EP2248919A1 - High corrosion-resistant, high-strength and non-magnetic stainless steel, high corrosion-resistant, high-strength and non-magnetic stainless steel product and method for producing the same - Google Patents
High corrosion-resistant, high-strength and non-magnetic stainless steel, high corrosion-resistant, high-strength and non-magnetic stainless steel product and method for producing the same Download PDFInfo
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- EP2248919A1 EP2248919A1 EP20100004443 EP10004443A EP2248919A1 EP 2248919 A1 EP2248919 A1 EP 2248919A1 EP 20100004443 EP20100004443 EP 20100004443 EP 10004443 A EP10004443 A EP 10004443A EP 2248919 A1 EP2248919 A1 EP 2248919A1
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- 238000005260 corrosion Methods 0.000 title claims abstract description 92
- 230000007797 corrosion Effects 0.000 title claims abstract description 85
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 50
- 239000010935 stainless steel Substances 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 66
- 239000010959 steel Substances 0.000 claims abstract description 66
- 239000012535 impurity Substances 0.000 claims abstract description 15
- 230000009467 reduction Effects 0.000 claims description 10
- 229910052715 tantalum Inorganic materials 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 9
- 229910052735 hafnium Inorganic materials 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 description 35
- 230000005389 magnetism Effects 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 21
- 229910052759 nickel Inorganic materials 0.000 description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- 229910052804 chromium Inorganic materials 0.000 description 14
- 229910052748 manganese Inorganic materials 0.000 description 14
- 229910052750 molybdenum Inorganic materials 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000003129 oil well Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 9
- 230000035699 permeability Effects 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 229910001566 austenite Inorganic materials 0.000 description 7
- 238000009412 basement excavation Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000001771 impaired effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229910052758 niobium Inorganic materials 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910000617 Mangalloy Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005482 strain hardening Methods 0.000 description 2
- 239000002887 superconductor Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 238000005728 strengthening Methods 0.000 description 1
- 239000008207 working material Substances 0.000 description 1
Classifications
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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
-
- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
-
- 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
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/22—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for drills; for milling cutters; for machine cutting tools
-
- 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
- C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
Definitions
- the present invention relates to a high corrosion-resistant, high-strength and non-magnetic stainless steel, a high-strength, high corrosion-resistant and non-magnetic stainless steel product and a method for producing the same. More particularly, the invention relates to a technique for producing a non-magnetic stainless steel which is capable of blocking the influence of earth magnetism and is particularly suitable for the use in oil well excavation, without impairing its characteristics (high corrosion resistance and high strength).
- a position for example, direction and inclination
- a measuring instrument is mounted in a drill collar in the vicinity of a bit.
- the drill collar and the like are required to be made of a non-magnetic steel, in order to block the influence of earth magnetism.
- Patent document 1 JP-A-53-117618 discloses a high-strength austenitic stainless steel containing C: 0.15% or less, Si: 0.1 to 2.0%, Mn: 7.0 to 18%, Ni: 0.50 to 6.0%, Cr: 15.0 to less than 21.0%, Mo: 0.5 to 4.0%, N: 0.20 to 0.60% and the balance composed of Fe and impurities, which is for the use to a body of rotation of a centrifuge or the like.
- Patent document 2 JP-A-59-104455 discloses a ultra-low temperature high-strength steel excellent in rust resistance, which contains C: 0.01 to 0.20 wt%, Si: 0.05 to 1.5 wt%, Mn: 16 to 27 wt%, Cr: 10 to 20 wt%, Cu: 0.1 to 4 wt%, N: 0.10 to 0.50 wt%, Al: 0.003 to 0.20 wt% and the balance composed of Fe and unavoidable impurities, which is for the use to a holding material of a superconductive electromagnet or a superconductor, or the like.
- Patent document 3 JP-A-59-205452 discloses a high-strength member for an instrument loaded on an undersea research ship, which contains C: 0.15% or less, Si: 0.1 to 2.0%, Mn: 7.0 to 18.0%, Ni: 0.50 to 6.0%, Cr: 15.0 to 26.0%, Mo: 0.5 to 4.0%, N: 0.2 to 0.6% and the balance substantially composed of Fe, and is subjected to hot working at a rolling reduction of 50% or more, wherein the finishing temperature of the hot working is from 800 to 1,000°C.
- Patent document 4 JP-A-61-143563 discloses a rust-resistant, ultra-low temperature high manganese high-strength steel containing C: 0.20% or less, Si: 0.05 to 2.5%, Mn: 16 to 35%, Cr: 10 to 20%, Ni: 0.1 to 8.0%, N: 0.10 to 0.50%, Al: 0.001 to 0.20%, S: 0.003% or less and the balance composed of Fe and unavoidable impurities, which is for the use to a holding material of a superconductive electromagnet or a superconductor, or the like.
- Patent document 5 JP-A-61-170545 discloses an ultra-low temperature high manganese steel excellent in rust resistance, which contains C: 0.20% or less, Si: 0.05 to 2.5%, Mn: 9 to 35%, Cr: 10 to 20%, Ni: 0.1 to 8.0%, N: 0.001 to 0.50%, Al: 0.001 to 0.20%, Ca: 0.001 to 0.020% and the balance composed of Fe and unavoidable impurities, for the use to a structure used in a fusion experimental reactor using a superconductive electromagnet, or the like.
- Patent document 6 JP-A-61-238943 discloses a high-strength non-magnetic stainless steel excellent in rust resistance, which contains C: 0.01 to 0.15 wt%, Si: 0.05 to 0.60 wt%, Mn: 16 to 25 wt%, S: 0.010 wt% or less, Ni: 4.0 wt% or less, Cr: 14 to 20 wt%, N: 0.3 to 0.6 wt%, O: 0.01 wt% or less, Al: 0.001 to 0.20 wt% and the balance composed of Fe and unavoidable impurities, and contains non-metallic inclusions in an area ratio of 0.10% or less, which is for the use to a precision equipment part (a micromotor shaft, a magnetic tape guide, a shaft or the like) that is required to avoid magnetism.
- a precision equipment part a micromotor shaft, a magnetic tape guide, a shaft or the like
- Patent document 7 JP-A-2004-052097 discloses an interdental brush wire containing, by mass, C: 0.07% or less, Si: 0.6% or less, Mn: 13 to 17%, Ni: 2.0 to 5.0%, Cr: 16.0 to 20.0%, Mo: 0.4 to 2.0%, N: 0.3 to 0.60% and Cu: 0.3 to 1.0%, which is for the use to the interdental brush wire.
- Patent document 8 JP-A-2004-156086 discloses a non-magnetic stainless steel containing C: 0.06% or less, Si: 0.40% or less, Mn: 15.5 to 17%, P: 0.040% or less, S: 0.010% or less, Cu: 0.35 to 2.00%, Ni: 2.50 to 4.00%, Cr: 17.0 to 21.0%, Mo+W: 0.5 to 1.5%, N: 0.42 to 0.65%, O: 0.01% or less, sol-Al: 0.05% or less, B: 0.001 to 0.010% and the balance substantially composed of Fe, which is for the use to a drill collar for oil well excavation.
- the recent oil well excavation region is versatile, and further high-corrosion resistant and high-strength stainless steels based on the assumption of non-magnetism have been demanded by the industrial world.
- the various types of steels described in the above-mentioned patent documents 1 to 8 have many problems to be solved.
- the high-strength austenitic stainless steel of patent document 1 and the high-strength member for an instrument loaded on an undersea research ship of patent document 3 have a concern that workability and corrosion resistance are deteriorated by crystallization of coarse carbides due to their excessive C content.
- the ultra-low temperature high-strength steel of patent document 2 and the rust-resistant, ultra-low temperature high manganese high-strength steel of patent document 4 have a concern that the required characteristics of non-magnetism, high strength and corrosion resistance are not satisfied due to their small N content.
