CN101057002A - Duplex stainless steel - Google Patents
Duplex stainless steel Download PDFInfo
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- CN101057002A CN101057002A CNA2005800380743A CN200580038074A CN101057002A CN 101057002 A CN101057002 A CN 101057002A CN A2005800380743 A CNA2005800380743 A CN A2005800380743A CN 200580038074 A CN200580038074 A CN 200580038074A CN 101057002 A CN101057002 A CN 101057002A
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- 229910001039 duplex stainless steel Inorganic materials 0.000 title abstract description 13
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 116
- 239000000956 alloy Substances 0.000 claims abstract description 116
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 40
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 31
- 229910052802 copper Inorganic materials 0.000 claims abstract description 26
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 24
- 238000005275 alloying Methods 0.000 claims description 10
- 238000003466 welding Methods 0.000 claims description 10
- 229910001256 stainless steel alloy Inorganic materials 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
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- 238000000576 coating method Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000004035 construction material Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 18
- 229910052759 nickel Inorganic materials 0.000 abstract description 6
- 229910052748 manganese Inorganic materials 0.000 abstract description 5
- 239000010949 copper Substances 0.000 description 31
- 239000011651 chromium Substances 0.000 description 30
- 230000007797 corrosion Effects 0.000 description 22
- 238000005260 corrosion Methods 0.000 description 22
- 229910052804 chromium Inorganic materials 0.000 description 18
- 230000003628 erosive effect Effects 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910001566 austenite Inorganic materials 0.000 description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 10
- 239000010937 tungsten Substances 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 9
- 239000011733 molybdenum Substances 0.000 description 9
- 239000011572 manganese Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000002349 favourable effect Effects 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
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- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910000885 Dual-phase steel Inorganic materials 0.000 description 1
- 101000918975 Sinapis alba Defensin-like protein 2 Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000003483 aging Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VCTOKJRTAUILIH-UHFFFAOYSA-N manganese(2+);sulfide Chemical group [S-2].[Mn+2] VCTOKJRTAUILIH-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 102220043852 rs72857097 Human genes 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
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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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3053—Fe as the principal constituent
-
- 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
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- 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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- 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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing 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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
-
- 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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/001—Austenite
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Heat Treatment Of Steel (AREA)
- Heat Treatment Of Sheet Steel (AREA)
Abstract
The present invention provides a duplex stainless steel alloy which contains in weight %: Cr 25- 35%, Ni 4-10%, Mo 1 -6%, N 0.3-0.6%, Mn greater than 0-3%, Si max 1.0%, C max 0.06%, Cu and/or W and/or Co 0.1-10%, W 0.1 -5%, balance Fe and normally occurring impurities wherein the ferrite content is 30-70%. The alloy has a yield point in tension being min 760 MPa.
Description
Technical field of the present invention and prior art
The present invention relates to a kind of double phase stainless steel alloy (duplex stainless steel), it has the ferrite content of high Cr, Mo and N content and 30-70%.
Duplex stainless steel is characterised in that to have the austenite-ferrite structure, and wherein two-phase has different chemical constitutions.Duplex stainless steel is subjected to people's attention as structured material, wherein not only needs high physical strength but also need good corrosion resistance.Because the nickel content in the duplex stainless steel is lower, thereby its cost is also lower, therefore be commonly used to substitute austenitic stainless steel and nickel-base alloy.
Because duplex stainless steel is to the various corrosive mediums that run in land/maritime environment CO for example
2, H
2S and muriate all have erosion resistance, so duplex stainless steel is widely used in the land or marine department of oil and gas industry.The umbilical pipeline, or " umbilical duct ", equipment on land or the sea and undersea device are interconnected, so that transport materials betwixt, for example crude oil and Sweet natural gas are transported to oil rig from the source, described umbilical pipeline is made by the duplex phase stainless tube that welds together usually.The down-hole pipe is the barrel that is installed in usually in the boring, and integrated production pipe (IPU) is the multiple-unit tube that comprises umbilical duct and down-hole pipe, and they also all are to be made by dual phase steel usually.
The down-hole pipe must be able to be resisted the corrosion of the seawater around it and the corrosion of its material that is transmitted.The end of down-hole pipe has screw thread, and connects into the length that needs by joint.Because the oil gas well location is in the place of the quite big degree of depth of b.s.l., so the length of down-hole pipe may be quite big.Requirement to the material that is used for the down-hole pipe can gather as follows:
Tension force yield-point minimum be 110ksi (per square inch thousand (kilo) number) (760MPa).
Opposing CO
2Or H
2The corrosion that S causes.
