'Al, de 0,1 à 1,0 % de Ti, de 3,0 à 6,0 % de Fe, de 2,5 à 4,0 % de Nb, de 0,01 à 0,50 % de Co, de 0,05 à 0,50 % de V, de 0,002 à 0,020 % de N, de 0,003 à 0,030 % de Sn, de 0,05 à 0,50 % de W, de 2,5 à 4,5 % de Nb + Ti + V, 0,40 % ou moins de Cu + 10 Sn, et le reste étant du Ni et des impuretés inévitables.
PCT/JP2022/009729 2021-07-13 2022-03-07 Alliage à base de ni-cr-mo pour tuyau soudé ayant une excellente aptitude au façonnage et une excellente résistance à la corrosion WO2023286338A1 (fr)

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CN202280049165.0A CN117651784A (zh) 2021-07-13 2022-03-07 加工性、耐腐蚀性优异的焊接管用Ni-Cr-Mo系合金
DE112022003529.3T DE112022003529T5 (de) 2021-07-13 2022-03-07 Ni-Cr-Mo-Legierung für geschweißte Rohre mit überlegener Verarbeitbarkeit und Korrosionsbeständigkeit

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JP2021115509A JP7009666B1 (ja) 2021-07-13 2021-07-13 加工性、耐食性に優れる溶接管用Ｎｉ－Ｃｒ－Ｍｏ系合金
JP2021-115509 2021-07-13

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53108022A (en) * 1977-03-04 1978-09-20 Hitachi Ltd Iron-nickel-chromium-molybdenum alloy of high ductility
JPH0483841A (ja) * 1990-07-26 1992-03-17 Nippon Yakin Kogyo Co Ltd 調理用シースヒータ被覆管材
JPH1030140A (ja) * 1996-07-15 1998-02-03 Sumitomo Metal Ind Ltd 耐食性と加工性に優れたニッケル基合金
JP2001509210A (ja) * 1997-01-29 2001-07-10 クルップ ファオ デー エム ゲゼルシャフト ミット ベシュレンクテル ハフツング 熱い塩素含有ガス及び塩化物に対する高い耐腐食性を有するオーステナイト系ニッケル−クロム−モリブデン−珪素−合金
JP2021183720A (ja) * 2020-05-22 2021-12-02 日本製鉄株式会社 Ｎｉ基合金管および溶接継手

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002275590A (ja) 2001-03-14 2002-09-25 Nisshin Steel Co Ltd 溶接部の加工性に優れた溶接用フェライト系ステンレス鋼
JP5111910B2 (ja) 2007-03-23 2013-01-09 新日鐵住金ステンレス株式会社 溶接部加工性および耐すき間腐食性に優れた表面疵の少ないフェライト系ステンレス鋼
JP6723210B2 (ja) 2017-09-14 2020-07-15 日本冶金工業株式会社 ニッケル基合金

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53108022A (en) * 1977-03-04 1978-09-20 Hitachi Ltd Iron-nickel-chromium-molybdenum alloy of high ductility
JPH0483841A (ja) * 1990-07-26 1992-03-17 Nippon Yakin Kogyo Co Ltd 調理用シースヒータ被覆管材
JPH1030140A (ja) * 1996-07-15 1998-02-03 Sumitomo Metal Ind Ltd 耐食性と加工性に優れたニッケル基合金
JP2001509210A (ja) * 1997-01-29 2001-07-10 クルップ ファオ デー エム ゲゼルシャフト ミット ベシュレンクテル ハフツング 熱い塩素含有ガス及び塩化物に対する高い耐腐食性を有するオーステナイト系ニッケル−クロム−モリブデン−珪素−合金
JP2021183720A (ja) * 2020-05-22 2021-12-02 日本製鉄株式会社 Ｎｉ基合金管および溶接継手

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