- the ultra-low temperature high-strength steel of patent document 2 has a further concern that corrosion resistance is deteriorated due to its excessive Mn content.
- the ultra-low temperature high manganese steel of patent document 5 has a concern that the required characteristics of non-magnetism, high strength and corrosion resistance are not satisfied, because the Cr content is rather small with respect to the Mn content, and the N content is also rather small.
- the Ni and N contents are rather small.
- Mn and Ni contents are excessively small.
- the non-magnetic stainless steel of patent document 8 the Ni and Mo contents are excessively small. Therefore, these alloys have a concern that the required characteristics of non-magnetism, high strength and corrosion resistance are not satisfied. As described above, even according to patent documents 1 to 8, no stainless steel satisfying the required characteristics has been obtained.
- the invention has been made in view of the above circumstances, and an object of the invention is to provide a high corrosion-resistant, high-strength and non-magnetic stainless steel having high corrosion resistance, high strength and non-magnetism; a high corrosion-resistant, high-strength and non-magnetic stainless steel product and a method for producing the same.
- an object of the invention is to provide a high corrosion-resistant, high-strength and non-magnetic stainless steel which blocks the influence of earth magnetism at the time of oil well evacuation, and not only can be applied to oil well excavation products covering a wide range of regions, but also is suitable as raw materials for various parts (various spring products, VTR guide pins and motor shafts); a high corrosion-resistant, high-strength and non-magnetic stainless steel product and a method for producing the same.
- the present inventors have made intensive studies, centering on application of Cr and Mo as corrosion resistance-improving elements, for realizing high corrosion resistance.
- the inventors have encountered a problem that "non-magnetism which is capable of blocking the influence of earth magnetism" required for a drill collar and the like of oil well evacuation and the like cannot be achieved, because an increase in Cr content and Mo content causes magnetization.
- the inventors have made further intensive studies. As a result, it has been found that when a composition balance is adjusted by making use of N and Ni, a stable non-magnetic austenite single-phase structure is obtained, even in the case where Cr and Mo are used to obtain high corrosion resistance.
- the invention has been made based on such a finding.
- the present invention provides a high corrosion-resistant, high-strength and non-magnetic stainless steel containing: C: 0.01% to 0.05% by mass, Si: 0.05% to 0.50% by mass, Mn: more than 16.0% by mass but 19.0% by mass or less, P: 0.040% by mass or less, S: 0.010% by mass or less, Cu: 0.50% to 0.80% by mass, Ni: 3.5% to 5.0% by mass, Cr: 17.0% to 21.0% by mass, Mo: 1.80% to 3.50% by mass, B: 0.0010% to 0.0050% by mass, O: 0.010% by mass or less, and N: 0.45% to 0.65% by mass, with the balance substantially composed of Fe and unavoidable impurities, the steel satisfying the following equations (1) to (4): Cr + 3.3 ⁇ Mo + 16 ⁇ N ⁇ 30 Cr / C ⁇ 330 Cr / Mn > 1.0 Ni + 3 ⁇ Cu / Cr + Mo > 0.25 wherein [Cr], [Mo], [N], [
- the high corrosion-resistant, high-strength and non-magnetic stainless steel according to the present invention may further contains at least one element selected from the group consisting of Ca, Mg and REM in a total content of 0.0001% to 0.0100% by mass.
- the high corrosion-resistant, high-strength and non-magnetic stainless steel according to the present invention may further contains at least one element selected from the group consisting of Nb, V, Ta and Hf in a total content of 0.1 % to 2.0% by mass.
- the high corrosion-resistant, high-strength and non-magnetic stainless steel according to the present invention may further contains A1 in a content of 0.001 % to 0.10% by mass.
- the high corrosion-resistant, high-strength and non-magnetic stainless steel according to the present invention may further contains at least one member selected from the group consisting of W and Co in a total content of 0.1% to 3.0% by mass.
- the present invention further provides a method for producing a high corrosion-resistant, high-strength and non-magnetic stainless steel product, which includes subjecting the steel according to the present invention to working under a temperature condition of 300°C to 900°C at a reduction of area of 15% to 40%.
- the present invention furthermore provides a high corrosion-resistant, high-strength and non-magnetic stainless steel product obtained by subjecting the steel according to the present invention to working under a temperature condition of 300°C to 900°C at a reduction of area of 15% to 40%.
- a high corrosion-resistant, high-strength and non-magnetic stainless steel product obtained by subjecting the steel according to the present invention to working under a temperature condition of 300°C to 900°C at a reduction of area of 15% to 40%.
- the resulting steel product include oil well evacuation products, spring products, VTR guide pins, motor shafts and the like.
- the high corrosion-resistant, high-strength and non-magnetic stainless steel and the high corrosion-resistant, high-strength and non-magnetic stainless steel product according to the invention have the above-mentioned component composition and satisfies the above-mentioned equations (1) to (4), so that they have high corrosion resistance, high strength and non-magnetism. Accordingly, they has effects of being able to block the influence of earth magnetism at the time of oil well evacuation to be applied to oil well excavation products covering a wide range of regions, and moreover, being-suitable as raw materials for various parts (various spring products, VTR guide pins and motor shafts).
- the resulting steel product can exhibit the same effects as described above.
- the high corrosion-resistant, high-strength and non-magnetic stainless steel according to this embodiment contains the following essential elements and selective elements and the balance substantially composed of Fe and unavoidable impurities, and satisfies relationship defined by equations (1) to (4) described later.
- equations (1) to (4) described later.
- all the percentages defined by mass are the same as those defined by weight, respectively.
- the high corrosion-resistant, high-strength and non-magnetic stainless steel according to this embodiment contains C, Si, Mn, Cu, Ni, Cr, Mo, B and N as essential elements, and the balance is substantially composed of Fe and unavoidable impurities.
- the unavoidable impurities as mentioned herein include, for example, P, S and O.
- the high corrosion-resistant, high-strength and non-magnetic stainless steel according to this embodiment may further contain the following selective elements, that is to say, at least one element selected from the group consisting of Ca, Mg and REM; the group consisting ofNb, V, Ta and Hf; Al; and the group consisting of W and Co.
- At least one element selected from the group consisting of Ca, Mg and REM in a total content of 0.0001% to 0.0100% by mass Ca, Mg and REM are selective elements, and elements effective for improving hot workability of the steel. Accordingly, they may be added in a total content of 0.0001 % by mass or less. However, excessive addition of these elements results in saturation of the effect, and conversely decreases hot workability. Accordingly, 0.0100% by mass is specified as the upper limit of the total content thereof. The total content thereof is more preferably 0.0050% by mass or less.
- REM means one containing Ce, La or an alloy thereof.
- Co is a selective element, and effective for obtaining an austenite single-phase structure to achieve high strength by solid solution strengthening. Accordingly, Co may be added as needed. However, excessive addition of Co causes a substantial increase in cost, so that 3.0% by mass is specified as the upper limit of the content of Co.
- the content of Co is more preferably 1.5% by mass or less.
- the high corrosion-resistant, high-strength and non-magnetic stainless steel according to this embodiment satisfies the following equations (1) to (4):
- the minimal amount thereof present in the steel is the smallest non-zero amount used in the inventive steels as summarized in Tables 1 and 2.
- the maximum amount thereof present in the steel is the maximum amount used in the inventive steels as summarized in Tables 1 and 2.
- the high-corrosion resistant, high strength and non-magnetic stainless steel according to this embodiment is obtained by
- the materials under test were processed to various test specimens.
- the tensile strength, the 0.2% yield strength and the elongation (%) were determined by preparing a JIS No. 4 test specimen from each of the materials under test, and measuring the breaking stress at the time when the tensile load is applied to a leading edge of the specimen in accordance with JIS Z 2241.