Good shock strength when being low to moderate-46 ℃ is at least 50J.
This material must be able to be made into the shape of seamless tube, and its form is for can produce screw thread and the fit engagement that is used for pipe.
US 6749697 discloses a kind of double phase stainless steel alloy with high-load Cr of containing of austenite-ferrite structure, Mo and N.Because this alloy show good corrosion, the good especially pitting resistance in the chloride environment and good weldability in high strength, the multiple bronsted lowry acids and bases bronsted lowry, so this alloy has satisfied above-mentioned requirements under hot extrusion and the last processing of annealed.The pitting resistance of alloy is described to anti-spot corrosion equivalents, PRE number=%Cr+3.3%Mo+16%N usually.Therefore according to this performance alloy is optimized.The PRE number of this alloy surpasses 40.Described alloy comprises (by weight percentage) C of 0.05% at the most, the Si of 0-2.0%, the Mn of 0-3.0%, the Cr of 25-35%, the Ni of 4-10%, the Mo of 2-6%, the N of 0.3-0.6%, the Fe of surplus and the impurity that exists usually, wherein ferrite content is 30-70%.
WO 03/020994 discloses a kind of alloy, it is characterized in that comprising Cu, the W of 0-3%, the N of 0.28-0.5% and the Co of 0-3.5% of Mo, 0-2% of Ni, 3-5 of Cr, 4.9-10% of Mn, the 24-30% of 0-3%.This alloy has high Cr, Mo and N content, and this has improved the pitting resistance of alloy, has increased the risk that makes the structural stability variation but then.By carrying out alloying with Co, think that this alloy structurally can be more stable, therefore can add 0.5%Co at least, preferred at least 1.5% and at the most 3.5% Co improving erosion resistance, and report has improved the stability of alloy.Because this alloy can comprise W, so the PRE number is revised so that comprise that weight is corresponding to half element W of Mo weight, i.e. PREW=%Cr+3.3% (%Mo+0.5%W)+16N.This alloy has the PRE/PREW number above 40.
US 6312532 discloses the double phase stainless steel alloy of the W of the Cu of N, 0.5-3% of Mo, 0.3-0.55% of Ni, 0-3% of Cr, 3-10% of the Mn, the 27-35% that comprise 0.3-4% and 2-5%.Because with W alloyization, this alloy shows high relatively erosion resistance in chloride environment.It is said with the Cu alloying and have high-load W or Mo can reduce separating out of slow when cooling intermetallic phase.When making large-sized stainless steel product, this character is extremely important, and the speed of cooling when making the large size stainless steel product is low relatively, and this has increased the risk that intermetallic phase is separated out usually under the temperature of about 700-1000 ℃ scope.This alloy has the PREW number above 40.This patent claims, in order to reach best effect, should add at least 2% W and the combination of Mo+0.5W and should not surpass 3.52.When using high-load Mo and W, the content of Cu should surpass 1.5% so that the structural stability maximum.If used a large amount of Cu, then the content of Mo should be low, to guarantee the good protection to intergranular corrosion.
The shortcoming of duplex stainless steel is, their high alloy content makes them, and for example σ (sigma) is mutually and χ (chi) formation sensitivity mutually to the intermetallic phase that causes in high temperature because of long-term exposure.σ is a kind of hard, crisp and intermetallic compound that is rich in Cr and Mo of very easily being etched mutually.χ is a kind of intermetallic compound with manganese sulfide structure mutually.
Significant intermetallic is separated out the forfeiture that may cause erosion resistance, and causes the flexible forfeiture sometimes.In addition, because phase between the low relatively inner precipitating metal of product of annealing postcooling speed, the production with large diameter thick and/or long pipe affects adversely.
The invention summary
The purpose of this invention is to provide a kind of high strength, good erosion resistance, good workability and duplex stainless steel that can weld of demonstrating.
By disclosed alloy among the US6749697 is optimized, realized this purpose, wherein utilized element Cu, W and Co knowledge to the influence of the structural stability of alloy and erosion resistance thereof, keep or improved the tensile property of alloy simultaneously.Realized this purpose by double phase stainless steel alloy with composition disclosed herein, the alloy (weight %) that promptly comprises following composition: the Cr of 25-35%, the Ni of 4-10%, the Mo of 1-6%, the N of 0.3-0.6%, Mn greater than 0 to 3%, 1.0% Si and 0.06% C at the most at the most, the Cu of 0.1-10% and/or W and/or Co, the W of 0.1-5%, the Fe of surplus and the impurity that usually exists, wherein ferrite content is 30-70%, and the tension force yield-point of described alloy minimum be 760MPa.