- the magnetic permeability was determined by performing measurement of the magnetic permeability according to the VSM method, taking the external magnetic field as 2,000 Oe.
- the corrosion resistance was evaluated by the 6% ferric chloride test (JIS G 0578) and the 10% oxalic acid etching test (JIS G 0571). The test results thereof are shown together in Tables 3 and 4.
- Inventive Steels 1 to 26 satisfied the required characteristics for all of strength (tensile strength ⁇ 1050 MPa, 0.2% yield strength ⁇ 968 MPa), workability (elongation ⁇ 25), non-magnetism (magnetic permeability ⁇ 1.010) and corrosion resistance (ferric chloride corrosion ⁇ 0.5, 10% oxalic acid etching: step).
- Inventive Steels 1 to 26 contained the components defined in Tables 1 and 2 in predetermined amounts, and satisfied equations (1) to (4) defined in Tables 1 and 2. It is therefore conceivable that corrosion resistance, strength and non-magnetism could be achieved at the same time.
- Inventive Steels 1 to 26 block the influence of earth magnetism at the time of oil well evacuation, and not only can be applied to oil well excavation products covering a wide range of regions, but also are suitable as raw materials for various parts (various spring products, VTR guide pins and motor shafts).
- Comparative Steels 1 to 10 did not satisfy the required characteristic for any one of strength (tensile strength ⁇ 1050 MPa, 0.2% yield strength ⁇ 968 MPa), workability (elongation ⁇ 25), non-magnetism (magnetic permeability ⁇ 1.010) and corrosion resistance (ferric chloride corrosion ⁇ 0.5, 10% oxalic acid etching: step). The reason for this is considered to be that Comparative Steels 1 to 10 did not contain the components defined in Table 2 in predetermined amounts, or did not satisfy any one of equations (1) to (4).
- Comparative Steel 1 did not satisfy equation 1 because of its small Mo content, and further did not satisfy equation 2 because of its excessive C content. Corrosion resistance is therefore considered to be impaired even when the Mn content is small.
- Comparative Steel 1 did not satisfy equation 4, it satisfied the required characteristic for magnetic permeability.
- Comparative Steel 2 contained Cr essential for securing corrosion resistance in a predetermined amount, but did not satisfy equation 1 because of its small Mo and N contents. Corrosion resistance is therefore considered to be impaired. Further, high magnetic permeability of Comparative Steel 2 is considered to be caused by the small N content.
- Comparative Steel 3 contained Cr essential for securing corrosion resistance in a predetermined amount, but did not satisfy equation 1 because of its small Mo and N contents, and did not satisfy equation 2 because of its excessive C content. Corrosion resistance is therefore considered to be impaired. Comparative Steels 4 and 5 did not satisfy equations (1) and (3) because of their excessively small Mo content, excessive Mn content and rather small Cr content. Corrosion resistance is therefore considered to be impaired. Comparative Steel 6 did not satisfy equation (4) because of its excessively small Cu content. Corrosion resistance is therefore considered to be impaired.
- Comparative Steel 7 satisfied equations (1) to (4), and satisfied the required characteristics of high corrosion resistance, non-magnetism and high strength, although the Cu, Ni and Mo contents were outside the predetermined ranges. However, it was revealed that Comparative Steel 7 was decreased in elongation to cause difficulty in working, which was unsuitable for actual production, because of its low working temperature. Comparative Steel 8 did not satisfy equation (1), because of its excessively small Cu and Mo contents. Corrosion resistance is therefore considered to be impaired. Further, in Comparative Steel 8, the working temperature was increased to 950°C. However, it was confirmed that an increase in working temperature was not so much effective for an increase in strength.
- Comparative Steels 9 and 10 did not satisfied equation (1) because of its excessively small Mo content, did not satisfy equation (3) in relation to the balance of the components, and was excessively small in Cu content. Corrosion resistance is therefore considered to be impaired. Further, both of these were high in magnetic permeability. Incidentally, in Comparative Steel 9, the reduction of area was as low as 10%, although the working temperature was low. It is therefore conceivable that deterioration of workability did not occur by high elongation and work hardening. On the other hand, in Comparative Steel 10, the working temperature was low, and moreover, the reduction of area was as high as 50%. It was therefore revealed that Comparative Steel 10 was increased in strength by work hardening, but decreased in elongation to cause difficulty in working, which was unsuitable for actual production.
- the high corrosion-resistant, high-strength and non-magnetic stainless steel, the high corrosion-resistant, high-strength and non-magnetic stainless steel product and the method for producing the same, according to the invention has the predetermined component composition, and the predetermined mutual relationship of the components is adjusted. Accordingly, the industrial use value thereof is high for steel product manufacturers.
- the high corrosion-resistant, high-strength and non-magnetic stainless steel according to the invention is expected to be applied to oil well excavation products and steel products such as spring, shaft, bolt and screw products.
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Abstract
Description
- The present invention relates to a high corrosion-resistant, high-strength and non-magnetic stainless steel, a high-strength, high corrosion-resistant and non-magnetic stainless steel product and a method for producing the same. More particularly, the invention relates to a technique for producing a non-magnetic stainless steel which is capable of blocking the influence of earth magnetism and is particularly suitable for the use in oil well excavation, without impairing its characteristics (high corrosion resistance and high strength).
- Conventionally, when an oil well is excavated using a drill, a position (for example, direction and inclination) of a tip of the drill from the earth's surface is identified by magnetic sensing to control the drill. Accordingly, a measuring instrument is mounted in a drill collar in the vicinity of a bit. In that case, for measuring the direction and inclination, the drill collar and the like are required to be made of a non-magnetic steel, in order to block the influence of earth magnetism. Conventionally, as steels for such a use, there have been used high Mn-based non-magnetic stainless steels such as 13Cr-18Mn-0.5Mo-2Ni-0.3N, 13Cr-21Mn-0.3N and 16.5Cr-16Mn-1Mo-1.3Ni-0.5Cu-0.4N.
- Further, as well-known improved techniques of this kind, there have been proposed, for example, techniques described in the following patent documents.
Patent document 1 (JP-A-53-117618 - Patent document 2 (
JP-A-59-104455 - Patent document 3 (
JP-A-59-205452 - Patent document 4 (
JP-A-61-143563 - Patent document 5 (
JP-A-61-170545 - Patent document 6 (
JP-A-61-238943 - Patent document 7 (
JP-A-2004-052097 - Patent document 8 (
JP-A-2004-156086 - As described above, a lot of stainless steels excellent in characteristics such as corrosion resistance and non-magnetism have been proposed.
- However, the recent oil well excavation region is versatile, and further high-corrosion resistant and high-strength stainless steels based on the assumption of non-magnetism have been demanded by the industrial world. Furthermore, the various types of steels described in the above-mentioned patent documents 1 to 8 have many problems to be solved. For example, the high-strength austenitic stainless steel of patent document 1 and the high-strength member for an instrument loaded on an undersea research ship of patent document 3 have a concern that workability and corrosion resistance are deteriorated by crystallization of coarse carbides due to their excessive C content.
The ultra-low temperature high-strength steel of patent document 2 and the rust-resistant, ultra-low temperature high manganese high-strength steel of patent document 4 have a concern that the required characteristics of non-magnetism, high strength and corrosion resistance are not satisfied due to their small N content. The ultra-low temperature high-strength steel of patent document 2 has a further concern that corrosion resistance is deteriorated due to its excessive Mn content. - The ultra-low temperature high manganese steel of patent document 5 has a concern that the required characteristics of non-magnetism, high strength and corrosion resistance are not satisfied, because the Cr content is rather small with respect to the Mn content, and the N content is also rather small.
In the high-strength non-magnetic stainless steel of patent document 6, the Ni and N contents are rather small. Further, in the interdental brush wire of patent document 7, Mn and Ni contents are excessively small. Moreover, in the non-magnetic stainless steel of patent document 8, the Ni and Mo contents are excessively small. Therefore, these alloys have a concern that the required characteristics of non-magnetism, high strength and corrosion resistance are not satisfied.
As described above, even according to patent documents 1 to 8, no stainless steel satisfying the required characteristics has been obtained. - The invention has been made in view of the above circumstances, and an object of the invention is to provide a high corrosion-resistant, high-strength and non-magnetic stainless steel having high corrosion resistance, high strength and non-magnetism; a high corrosion-resistant, high-strength and non-magnetic stainless steel product and a method for producing the same.
In particular, an object of the invention is to provide a high corrosion-resistant, high-strength and non-magnetic stainless steel which blocks the influence of earth magnetism at the time of oil well evacuation, and not only can be applied to oil well excavation products covering a wide range of regions, but also is suitable as raw materials for various parts (various spring products, VTR guide pins and motor shafts); a high corrosion-resistant, high-strength and non-magnetic stainless steel product and a method for producing the same. - In order to solve the above-mentioned problems, the present inventors have made intensive studies, centering on application of Cr and Mo as corrosion resistance-improving elements, for realizing high corrosion resistance. However, the inventors have encountered a problem that "non-magnetism which is capable of blocking the influence of earth magnetism" required for a drill collar and the like of oil well evacuation and the like cannot be achieved, because an increase in Cr content and Mo content causes magnetization. Then, the inventors have made further intensive studies. As a result, it has been found that when a composition balance is adjusted by making use of N and Ni, a stable non-magnetic austenite single-phase structure is obtained, even in the case where Cr and Mo are used to obtain high corrosion resistance.
The invention has been made based on such a finding. - Namely the present invention provides a high corrosion-resistant, high-strength and non-magnetic stainless steel containing: C: 0.01% to 0.05% by mass, Si: 0.05% to 0.50% by mass, Mn: more than 16.0% by mass but 19.0% by mass or less, P: 0.040% by mass or less, S: 0.010% by mass or less, Cu: 0.50% to 0.80% by mass, Ni: 3.5% to 5.0% by mass, Cr: 17.0% to 21.0% by mass, Mo: 1.80% to 3.50% by mass, B: 0.0010% to 0.0050% by mass, O: 0.010% by mass or less, and N: 0.45% to 0.65% by mass, with the balance substantially composed of Fe and unavoidable impurities, the steel satisfying the following equations (1) to (4):
wherein [Cr], [Mo], [N], [C], [Mn], [Ni] and [Cu] represent the content of Cr, the content of Mo, the content of N, the content of C, the content of Mn, the content of Ni, and the content of Cu in the steel in terms of mass %, respectively. - The high corrosion-resistant, high-strength and non-magnetic stainless steel according to the present invention may further contains at least one element selected from the group consisting of Ca, Mg and REM in a total content of 0.0001% to 0.0100% by mass.
The high corrosion-resistant, high-strength and non-magnetic stainless steel according to the present invention may further contains at least one element selected from the group consisting of Nb, V, Ta and Hf in a total content of 0.1 % to 2.0% by mass.
The high corrosion-resistant, high-strength and non-magnetic stainless steel according to the present invention may further contains A1 in a content of 0.001 % to 0.10% by mass.
The high corrosion-resistant, high-strength and non-magnetic stainless steel according to the present invention may further contains at least one member selected from the group consisting of W and Co in a total content of 0.1% to 3.0% by mass. - The present invention further provides a method for producing a high corrosion-resistant, high-strength and non-magnetic stainless steel product, which includes subjecting the steel according to the present invention to working under a temperature condition of 300°C to 900°C at a reduction of area of 15% to 40%.
- The present invention furthermore provides a high corrosion-resistant, high-strength and non-magnetic stainless steel product obtained by subjecting the steel according to the present invention to working under a temperature condition of 300°C to 900°C at a reduction of area of 15% to 40%. Examples of the resulting steel product include oil well evacuation products, spring products, VTR guide pins, motor shafts and the like.
- The high corrosion-resistant, high-strength and non-magnetic stainless steel and the high corrosion-resistant, high-strength and non-magnetic stainless steel product according to the invention have the above-mentioned component composition and satisfies the above-mentioned equations (1) to (4), so that they have high corrosion resistance, high strength and non-magnetism. Accordingly, they has effects of being able to block the influence of earth magnetism at the time of oil well evacuation to be applied to oil well excavation products covering a wide range of regions, and moreover, being-suitable as raw materials for various parts (various spring products, VTR guide pins and motor shafts).
In accordance with the method for producing a high corrosion-resistant, high-strength and non-magnetic stainless steel product according to the invention, the resulting steel product can exhibit the same effects as described above. - A high corrosion-resistant, high-strength and non-magnetic stainless steel according to one embodiment of the invention will be described below.
The high corrosion-resistant, high-strength and non-magnetic stainless steel according to this embodiment contains the following essential elements and selective elements and the balance substantially composed of Fe and unavoidable impurities, and satisfies relationship defined by equations (1) to (4) described later. Herein, in the present specification, all the percentages defined by mass are the same as those defined by weight, respectively. - The high corrosion-resistant, high-strength and non-magnetic stainless steel according to this embodiment contains C, Si, Mn, Cu, Ni, Cr, Mo, B and N as essential elements, and the balance is substantially composed of Fe and unavoidable impurities. The unavoidable impurities as mentioned herein include, for example, P, S and O.