Have high-load Cr, Mo and N and comprise W or this alloy of W and Cu and/or Co has wonderful good mechanical properties and corrosive nature, particularly about the corrosive nature of the spot corrosion in the chloride environment.High-load Cr, Mo and N make alloy have very high strength, have good workability simultaneously, especially are hot extruded into the goods such as seamless tube.The interpolation of W or W and Cu and/or Co has strengthened the corrosion resistance of alloy in sour environment, has improved the structural stability of alloy and the weldability of alloy, and gives the more on the whole resistance of the corrosive attack of some types that alloy causes seawater.
Alloy of the present invention also has the high-resistance of the stress corrosion crack that hydrogen sulfide is caused except showing good mechanical property.This alloy has good hot workability, is easy to rolling and is very suitable for the application that need weld, for example makes to be used for butt welding weldless steel tube and the seam welded tube that various coil pipes are used.Therefore this alloy is specially adapted to hydraulicefficiency pipe for example umbilical duct, down-hole pipe and IPU.Yet, be the unusual combination of high tensile yield-point and high impact toughness according to the outstanding feature of alloy of the present invention.
The inventor find the tension force yield-point of double phase stainless steel alloy and form between have a following relation:
R
p0.2＝31.6％Cr+34(％Mo+％W)+153％N+10.2％Cu-426.
Because tungsten is promoting intermetallic phase for example not have molybdenum effective aspect the separating out of σ phase, therefore use aspect corrosion is chemical to the effect of the molybdenum tungsten similar and come molybdenum in the part instead of alloy with effect.Partly substitute the low-temperature impact toughness that molybdenum has also improved alloy with tungsten.Utilize molybdenum and tungsten to improve the erosion resistance of double phase stainless steel alloy simultaneously.In addition and since molybdenum than the tungsten costliness many, therefore substituting molybdenum with tungsten provides cost more effective alloy.
The interpolation of W or W and Cu and/or Co also is important for suppressing separating out of intermetallic phase.By adding W and Cu (wherein W to small part substituted Mo) simultaneously, the pitting resistance and the resistance to intergranular corrosion of alloy are further enhanced.Yet the combination of high-load W and high-load Cr and Mo has increased the risk that intergranular is separated out, so the content of W should be restricted to 5 weight % at the most.
According to embodiment of the present invention, this alloy comprises the N of 0.40-0.55%.Found that this high-load nitrogen produces the particularly advantageous combination of high tensile yield-point and high impact toughness.
According to another embodiment of the present invention, double phase stainless steel alloy wherein of the present invention comprises tungsten, satisfies following relation:
0.5 (%W)+1 (%Mo)=2-10%, or preferred 3-7%,
Wherein (%W) and (%Mo) be meant the weight percentage of tungsten and molybdenum respectively.
According to another embodiment of the present invention, adopt conventional metallurgical method for example in electric arc furnace, to melt and make this alloy.Therefore can melt alloy of the present invention fast, and adopt conventional technology and equipment that it is cast.As possibility, can make this alloy by powder metallurgic method.
According to another embodiment of the present invention, this alloy comprises the alloying additive of 1 weight % at the most, adds these alloy additive and be the reason for metallurgical technology or hot workability.
The invention still further relates to goods or any other goods of tubing, wire rod, band, pole stock, sheet material or bar form with high intensity and/or good erosion resistance, these goods comprise the alloy according to above-mentioned disclosed arbitrary embodiment.Described goods can be the wiring of seamless tube, welding wire, seam welded tube, flange, junctor, spinner blade, fan, oil cargo tank, welding material or high strength high-resistance.Described goods or make or comprise the coating of alloy of the present invention by alloy of the present invention.As possibility, described goods comprise metallurgy or mechanical bond (or coating) at the body material alloy of the present invention on the carbon steel for example.
Because alloy of the present invention has good structural stability and weldability, so its Application Areas is much larger than the Application Areas of the alloy of prior art.
Plan to be used as construction material, machinery or structure unit, for example the umbilical duct in briny environment, chloride environment, corrosive environment, chemical device, the paper industry, down-hole pipe or integrated production unit (IPU) according to the alloy and the goods special (but not exclusive) of above-mentioned arbitrary embodiment; Perhaps as welding wire.
To know other advantage of the present invention and favorable characteristics by following explanation and other dependent claims.
The accompanying drawing summary
In the accompanying drawings:
Fig. 1 is the impelling strength of test furnace charge (charge) of alloy according to embodiments of the present invention and the coordinate diagram of tension force yield-point relation.