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- (1) 0.01% ≤ C ≤ 0.05% by mass
C is an essential element which is indispensable as an austenite-forming element, and contributes to strength. Accordingly, 0.01 % by mass is specified as the lower limit of the content of C. Further, excessive addition of C causes coarse carbides to crystallize, thereby deteriorating workability and corrosion resistance. Accordingly, 0.05% by mass is specified as the upper limit of the content of C. The content of C is more preferably from 0.03% to 0.05% by mass. -
- (2) 0.05% ≤ Si ≤ 0.50% by mass
Si is an essential element added as a deoxidizer for the steel, so that 0.05% by mass is specified as the lower limit of the content of Si. However, an excessive content of Si causes a decrease in toughness to deteriorate hot workability, so that 0.50% by mass is specified as the upper limit of the content of Si. The content of Si is more preferably from 0.10% to 0.30% by mass. -
- (3) 16.0% < Mn ≤ 19.0% by mass
Mn is an essential element acting as a deoxidizer for the steel. In order to secure the dissolved amount of N, Mn should be contained in an amount of more than 16.0% by mass. On the other hand, Mn deteriorates corrosion resistance, so that 19.0% by mass is specified as the upper limit of the content of Mn. The content of Mn is more preferably more than 16.0% by mass but 17.0% by mass or less. -
- (4) P ≤ 0.040% by mass
P is an unavoidable impurity, segregates in a grain boundary to heighten the corrosion susceptibility of the grain boundary and deteriorate the toughness. Accordingly, the content of P is preferably as low as possible. However, an excessive reduction thereof causes an increase in cost, so that the content of P is specified as 0.040% by mass or less. The content of P is more preferably 0.030% by mass or less. -
- (5) S ≤ 0.010% by mass
S is an unavoidable impurity, and deteriorates hot workability, so that 0.010% by mass is specified as the upper limit of the content of S. From the viewpoint of a balance with production cost, the content of S is more preferably 0.005% by mass or less. -
- (6) 0.50% ≤ Cu ≤ 0.80% by mass
Cu is an essential element, effective for improving corrosion resistance, particularly corrosion resistance in a reducing acid environment, and effective for obtaining an austenite single-phase structure. Accordingly, 0.50% by mass is specified as the lower limit of the content of Cu. On the other hand, excessive addition of Cu deteriorates hot workability, so that 0.80% by mass is specified as the upper limit of the content of Cu. -
- (7) 3.5% ≤ Ni ≤ 5.0% by mass
Ni is an essential element, effective for improving corrosion resistance, particularly corrosion resistance in a reducing acid environment, and provides an austenite single-phase structure at the time of solution treatment. Accordingly, 3.5% by mass is specified as the lower limit of the content ofNi. On the other hand, excessive addition of Ni causes an increase in cost, so that 5.0% by mass is specified as the upper limit of the content of Ni. The content of Ni is more preferably from 3.5% to 4.5% by mass, from the viewpoint of a balance between characteristics and cost. -
- (8) 17.0% ≤ Cr ≤ 21.0% by mass
Cr is an essential element from the viewpoint of securing corrosion resistance, and in order to secure the dissolved amount ofN, 17.0% by mass is specified as the lower limit of the content of Cr. On the other hand, excessive addition of Cr impairs hot workability and causes a decrease in toughness, so that 21.0% by mass is specified as the upper limit of the content of Cr. The content of Cr is more preferably from 18.0% to 19.5% by mass. -
- (9) 1.80% ≤ Mo ≤ 3.50% by mass
Mo is an essential element, which provides necessary corrosion resistance and is capable of further improving strength. Accordingly, 1.80% by mass is specified as the lower limit of the content of Mo. On the other hand, excessive addition of Mo impairs hot workability, and causes an increase in cost. Accordingly, 3.50% by mass is specified as the upper limit of the content of Mo. The content of Mo is more preferably from 2.00% to 2.50% by mass. -
- (10) 0.0010% ≤ B ≤ 0.0050% by mass
B is an essential element effective for improving hot workability of the steel, so that 0.0010% by mass is specified as the lower limit of the content of B. On the other hand, excessive addition of B forms nitrides such as BN to deteriorate workability, so that 0.0050% by mass is specified as the upper limit of the content of B. The content of B is more preferably 0.0030% by mass or less. -
- (11) O ≤ 0.010% by mass
O is an unavoidable impurity, which forms harmful oxides which exert an adverse effect on cold workability, fatigue characteristics or the like. Accordingly, the O content should be restrained as low as possible, and 0.010% by mass is specified as the upper limit of the content of O. From the viewpoint of a balance with production cost, the content of O is more preferably 0.007% by mass or less, and still more preferably 0.005% by mass or less. -
- (12) 0.45% ≤ N ≤ 0.65% by mass
N is an essential element necessary for obtaining non-magnetism, high strength and good corrosion resistance, and 0.45% by mass is specified as the lower limit of the content of N. On the other hand, excessive addition of N causes N blow, so that 0.65% by mass is specified as the upper limit of the content of N. The content of N is more preferably from 0.50% to 0.60% by mass. - The high corrosion-resistant, high-strength and non-magnetic stainless steel according to this embodiment may further contain the following selective elements, that is to say, at least one element selected from the group consisting of Ca, Mg and REM; the group consisting ofNb, V, Ta and Hf; Al; and the group consisting of W and Co. (13) At least one element selected from the group consisting of Ca, Mg and REM in a total content of 0.0001% to 0.0100% by mass
Ca, Mg and REM are selective elements, and elements effective for improving hot workability of the steel. Accordingly, they may be added in a total content of 0.0001 % by mass or less. However, excessive addition of these elements results in saturation of the effect, and conversely decreases hot workability. Accordingly, 0.0100% by mass is specified as the upper limit of the total content thereof. The total content thereof is more preferably 0.0050% by mass or less. Incidentally, in this embodiment, REM means one containing Ce, La or an alloy thereof. -
- (14) At least one element selected from the group consisting of Nb, V, Ta and Hf in a total content of 0.1% to 2.0% by mass
Nb, V, Ta and Hf are selective elements, and these have an effect of forming carbides or carbonitrides to miniaturize grains of the steel, thereby increasing toughness. Accordingly, 0.1 % by mass is specified as the lower limit of the total content ofNb, V, Ta and Hf. On the other hand, excessive addition of Nb, V, Ta and Hf causes an increase in cost, so that 2.0% by mass in total is specified as the upper limit. The content of Nb, V, Ta and Hf is more preferably 1.0% by mass or less. -
- (15) 0.001% ≤ Al ≤ 0.10% by mass
Al is a strong deoxidizing element, and is also a selective element which is added for decreasing O as much as possible, as needed. For the content of Al, 0.001 % by mass is specified as the lower limit, at which the effect thereof can be confirmed. On the other hand, excessive addition of Al deteriorates hot workability, so that 0.10% by mass is specified as the upper limit of the content of Al. The content of Al is more preferably 0.050% by mass, and still more preferably 0.010% by mass. -
- (16) At least one element selected from the group consisting of W and Co in a total content of 0.1 % to 3.0% by mass
W is a selective element, and has an effect of improving corrosion resistance and forming a carbide or a carbonitride to miniaturize grains, thereby increasing toughness. Accordingly, W may be added in an amount of 0.1% to 3.0% by mass. On the other hand, excessive addition of W causes an increase in cost, so that the content of W is more preferably 2.0% by mass or less. - Co is a selective element, and effective for obtaining an austenite single-phase structure to achieve high strength by solid solution strengthening. Accordingly, Co may be added as needed. However, excessive addition of Co causes a substantial increase in cost, so that 3.0% by mass is specified as the upper limit of the content of Co. The content of Co is more preferably 1.5% by mass or less.
- The high corrosion-resistant, high-strength and non-magnetic stainless steel according to this embodiment satisfies the following equations (1) to (4):
- (17)
PI (Pitting Index) is a value indicating corrosion resistance, and defined by [Cr], [Mo] and [N]. The larger value shows the better corrosion resistance, so that PI is specified as 30 or more. In order to make it possible to use the steel under a severe corrosive environment, the value of equation (1) is more preferably 33 or more. -
- (18)
C combines with Cr to form a carbide, thereby decreasing the content of Cr in the matrix and thus causing deterioration of corrosion resistance. For this reason, equation (2) becomes a relational expression which can be used as an index of corrosion resistance. Accordingly, the larger the Cr content to the C content is, the more the deterioration of corrosion resistance can be inhibited. The value of equation (2) is therefore specified as 330 or more. -
- (19)
Both Cr and Mn are added in order to sufficiently dissolve N. However, Mn deteriorates corrosion resistance, so that it becomes necessary to balance with Cr as an element for improving corrosion resistance. Accordingly, in order to sufficiently maintain corrosion resistance by compensating for deterioration of corrosion resistance caused by addition of Mn, the value of equation (3) is specified as exceeding 1.0. -
- (20)
Both Cr and Mo are added for sufficiently securing corrosion resistance. However, associated therewith, stability of an austenite single phase deteriorates. Accordingly, in order to stabilize the austenite phase, Ni and Cu as austenite-forming elements are allowed to be contained in predetermined amounts, thereby inhibiting deterioration of the stability of the austenite single phase. Further, an increase in weight of Cr and addition of Mo act toward a direction impairing non-magnetism, so that non-magnetism is maintained by Ni and Cu. In view of these circumstances, equation (4) defines a quantitative relation in which Ni and Cu should satisfy with respect to Cr and Mo. The value of equation (4) is specified as exceeding 0.25, but it is more preferably 0.30 or more. - In this regard, with regard to each element contained in the steel of the invention, according to an embodiment, the minimal amount thereof present in the steel is the smallest non-zero amount used in the inventive steels as summarized in Tables 1 and 2. According to a further embodiment, the maximum amount thereof present in the steel is the maximum amount used in the inventive steels as summarized in Tables 1 and 2.
- The high-corrosion resistant, high strength and non-magnetic stainless steel according to this embodiment is obtained by
- (1) melting a steel ingot containing the above-mentioned specified components in specified amounts so as to satisfy the specified relations,
- (2) processing it to an appropriate shape and size by hot working, and then,
- (3) subjecting it to solution treatment (1050°C to 1150°C).
The high-corrosion resistant, high strength and non-magnetic stainless steel product according to this embodiment is obtained by, in addition to the above-mentioned steps, - (4) further subjecting the above-mentioned stainless steel to warm working (300°C to 900°C, reduction of area: 15% to 40%). Cutting or the like may be further performed as needed. The reason for specifying the lower limit temperature as 300°C is that the lower working temperature contributes to higher strength, whereas deteriorates elongation and drawing, resulting in difficulty in working.
- A 50 kg steel ingot having each component composition (the balance is composed of Fe and unavoidable impurities) shown in Tables 1 and 2 was melted in a high-frequency induction furnace, and a rod stock having a diameter of 20 mm was prepared by hot forging processing, followed by solution treatment at 1050°C to 1150°C. The values of the above-mentioned equations (1) to (4) are shown together in Table 2. In the tables 1 and 2, "-" means that a corresponding element is not added or unavoidably contained even though it should not be added.
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Table 1 Component Composition (unit: % by mass) and Values of Equations (1) to (4) C Si Mn P S Cu Ni Cr Mo B O N Ca, Mg. REM Nb, V, Ta, Hf Al W, Co PI Cr/C Cr/Mn (Ni+3Cu)/ (Cr+Mo) 1 0.03 0.18 16.9 0.002 0.001 0.52 5.0 19.3 1.89 0.0038 0.005 0.48 Ca:0.0009 - - W:1.8 31.2 643 1.14 0.31 2 0.02 0.48 16.1 0.018 0.002 0.65 3.6 18.8 1.94 0.0014 0.008 0.52 - Nb:0.48 0.002 - 33.5 940 1.17 0.27 3 0.04 0.13 18.7 0.028 0.002 0.53 4.5 18.9 2.11 0.0023 0.006 0.54 - - - - 34.5 473 1.01 0.29 4 0.03 0.31 18.9 0.037 0.003 0.55 4.4 19.3 1.96 0.0021 0.004 0.55 - - 0.002 - 34.6 643 1.02 0.28 5 0.04 0.21 16.1 0.011 0.003 0.62 3.6 18.7 2.05 0.0025 0.007 0.55 - - - - 34.3 468 1.16 0.26 6 0.02 0.49 16.2 0.009 0.004 0.59 4.9 20.1 2.77 0.0013 0.003 0.63 Ca:0.0020 - - - 39.3 1005 1.24 0.29 7 0.03 0.25 16.3 0.025 0.002 0.61 3.5 18.8 1.95 0.0021 0.004 0.56 - - 0.003 - 34.2 627 1.15 0.26 8 0.01 0.12 17.4 0.029 0.008 0.74 5.4 19.8 1.82 0.0028 0.007 0.64 - V:0.78 - Co:1.2 36.0 1980 1.14 0.35 9 0.05 0.46 18.8 0.032 0.005 0.60 4.6 18.9 2.00 0.0032 0.008 0.54 Mg:0.0012 - 0.005 - 34.1 378 1.01 0.31 Inventive steel 10 0.03 0.28 16.0 0.027 0.003 0.58 3.6 18.5 2.16 0.0048 0.007 0.55 - 0.003 - 34.4 617 1.16 0.26 11 0.05 0.29 17.4 0.023 0.003 0.79 3.8 17.6 2.54 0.0019 0.007 0.49 - Nb:0.35 0.002 Co:0.6 33.8 352 1.01 0.31 12 0.02 0.28 18.3 0.006 0.004 0.58 4.5 17.9 2.33 0.0024 0.005 0.65 Mg:0.0009 Ta:0.52 0.004 - 36.0 895 1.01 0.31 13 0.04 0.29 18.6 0.027 0.002 0.64 4.9 19.2 2.76 0.0022 0.005 0.55 - - - - 37.1 480 1.03 0.31 14 0.03 0.39 18.9 0.029 0.001 0.61 4.5 19.1 1.94 0.0020 0.004 0.54 - - 0.003 - 34.1 637 1.01 0.30 15 0.04 0.22 18.8 0.020 0.004 0.57 5.0 18.8 2.01 0.0019 0.003 0.57 - - 0.002 - 34.6 470 1.00 0.32 16 0.05 0.38 17.7 0.017 0.001 0.55 4.6 18.0 1.85 0.0034 0.001 0.63 - V:0.32 0.001 - 34.2 360 1.02 0.31 17 0.05 0.24 18.5 0.032 0.002 0.52 5.0 19.0 2.84 0.0028 0.004 0.53 - - - - 36.9 380 1.03 0.30 18 0.03 0.29 18.8 0.030 0.001 0.63 4.6 19.2 2.11 0.0031 0.002 0.55 - - 0.004 W:0.8 35.4 640 1.02 0.30 19 0.04 0.27 18.5 0.028 0.003 0.50 4.4 18.6 2.22 0.0030 0.003 0.54 - - 0.001 - 34.6 465 1.01 0.28 20 0.02 0.11 16.6 0.025 0.002 0.68 4.1 19.6 2.03 0.0029 0.003 0.51 REM:0.0014 Hf:0.28 0.003 W:2.5 35.7 980 1.18 0.28 -
Table 2 Component Composition (unit: % by mass) and Values of Equations (1) to (4) C Si Mn P S Cu Ni Cr Mo B O N Ca,Mg. REM Nb, V, Ta, Hf Al W, Co PI Cr/C Cr/Mn (Ni+3Cu)/ (Cr+Mo) 21 0.04 0.22 18.9 0.025 0.001 0.62 4.9 19.1 2.94 0.0033 0.006 0.56 0.002 37.8 478 1.01 0.31 22 0.04 0.18 16.7 0.033 0.001 0.57 4.3 18.2 1.88 0.0041 0.004 0.49 Mg:0.017 32.2 455 1.09 0.30 23 0.03 0.28 16.3 0.029 0.002 0.71 3.6 19.3 1.91 0.0025 0.005 0.54 0.001 34.2 643 1.18 0.27 Inventive steel 24 0.04 0.18 16.3 0.014 0.002 0.74 3.5 18.8 1.83 0.0016 0.006 0.55 33.6 470 1.15 0.28 25 0.01 0.47 16.9 0.027 0.003 0.61 5.5 19.1 2.32 0.0023 0.005 0.52 Hf:0.19 0.002 35.1 1910 1.13 0.34 26 0.04 0.30 17.7 0.032 0.001 0.58 3.9 17.8 2.10 0.0026 0.003 0.47 REM:0.0019 Co:0.8 32.3 445 1.01 0.28 1 0.09 0.33 14.8 0.023 0.003 0.32 3.0 19.4 0.02 0.013 0.54 28.1 216 1.31 0.20 2 0.05 0.43 1.5 0.019 0.004 0.26 8.5 18.2 0.23 0.009 0.04 19.6 364 12.13 0.50 3 0.07 0.29 1.2 0.027 0.002 0.23 12.1 18.3 0.03 0.008 0.03 18.9 261 15.25 0.70 4 0.05 0.33 21.0 0.031 0.003 0.23 4.1 16.8 0.43 0.007 0.46 25.6 336 0.80 0.28 Comparative steel 5 0.03 0.29 19.8 0.022 0.002 0.54 3.7 17.2 1.22 0.009 0.48 28.9 573 0.87 0.29 6 0.04 0.32 16.2 0.028 0.004 0.11 3.6 18.4 2.41 0.006 0.51 34.5 460 1.14 0.19 7 0.03 0.43 17.2 0.021 0.003 0.32 5.2 19.2 1.45 0.004 0.49 31.8 640 1.12 0.30 8 0.04 0.32 16.3 0.026 0.002 0.25 3.9 17.3 0.90 0.006 0.55 29.1 433 1.06 0.26 9 0.05 0.51 18.9 0.034 0.004 0.19 4.8 18.1 1.11 0.005 0.50 29.8 362 0.96 0.28 10 0.03 0.29 16.8 0.039 0.003 0.34 3.4 16.3 0.33 0.003 0.58 26.7 543 0.97 0.27
The tensile strength, the 0.2% yield strength and the elongation (%) were determined by preparing a JIS No. 4 test specimen from each of the materials under test, and measuring the breaking stress at the time when the tensile load is applied to a leading edge of the specimen in accordance with JIS Z 2241.