Fig. 2 be show the tension force yield-point observed value of the test furnace charge of alloy according to embodiments of the present invention and the predictor of the formula that draws according to the inventor between the graphic representation of relation.
Invention is described
The principle and advantage of alloy of the present invention, and the selection that needs scope that makes alloy have the alloy composition element of unexpected superiority can be presented below.
Chromium (Cr) be improve to the resistivity of multiple form of corrosion very effective element.In addition, chromium has improved the intensity of alloy.High chromium content is hinting that also N has fabulous solvability in material.The chromium content of therefore wishing to keep high as far as possible is to improve intensity and erosion resistance.For fabulous strength property and erosion resistance, the content of chromium should be 25 weight % at least, preferably is at least 28 weight %.But its content should not surpass 33%.Yet high-load Cr has increased the risk that forms the intermetallic precipitate.Therefore chromium content preferably is no more than 35 weight %.
Nickel (Ni) adds in the alloy as austenite stabilizer element and with suitable level, so that obtain the austenite and the ferrite content of needs respectively.But in order to obtain the ferrite content of 30-70%, the content of nickel should be at least 4 weight %, preferably is at least 5 weight %, and should not surpass 10 weight %, preferably is no more than 9 weight %.
Molybdenum (Mo) is the effective element that improves the erosion resistance in chloride environment and in reductive acid.Too high Mo content combines with high Cr content and means that the risk that forms the intermetallic precipitate increases.Because Mo has improved the intensity of alloy, so the content of Mo should be at least 1 weight %, preferably is at least 3 weight %, it should not surpass 6 weight %, preferably is no more than 5 weight %.
Nitrogen (N) is unusual effective elements, and its part improves the erosion resistance of material, and part improves the structural stability and the intensity of material.In addition, high N content has improved the recasting (reformation) of austenite after welding, and this has guaranteed the superperformance of welding joint.In order to reach better effect, should add the N of at least 0.3 weight %.High-load N has increased the risk that chromium nitride is separated out, especially when the content of chromium is also high.In addition, high nitrogen content is hinting the risk that porosity increases, because will be above the solubleness of nitrogen in molten steel or welding pool.Therefore the content of nitrogen should be defined as the highest 0.60 weight %, preferably is at least 0.40 weight % and should not surpasses the N of 0.55 weight %.
Adding manganese (Mn) is in order to increase the solubleness of nitrogen in material in addition.Yet there is other element that this solubleness is had bigger influence.Manganese and high-load sulphur are in conjunction with the formation that can also cause manganese sulfide, and manganese sulfide can serve as the initiation point of pitting attack.Therefore the content of manganese should be defined as greater than 0 weight %, preferably is at least 0.5 weight %, and it should not surpass 3 weight %, and preliminary election is no more than 1.5 weight %.
Silicon (Si) is used as reductor in the steel production process, and it also can improve the flowability when producing and welding.Known high silicone content has been kept separating out of intermetallic phase.The silicone content that improves demonstrates astoundingly and can advantageously reduce σ and separate out mutually.Therefore should choose the silicon that allows to comprise certain content wantonly.Yet the content of silicon should be restricted to 1.0 weight % at the most.Can be added into many 0.15% or 0.10% silicon among the embodiment.
Carbon (C) has been strengthened stainless steel, has but promoted the formation to the deleterious precipitate of erosion resistance, therefore must regard carbon as pollutent in the present invention.The solubleness of carbon in ferrite and austenite all is limited, and this is hinting the risk that chromium carbide is separated out.Therefore carbon content should be restricted to 0.05 weight % at the most, preferred 0.03 weight % at the most, and 0.02 weight % at the most most preferably.
The adding of copper (Cu) is in order to improve duplex stainless steel to the particular etch environment erosion resistance in sour environment (for example sulfuric acid) for example, and copper has also reduced the susceptibility of alloy counter stress corrosion cracking and the effect of age hardening is provided.In material, find that copper has reduced the speed of separating out of intermetallic phase when slowly cooling off with high relatively Mo and/or W content.Its reason may be that separating out of rich austenitic iron/nickel/chromium/copper or ε (epsilon) phase suppressed for example separating out of σ phase of other intermetallic phase.Because separating out of ε phase can be to the negative impact of corrosive nature generation as the σ phase, the appearance of a small amount of rich copper ε phase is the positive factor in the alloy of the present invention.Yet high copper content means the limit that has surpassed solubleness, so copper content should be restricted to 5 weight % at the most.When having copper, then copper content should be at least 0.1 weight %, preferably is at least 0.8 weight %, and should not surpass 5 weight %, preferably is no more than 3.5 weight %.