The magnetic permeability was determined by performing measurement of the magnetic permeability according to the VSM method, taking the external magnetic field as 2,000 Oe.
The corrosion resistance was evaluated by the 6% ferric chloride test (JIS G 0578) and the 10% oxalic acid etching test (JIS G 0571).
The test results thereof are shown together in Tables 3 and 4. -
Table 3 Test results 1 Working Method Tensile Strength (MPa) 0.2% Yield Strength (MPa) Elongation (%) Magnetic Permeability Ferric Chloride Corrosion (g/m2·h) 10% Oxalic Acid Etching 1 300°C warm working-reduction of area 30% 1151 1053 41 1.004 0.14 step 2 300°C warm working-reduction of area 30% 1250 1148 39 1.003 0.29 step 3 300°C warm working-reduction of area 30% 1294 1179 38 1.002 0.25 step 4 300°C warm working-reduction of area 30% 1321 1217 38 1.004 0.26 step 5 300°C warm working-reduction of area 30% 1304 1201 38 1.006 0.29 step 6 300°C warm working-reduction of area 30% 1512 1386 32 1.002 0.31 step 7 300°C warm working-reduction of area 30% 1344 1232 37 1.007 0.29 step 8 300°C warm working-reduction of area 30% 1536 1408 30 1.008 0.28 step 9 300°C warm working-reduction of area 30% 1295 1191 38 1.003 0.25 step Inventive steel 10 300°C warm working-reduction of area 30% 1318 1211 37 1.002 0.29 step 11 300°C warm working-reduction of area 30% 1176 1078 41 1.004 0.25 step 12 300°C warm working-reduction of area 30% 1560 1430 30 1.006 0.24 step 13 300°C warm working-reduction of area 30% 1331 1217 38 1.003 0.26 step 14 300°C warm working-reduction of area 30% 1298 1190 37 1.004 0.25 step 15 300°C warm working-reduction of area 30% 1368 1254 36 1.006 0.25 step 16 300°C warm working-reduction of area 30% 1523 1389 31 1.003 0.25 step 17 300°C warm working-reduction of area 30% 1272 1166 38 1.002 0.26 step 18 300°C warm working-reduction of area 30% 1322 1211 37 1.007 0.26 step 19 300°C warm working-reduction of area 30% 1296 1188 38 1.003 0.25 step 20 300°C warm working-reduction of area 30% 1224 1122 40 1.007 0.30 step 21 300°C warm working-reduction of area 30% 1348 1236 36 1.007 0.25 step 22 300°C warm working-reduction of area 30% 1176 1078 43 1.002 0.27 step 23 300°C warm working-reduction of area 30% 1299 1182 39 1.002 0.30 step Inventive steel 24 300°C warm working-reduction of area 30% 1320 1210 36 1.005 0.29 step 25 300°C warm working-reduction of area 30% 1248 1144 38 1.002 0.28 step 26 300°C warm working-reduction of area 30% 1128 1034 39 1.002 0.25 step 1 300°C warm working-reduction of area 30% 1345 1233 35 1.015 1.3 step 2 300°C warm working-reduction of area 30% 877 768 51 1.135 15.0 step 3 300°C warm working-reduction of area 30% 943 892 49 1.007 1.5 step 4 300°C warm working-reduction of area 30% 1175 1087 41 1.004 4.3 step Comparative steel 5 300°C warm working-reduction of area 30% 1189 1101 40 1.005 3.9 step 6 300°C warm working-reduction of area 30% 1204 1108 39 1.022 2.1 step 7 Working temperature 250°C -reduction of area 30% 1401 1345 17 1.018 0.4 step 8 Working temperature 950°C -reduction of area 30% 1189 1008 41 1.027 1.4 ditch 9 Working temperature 300°C -reduction of area 10% 1064 971 43 1.035 0.5 step 10 Working temperature 300°C -reduction of area 50% 1389 1312 19 1.048 4.1 ditch -
Table 4 Test results 2 Working Method Tensile Strength (MPa) 0.2% Yield Strength (MPa) Elongation (%) Magnetic Permeability Ferric Chloride Corrosion (g/m2·h) 10% Oxalic Acid Etching 1 900°C warm working-reduction of area 30% 1085 982 43 1.003 0.35 step 2 900°C warm working-reduction of area 30% 1175 1059 41 1.008 0.32 step 3 900°C warm working-reduction of area 30% 1213 1097 38 1.007 0.31 step 4 900°C warm working-reduction of area 30% 1245 1120 39 1.002 0.30 step 5 900°C warm working-reduction of area 30% 1235 1117 39 1.002 0.30 step 6 900°C warm working-reduction of area 30% 1421 1287 36 1.003 0.26 step 7 900°C warm working-reduction of area 30% 1263 1144 39 1.002 0.30 step 8 900°C warm working-reduction of area 30% 1443 1307 35 1.002 0.26 step 9 900°C warm working-reduction of area 30% 1222 1109 40 1.007 0.31 step Inventive steel 10 900°C warm working-reduction of area 30% 1242 1121 38 1.002 0.30 step 11 900°C warm working-reduction of area 30% 1105 1001 43 1.004 0.34 step 12 900°C warm working-reduction of area 30% 1466 1328 35 1.003 0.26 step 13 900°C warm working-reduction of area 30% 1247 1128 40 1.004 0.30 step 14 900°C warm working-reduction of area 30% 1214 1099 40 1.003 0.31 step 15 900°C warm working-reduction of area 30% 1286 1164 39 1.002 0.29 step 16 900°C warm working-reduction of area 30% 1422 1290 36 1.004 0.26 step 17 900°C warm working-reduction of area 30% 1195 1083 40 1.003 0.31 step 18 900°C warm working-reduction of area 30% 1250 1129 39 1.004 0.30 step 19 900°C warm working-reduction of area 30% 1218 1103 41 1.002 0.31 step 20 900°C warm working-reduction of area 30% 1150 1042 43 1.007 0.33 step 21 900°C warm working-reduction of area 30% 1260 1143 38 1.002 0.30 step 22 900°C warm working-reduction of area 30% 1105 1001 43 1.003 0.34 step 23 900°C warm working-reduction of area 30% 1210 1101 40 1.004 0.31 step Inventive steel 24 900°C warm working-reduction of area 30% 1240 1123 39 1.002 0.30 step 25 900°C warm working-reduction of area 30% 1173 1062 42 1.007 0.32 step 26 900°C warm working-reduction of area 30% 1060 970 45 1.002 0.35 step 1 900°C warm working-reduction of area 30% 1243 1147 38 1.017 2.40 ditch 2 900°C warm working-reduction of area 30% 775 682 62 1.018 18.9 ditch 3 900°C warm working-reduction of area 30% 841 806 50 1.005 2.3 ditch Comparative steel 4 900°C warm working-reduction of area 30% 1017 962 48 1.003 5.8 ditch 5 900°C warm working-reduction of area 30% 1043 977 46 1.004 4.1 step 6 900°C warm working-reduction of area 30% 1023 982 47 1.014 2.8 step 7 8 9 10 - Inventive Steels 1 to 26 satisfied the required characteristics for all of strength (tensile strength ≥ 1050 MPa, 0.2% yield strength ≥ 968 MPa), workability (elongation ≥ 25), non-magnetism (magnetic permeability ≤ 1.010) and corrosion resistance (ferric chloride corrosion < 0.5, 10% oxalic acid etching: step). Inventive Steels 1 to 26 contained the components defined in Tables 1 and 2 in predetermined amounts, and satisfied equations (1) to (4) defined in Tables 1 and 2. It is therefore conceivable that corrosion resistance, strength and non-magnetism could be achieved at the same time.