Tungsten (W) has improved the erosion resistance that reaches in the reductive acid in chloride environment, and has improved the pitting resistance and the anti-crevice corrosion of alloy.Found that substituting Mo with W carries out the low temperature impact strength that alloying has improved alloy.In order to reduce the risk that resistance to intergranular corrosion worsens, carry out alloying with W and Cu simultaneously, wherein with the elements Mo in the W instead of alloy so that improve corrosion resistance.Yet too high W content and the combination of high Cr content have increased for example risk separated out mutually of σ of intermetallic phase.Therefore when having tungsten, W content should be restricted at least 0.1 weight %, and should not surpass 5 weight %, preferably be no more than 3 weight %, and minimum can be 1 weight %.
The interpolation of cobalt (Co) is used for reducing separating out of σ phase.It has strengthened the erosion resistance and the structural stability of alloy.As nickel and silicon, cobalt is dissolved in ferrite matrix, and reinforced ferrite.Cobalt also is tending towards making austenite stable.Therefore when having cobalt, cobalt contents should be preferably greater than 0.5 greater than 0%, and should not surpass 3.5%, preferably is no more than 2% Co.
Ferrite: in order to obtain favorable mechanical performance and erosion resistance and good weldability and workability, ferritic content is important.From the viewpoint of corrosion and welding, wish to obtain good performance with the ferrite content of 30-70%.High ferrite content causes the deterioration of low-temperature impact toughness and anti-hydrogen embrittlement.Therefore ferritic content is at least 30%, is at most 70%, preferably is at least 35%, and should not surpass 55%, and all the other are austenite.
The alloying additive: owing to the reason of metallurgical technology is purified and is removed the element that S or O add in order to obtain melt, or the element that adds for the workability of improving material.The example of such element is Al, B, Ca, Ce and Mg.In order to make these elements not produce harmful effect to the performance of alloy, the level of independent every kind of element should be lower than 0.1%.The aggregate level of alloying additive should be lower than 1%, and preferably at the most 0.1%.
Simulation embodiment:
Adopt calculation of thermodynamics program ThermoCalc Version Q to carry out 21 kinds of different simulations of forming.Table 1 has provided the composition of test furnace charge.
Table 2 has provided ferritic phase and the austenite composition in mutually respectively.Table 3 comprises by calculating the parameter that phasor obtains; For example in the amount of 900 ℃ of following σ phases, the top temperature of σ phase (SIGMA), promptly σ begins to separate out by thermodynamic(al)equilibrium mutually under this temperature, this means that this parameter is measuring of alloy structure stability; Chromium nitride Cr
2The top temperature that the top temperature of N and rich chromium austenite are separated out mutually.
Observed result:
The increase of W content has improved the balance of PREW number (PRENW) between austenite and the ferrite among the alloy 1-4.The Cr content of austenite in mutually also reduces.High Cr content is hinting the risk of (46 ℃) shock strength difference under the low temperature, therefore increases the shock strength (referring to table 2, alloy 1-4) that W content has improved alloy.
In containing the alloy of W, Cu reduced the σ phase top temperature (referring to table 3, comparative alloy 3 and 4 and alloy 7 and 8).
The W that substitutes Mo should provide the tensile yield limit of raising, because W is bigger atom, it should have bigger influence to solution hardening.By substituting Mo with 1: 2 ratio with W, structural stability is constant substantially but obtained better intensity.
Co has reduced the risk that σ separates out mutually by reducing the maximum temperature of separating out mutually for σ.(referring to table 3, relatively alloy 10 and alloy 11 mutually, and relatively alloy 1 and alloy 9).
The test implementation example
Make 16 test furnace charges by the steel billet (bloom) of casting 170kg.With the circular bar of steel billet forge hot, therefrom choose the test materials that is used to study burn into intensity and structural stability.
Table 4 provided 16 quilts well forge hot to become diameter be the composition of test furnace charge of the circular bar of 40mm.
For the structural stability of research trial furnace charge, under 7 temperature (being spaced apart 50 ℃) of 900-1200 ℃ of scope, the test board of being made by this bar is carried out solution heat treatment.The possible thermal treatment temp of the best by determining to have the minimum level intermetallic phase with opticmicroscope research.Before taking out test materials, under this temperature, described material was carried out solution heat treatment 5 minutes then.And measure ferritic content by under opticmicroscope (LOM), carrying out several points.The result is shown in the table 5.
Structural stability for the confirmed test furnace charge is heated rapidly to melting temperature with test materials, then anneals 3 minutes and is cooled to room temperature with the speed of cooling of-17.5 ℃/minute and-100 ℃/minute.Then by the image that derives from the BSE-detector in the scanning electronic microscope (SEM) is carried out the amount that image analysis comes σ phase in the determination test furnace charge.The result is shown in the table 6.
Discovery will obtain good structural stability, must to alloy element for example the amount of Cr, Mo and W limit, but the content that increases nitrogen produces the structural stability of improvement.Observed two important relationship, promptly when needing good structural stability, it is favourable substituting Mo with W.In addition, high-load N is favourable to structural stability.Embodiment shows that 5542 have than 5543 much better structural stabilities, and wherein essential distinction is that W is with the alternative Mo of 2: 1 relation (every %Mo is replaced by 2% W).
The physical strength of determination test furnace charge at room temperature, and measure impelling strength down room temperature and-50 ℃.The result is shown in the table 7.Yet many test bars show crackle.This result shows also on the figure of Fig. 1 that Fig. 1 is the graph of a relation of impelling strength and tension force yield-point.
Tension force yield-point R
P0.2Greatly depend on the solution treatment element.Satisfy following relational expression and have goodish dependency between tension force yield-point and the composition:
R
p0.2＝31.6％Cr+34(％Mo+％W)+153％N+10.2％Cu-426
Accompanying drawing 2 shows the R of test furnace charge
P0.2Observed value and according to the relation between the predictor of this relational expression.This relational expression shows N to the having the greatest impact of high tension force yield-point, and chromium, molybdenum and tungsten have identical influence.Because the W element can not produce negative impact as Mo to structural stability, therefore carrying out the content that alloying reduces Mo simultaneously with W is favourable to avoiding producing the structural stability problem.Yet Mo has bigger influence to corrosive nature.In order to keep structural stability, can carry out alloying with W and optimize the tension force yield-point, wherein W substitutes Mo with coefficient 2, this means that then W content increases by 2% if Mo content reduces by 1%.
More clearly the showing of test furnace charge 5536 and furnace charge 5542 and 5548, content by reducing Mo and N and the content that increases W and Cu simultaneously might improve the tension force yield-point of material.
The problem of high-tensile meterial is to be difficult to obtain the combination of good impelling strength and high tensile yield-point usually.The present invention proves, for having R
P0.2The furnace charge that surpasses the ultra-high tension yield-point of 800MPa can obtain acceptable impelling strength down at-50 ℃ for the furnace charge that wherein W and Cu content are high and while N content reduces.Might obtain the combination of these two key propertys of material of construction in view of the above, be difficult to so far obtain this combination for duplex stainless steel.
According to ASTM G48C and MTI-2, measured the resistivity of test materials to spot corrosion and crevice corrosion.Critical spot corrosion temperature (CPT) and critical crevice corrosion temperature (CCT) have been measured and shown in the table 8.Yet crackle has appearred in several test bars.Measure ferrite and austenite composition mutually respectively by microprobe analysis (EPMA), the results are shown in table 9.Can calculate each phase and total PRE number of forming according to PRE=%Cr+3.3 (%Mo+0.5%W)+16%N.As much as possible at austenite balance PRE number mutually and between the ferritic phase.
In table 10, the character of test materials carried out contrasting that (positive/negative+0-) is wherein according to the forging property of material being evaluated to the rate range of 5 (best) from 0 (the poorest).
About the combination of erosion resistance, tension force yield-point and impelling strength, seem that furnace charge 5548 is for best.Has the Cu content of about 2 weight %, the W content of about weight 4% and the Co content of about 0.1 weight % by visible this furnace charge of table 4.Therefore, it is favourable having all these three kinds of elements in the alloy.
Form and can wherein consider all these character according to the best of double phase stainless steel alloy of the present invention for as follows:
Alloy has high-load Cr, Cu and W and has not the N content that can have a negative impact to low-temperature impact toughness.Content to Mo limits the feasible requirement of satisfying good structural stability.Can obtain high tension force yield-point when N content is high.If increase the content of W or Cu, then might reduce the content of N and not reduce the tension force yield-point.When lower and content W and Cu of the content of N is high, then can obtain the combination of acceptable low-temperature impact toughness and high tension force yield-point.
Claims (21)
1. double phase stainless steel alloy is characterized in that this alloy comprises in weight percentage:
The Cr of 25-35%
The Ni of 4-10%
The Mo of 1-6%
The N of 0.3-0.6%
Mn greater than 0-3%
1.0% Si at the most
0.06% C at the most
The Cu of 0.1-10% and/or W and/or Co
The W of 0.1-5%
The Fe of surplus and the impurity that exists usually, wherein ferrite content is 30-70%, and this alloy has the tension force yield-point of minimum 760Mpa.