Accordingly, it has become clear that Inventive Steels 1 to 26 block the influence of earth magnetism at the time of oil well evacuation, and not only can be applied to oil well excavation products covering a wide range of regions, but also are suitable as raw materials for various parts (various spring products, VTR guide pins and motor shafts). - On the other hand, Comparative Steels 1 to 10 did not satisfy the required characteristic for any one of strength (tensile strength ≥ 1050 MPa, 0.2% yield strength ≥ 968 MPa), workability (elongation ≥ 25), non-magnetism (magnetic permeability ≤ 1.010) and corrosion resistance (ferric chloride corrosion < 0.5, 10% oxalic acid etching: step). The reason for this is considered to be that Comparative Steels 1 to 10 did not contain the components defined in Table 2 in predetermined amounts, or did not satisfy any one of equations (1) to (4).
- For example, Comparative Steel 1 did not satisfy equation 1 because of its small Mo content, and further did not satisfy equation 2 because of its excessive C content. Corrosion resistance is therefore considered to be impaired even when the Mn content is small. Incidentally, although Comparative Steel 1 did not satisfy equation 4, it satisfied the required characteristic for magnetic permeability.
Comparative Steel 2 contained Cr essential for securing corrosion resistance in a predetermined amount, but did not satisfy equation 1 because of its small Mo and N contents. Corrosion resistance is therefore considered to be impaired. Further, high magnetic permeability of Comparative Steel 2 is considered to be caused by the small N content. - Comparative Steel 3 contained Cr essential for securing corrosion resistance in a predetermined amount, but did not satisfy equation 1 because of its small Mo and N contents, and did not satisfy equation 2 because of its excessive C content. Corrosion resistance is therefore considered to be impaired.
Comparative Steels 4 and 5 did not satisfy equations (1) and (3) because of their excessively small Mo content, excessive Mn content and rather small Cr content. Corrosion resistance is therefore considered to be impaired.
Comparative Steel 6 did not satisfy equation (4) because of its excessively small Cu content. Corrosion resistance is therefore considered to be impaired. - Comparative Steel 7 satisfied equations (1) to (4), and satisfied the required characteristics of high corrosion resistance, non-magnetism and high strength, although the Cu, Ni and Mo contents were outside the predetermined ranges. However, it was revealed that Comparative Steel 7 was decreased in elongation to cause difficulty in working, which was unsuitable for actual production, because of its low working temperature.
Comparative Steel 8 did not satisfy equation (1), because of its excessively small Cu and Mo contents. Corrosion resistance is therefore considered to be impaired. Further, in Comparative Steel 8, the working temperature was increased to 950°C. However, it was confirmed that an increase in working temperature was not so much effective for an increase in strength. - Comparative Steels 9 and 10 did not satisfied equation (1) because of its excessively small Mo content, did not satisfy equation (3) in relation to the balance of the components, and was excessively small in Cu content. Corrosion resistance is therefore considered to be impaired. Further, both of these were high in magnetic permeability. Incidentally, in Comparative Steel 9, the reduction of area was as low as 10%, although the working temperature was low. It is therefore conceivable that deterioration of workability did not occur by high elongation and work hardening. On the other hand, in Comparative Steel 10, the working temperature was low, and moreover, the reduction of area was as high as 50%. It was therefore revealed that Comparative Steel 10 was increased in strength by work hardening, but decreased in elongation to cause difficulty in working, which was unsuitable for actual production.
- Although one embodiment of the invention has been described above, the invention is not construed as being limited to the above-mentioned embodiment, and all modifications are possible based on the usual knowledge of those skilled in the art without departing from the spirit thereof. Such modifications should be construed as being included in the scope of the invention.
- The high corrosion-resistant, high-strength and non-magnetic stainless steel, the high corrosion-resistant, high-strength and non-magnetic stainless steel product and the method for producing the same, according to the invention, has the predetermined component composition, and the predetermined mutual relationship of the components is adjusted. Accordingly, the industrial use value thereof is high for steel product manufacturers. The high corrosion-resistant, high-strength and non-magnetic stainless steel according to the invention is expected to be applied to oil well excavation products and steel products such as spring, shaft, bolt and screw products.
- The present application is based on Japanese Application No.
2009-108189 filed April 27, 2009 2009-123661 filed May 22, 2009 2010-015591 filed January 27, 2010
Claims (7)
- A high corrosion-resistant, high-strength and non-magnetic stainless steel comprising:C: 0.01% to 0.05% by mass,Si: 0.05% to 0.50% by mass,Mn: more than 16.0% by mass but 19.0% by mass or less,P: 0.040% by mass or less,S: 0.010% by mass or less,Cu: 0.50% to 0.80% by mass,Ni: 3.5% to 5.0% by mass,Cr: 17.0% to 21.0% by mass,Mo: 1.80% to 3.50% by mass,B: 0.0010% to 0.0050% by mass,O: 0.010% by mass or less, andN: 0.45% to 0.65% by mass,with the balance substantially composed of Fe and unavoidable impurities,
- The high corrosion-resistant, high-strength and non-magnetic stainless steel according to claim 1, which further comprises at least one element selected from the group consisting of Ca, Mg and REM in a total content of 0.0001 % to 0.0100% by mass.
- The high corrosion-resistant, high-strength and non-magnetic stainless steel according to claim 1 or 2, which further comprises at least one element selected from the group consisting ofNb, V, Ta and Hf in a total content of 0.1 % to 2.0% by mass.
- The high corrosion-resistant, high-strength and non-magnetic stainless steel according to any one of claims 1 to 3, which further comprises Al in a content of 0.001% to 0.10% by mass.
- The high corrosion-resistant, high-strength and non-magnetic stainless steel according to any one of claims 1 to 4, which further comprises at least one member selected from the group consisting of W and Co in a total content of 0.1% to 3.0% by mass.
- A method for producing a high corrosion-resistant, high-strength and non-magnetic stainless steel product, which comprises subjecting the steel according to any one of claims 1 to 5 to working under a temperature condition of 300°C to 900°C at a reduction of area of 15% to 40%.
- A high corrosion-resistant, high-strength and non-magnetic stainless steel product obtained by subjecting the steel according to any one of claims 1 to 5 to working under a temperature condition of 300°C to 900°C at a reduction of area of 15% to 40%.
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JP2009123661 | 2009-05-22 | ||
JP2010015591A JP5526809B2 (en) | 2009-04-27 | 2010-01-27 | High corrosion resistance, high strength, non-magnetic stainless steel and high corrosion resistance, high strength, non magnetic stainless steel products and methods for producing the same |
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US20100272593A1 (en) | 2010-10-28 |
EP2248919B1 (en) | 2015-10-21 |
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JP5526809B2 (en) | 2014-06-18 |
JP2011006776A (en) | 2011-01-13 |
CN101921970B (en) | 2014-03-12 |
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