2. according to the alloy of claim 1, it is characterized in that this alloy comprises the Cu of 0.1-5%.
3. according to the alloy of claim 1, it is characterized in that this alloy comprises the Cu of 0.1-3%.
4. according to the alloy of claim 2 or 3, it is characterized in that this alloy comprises minimum 0.8% Cu.
5. according to each alloy of aforementioned claim, it is characterized in that this alloy comprises at the most 0.15% Si and 0.05% C at the most.
6. according to each alloy of aforementioned claim, it is characterized in that this alloy comprises at the most 0.1% Si and 0.05% C at the most.
7. according to each alloy of aforementioned claim, it is characterized in that this alloy comprises the N of 0.40-0.55%.
8. according to each alloy of aforementioned claim, it is characterized in that this alloy comprises the W of 1-3% weight.
9. according to each alloy of aforementioned claim, it is characterized in that satisfying following relational expression: 0.5 (%W)+1 (%Mo)=2-10%.
10. according to each alloy of aforementioned claim, it is characterized in that satisfying following relational expression: 0.5 (%W)+1 (%Mo)=3-7%.
11., it is characterized in that this alloy comprises the Co greater than 0-3.5% according to the alloy of claim 1.
12., it is characterized in that this alloy comprises the Cr of 28-33 weight % according to the alloy of claim 1.
13., it is characterized in that this alloy comprises the Mn of 0.5-1.5 weight % according to the alloy of claim 1.
14., it is characterized in that this alloy comprises the Ni of 5-9 weight % according to the alloy of claim 13.
15., it is characterized in that this alloy comprises the ferrite of 35-55% according to the alloy of claim 1.
16., it is characterized in that this alloy is by conventional metallurgical method manufacturing according to each alloy of aforementioned claim.
17., it is characterized in that this alloy comprises the other alloying additive that total amount mostly is 1 weight % most according to each alloy of aforementioned claim.
18. the goods of a tubing, wire rod, band, pole stock, sheet material or bar form is characterized in that these goods comprise according to each alloy among the claim 1-17.
19., it is characterized in that these goods are by making according to each alloy among the claim 1-17 according to the goods of claim 18.
20., it is characterized in that these goods comprise coating or the coating according to each alloy among the claim 1-17 according to the goods of claim 18.
21. according to each alloy among the claim 1-17, perhaps according to each goods among the claim 18-20 as the application of construction material, machinery or structure unit, for example umbilical duct in briny environment, chloride environment, corrosive environment, chemical device, the paper industry, down-hole pipe or integrated production unit (IPU); Perhaps it is as the application of welding wire.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE04026985 | 2004-11-04 | ||
| SE0402698A SE528782C2 (en) | 2004-11-04 | 2004-11-04 | Duplex stainless steel with high yield strength, articles and use of the steel |
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| CN101057002A true CN101057002A (en) | 2007-10-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA2005800380743A Pending CN101057002A (en) | 2004-11-04 | 2005-11-04 | Duplex stainless steel |
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|---|---|
| US (1) | US20080138232A1 (en) |
| EP (1) | EP1812614A4 (en) |
| JP (1) | JP2008519165A (en) |
| KR (1) | KR20070073870A (en) |
| CN (1) | CN101057002A (en) |
| AU (1) | AU2005301376B2 (en) |
| CA (1) | CA2586452A1 (en) |
| NO (1) | NO341532B1 (en) |
| SE (1) | SE528782C2 (en) |
| WO (1) | WO2006049572A1 (en) |
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| CN103975088A (en) * | 2011-11-04 | 2014-08-06 | 奥托库姆普联合股份公司 | Duplex stainless steel |
| CN104822487A (en) * | 2012-11-28 | 2015-08-05 | 山特维克知识产权股份有限公司 | Welding material for weld cladding |
| CN111868278A (en) * | 2017-12-22 | 2020-10-30 | 吐巴塞克斯创新A.I.E.公司 | Corrosion resistant duplex stainless steel |
| CN113981724A (en) * | 2021-09-26 | 2022-01-28 | 江苏亚盛金属制品有限公司 | High-strength corrosion-resistant steel wire rope for mooring in ocean engineering and manufacturing method thereof |
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| CN111719090A (en) * | 2013-12-27 | 2020-09-29 | 山特维克知识产权股份有限公司 | Corrosion resistant duplex steel alloy, objects made therefrom and method of making the alloy |
| KR20240042679A (en) * | 2015-07-20 | 2024-04-02 | 산드빅 인터렉츄얼 프로퍼티 에이비 | Duplex stainless steel and formed object thereof |
| WO2017014632A1 (en) | 2015-07-20 | 2017-01-26 | Stamicarbon B.V. | Duplex stainless steel and use thereof |
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| WO2023198720A1 (en) * | 2022-04-12 | 2023-10-19 | Alleima Tube Ab | New duplex stainless steel |
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| JP2500162B2 (en) * | 1991-11-11 | 1996-05-29 | 住友金属工業株式会社 | High strength duplex stainless steel with excellent corrosion resistance |
| SE501321C2 (en) * | 1993-06-21 | 1995-01-16 | Sandvik Ab | Ferrite-austenitic stainless steel and use of the steel |
| JPH0813094A (en) * | 1994-06-24 | 1996-01-16 | Sumitomo Metal Mining Co Ltd | Duplex stainless cast steel and production thereof |
| JPH09209087A (en) * | 1996-02-01 | 1997-08-12 | Sumitomo Metal Mining Co Ltd | Duplex stainless steel |
| EP0867256B1 (en) * | 1996-09-13 | 2001-12-19 | Sumitomo Metal Industries, Ltd. | Welding material for stainless steels |
| SE9902346L (en) * | 1999-06-21 | 2000-08-07 | Sandvik Ab | Use of a stainless steel alloy such as umbilical tube in marine environment |
| SE513247C2 (en) * | 1999-06-29 | 2000-08-07 | Sandvik Ab | Ferrite austenitic steel alloy |
| SE514816C2 (en) * | 2000-03-02 | 2001-04-30 | Sandvik Ab | Duplex stainless steel |
| SE524951C2 (en) * | 2001-09-02 | 2004-10-26 | Sandvik Ab | Use of a duplex stainless steel alloy |
| SE524952C2 (en) * | 2001-09-02 | 2004-10-26 | Sandvik Ab | Duplex stainless steel alloy |
| SE525252C2 (en) * | 2001-11-22 | 2005-01-11 | Sandvik Ab | Super austenitic stainless steel and the use of this steel |
| KR100460346B1 (en) * | 2002-03-25 | 2004-12-08 | 이인성 | Super duplex stainless steel with a suppressed formation of intermetallic phases and having an excellent corrosion resistance, embrittlement resistance, castability and hot workability |
-
2004
- 2004-11-04 SE SE0402698A patent/SE528782C2/en unknown
-
2005
- 2005-11-04 JP JP2007540286A patent/JP2008519165A/en active Pending
- 2005-11-04 US US11/666,903 patent/US20080138232A1/en not_active Abandoned
- 2005-11-04 KR KR1020077010126A patent/KR20070073870A/en not_active Application Discontinuation
- 2005-11-04 EP EP05799601A patent/EP1812614A4/en not_active Withdrawn
- 2005-11-04 CN CNA2005800380743A patent/CN101057002A/en active Pending
- 2005-11-04 WO PCT/SE2005/001661 patent/WO2006049572A1/en active Application Filing
- 2005-11-04 AU AU2005301376A patent/AU2005301376B2/en not_active Ceased
- 2005-11-04 CA CA002586452A patent/CA2586452A1/en not_active Abandoned
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| CN103975088A (en) * | 2011-11-04 | 2014-08-06 | 奥托库姆普联合股份公司 | Duplex stainless steel |
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| CN103438951A (en) * | 2013-09-06 | 2013-12-11 | 高正 | Alloy steel wear-resisting anti-blocking type air volume and air velocity transducer |
| CN111868278A (en) * | 2017-12-22 | 2020-10-30 | 吐巴塞克斯创新A.I.E.公司 | Corrosion resistant duplex stainless steel |
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Also Published As
| Publication number | Publication date |
|---|---|
| NO20072275L (en) | 2007-06-13 |
| CA2586452A1 (en) | 2006-05-11 |
| US20080138232A1 (en) | 2008-06-12 |
| AU2005301376B2 (en) | 2010-04-22 |
| SE0402698L (en) | 2006-05-05 |
| WO2006049572A1 (en) | 2006-05-11 |
| JP2008519165A (en) | 2008-06-05 |
| AU2005301376A1 (en) | 2006-05-11 |
| EP1812614A1 (en) | 2007-08-01 |
| SE528782C2 (en) | 2007-02-13 |
| SE0402698D0 (en) | 2004-11-04 |
| KR20070073870A (en) | 2007-07-10 |
| NO341532B1 (en) | 2017-12-04 |
| EP1812614A4 (en) | 2009-11-18 |
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