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CN101815803A - Duplex stainless steel wire material, steel wire, bolt, and method for production of the bolt - Google Patents

Duplex stainless steel wire material, steel wire, bolt, and method for production of the bolt Download PDF

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Publication number
CN101815803A
CN101815803A CN200880110225A CN200880110225A CN101815803A CN 101815803 A CN101815803 A CN 101815803A CN 200880110225 A CN200880110225 A CN 200880110225A CN 200880110225 A CN200880110225 A CN 200880110225A CN 101815803 A CN101815803 A CN 101815803A
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Prior art keywords
steel wire
cold
bolt
wire rod
phase
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CN101815803B (en
Inventor
高野光司
柘植信二
天藤雅之
森祐司
多田好宣
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Nippon Steel Stainless Steel Corp
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Nippon Steel and Sumikin Stainless Steel Corp
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Priority claimed from JP2007264992A external-priority patent/JP5171197B2/en
Priority claimed from JP2007264993A external-priority patent/JP5171198B2/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/004Heat treatment of ferrous alloys containing Cr and Ni
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/02Hardening by precipitation
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/06Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/0093Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for screws; for bolts
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C21D9/54Furnaces for treating strips or wire
    • C21D9/56Continuous furnaces for strip or wire
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/001Ferrous alloys, e.g. steel alloys containing N
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/002Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/001Austenite
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    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/005Ferrite
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D7/00Modifying the physical properties of iron or steel by deformation
    • C21D7/02Modifying the physical properties of iron or steel by deformation by cold working
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/06Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
    • C21D8/065Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires of ferrous alloys
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/02Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for springs
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C21D9/525Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length for wire, for rods

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  • Metallurgy (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Heat Treatment Of Steel (AREA)
  • Heat Treatment Of Articles (AREA)

Abstract

Disclosed is an austenite-ferrite duplex steel wire material for a high-strength, high-corrosion-resistant bolt, which has excellent cold forgeability. The steel wire material comprises the following components (by mass): C: 0.005-0.05%, Si: 0.1-1.0%, Mn: 0.1-10.0%, Ni: 1.0-6.0%, Cr: 19.0-30.0%, Cu: 0.05-3.0% and N: 0.005-0.20%, with the remainder being Fe and substantially unavoidable impurities, wherein the total content of C and N is 0.20% or less, the M value represented by the formula (a) below is 60 or less, the F value represented by the formula (b) is 45 to 85, and the tensile strength is 550 to 750 N/mm2. M = 551-462(C+N)-9.2Si-8.1Mn-29(Ni+Cu)-13.7Cr-18.5Mo (a) F = 5.6Cr-7.1Ni+2.4Mo+15Si-3.1Mn-300C-134N-26.6 (b).

Description

Two phase stainless steel wire rod, steel wire and bolt and manufacture method thereof
Technical field
The present invention relates to the two phase stainless steel wire rod of excellent in cold forging property, and provide at an easy rate and for example have and the equal corrosion proof high strength bolt of SUS304.
The present invention relates to the good soft two phase stainless steel wire rod of cold-workability, be specifically related to provide at an easy rate the good soft two phase stainless steel wire rod of cold-workability that for example has strong cold working parts such as the corrosion proof screw equal, pin, wire netting, steel wire, wirerope, spring, given magnetizability simultaneously with SUS304, SUS316 with magnetizability.
The application based on October 10th, 2007 spy in Japanese publication be willing to 2007-264992 number, on October 10th, 2007 spy in Japanese publication be willing to advocate right of priority for 2007-264993 number, quote its content here.
Background technology
So far, be 700N/mm as intensity 2High strength, the high anti-corrosion bolt of level are extensive use of the SUS304 wire rod., in recent years, be that the center further requires bolt high strength (lightweight) with fields such as automobile, household electrical appliances.In addition, the SUS304 bolt makes price height so strong request cost degradation because of the Ni raw material that contains high price more.
So far, the high strength of bolt, for example the SUS630 bolt with martensitic stainless steel comes corresponding (for example, patent documentation 1).
, although SUS630 bolt excellent strength, not only solidity to corrosion is bad, and also obvious deterioration of cold forging, thereby manufacturing cost increases considerably, and uses to be subjected to very big restriction.
In addition, also proposed manufacturing good and cheap about 13%Cr be the high strength bolt (patent documentation 2) of martensitic stainless steel system., solidity to corrosion is not so good, and use is restricted.
The high strength bolt (patent documentation 3) of the austenite stainless steel system of high (C+N) amount has been proposed in addition., because of the cold forging difference makes manufacturing cost increase substantially, thereby do not accepted by market.
On the other hand, in recent years, the two phase stainless steel (patent documentation 4~6) of the cheapness that the low Ni that has proposed the use of inhibition high price Ni is.
, in two phase stainless steel in the past, cold forging is poor, and the manufacturing cost height, so the bolt of two phase stainless steel system does not occur on market.
More than, former stainless steel bolt and bolt be with in the STAINLESS STEEL WIRE, also do not have high anti-corrosion, high strength, high cold forging, goods cheaply concurrently.
About requiring goods such as corrosion proof screw, pin, wire netting, steel wire, use austenite stainless steel wire rods such as SUS304, SUSXM7, make by stretching or strong cold working such as cold forging, bending machining.In the cold working of wire rod, different with the press formability of the steel plate of the high elongation property that requires material, require soft and high tension fracture shrink characteristics (not requiring high elongation property).So-called soft, by the tensile strength of wire rod, require to be 700N/mm 2Below, be preferably 650N/mm 2Below.
,, added the Ni of a large amount of high prices, although therefore manufacturing process cheapness has the high defective of goods price as the goods of austenite stainless steel.
In addition, austenite stainless steel does not have magnetic, therefore when linking operation, fastening piece makes on the instrument that because of not being attached to operation is poor, by wire netting, sieve aperture (particularly travelling belt of using of food etc.) when generating material comes off and sneaks in the food, can not sneak into etc. with the Magnetic Sensor inspection, more inconvenient because of there not being magnetic.
About requiring magnetic, corrosion proof goods, proposed by the manufacturing of ferrite-group stainless steel wire rod, low C, N, added the ferrite-group stainless steel wire rod (patent documentation 7~9) of Nb.
, the solidity to corrosion deficiency of cold-worked article not only, and also the surface imperfection during because of rod rolling makes manufacturing cost increase under the situation of high Cr system.
On the other hand, in recent years, the multiple two phase stainless steel (patent documentation 10~12) that has reduced the cheapness of Ni has been proposed also.
In patent documentation 10, put down in writing the good high strength two phase stainless steel of nitrogen, Young's modulus that low Ni is, contains the raising intensity more than 0.04%., in order to improve intensity, added and surpassed 1% Si, and 0.04% above nitrogen, put down in writing in an embodiment and surpass 80kg/mm 2High strength, but do not consider soft, high tension fracture shrink characteristics, the cold-workability of wire rod is difficult in fact.
The two phase stainless steel of in patent documentation 11, having put down in writing low Ni system, having contained nitrogen more than 0.05%, have solidity to corrosion and good weldability.; about not record of cold-workability, the preferable range that improves the nitrogen of intensity is 0.06~0.12%, has put down in writing the steel (low Si steel) that contains the nitrogen more than 0.13% in an embodiment; do not consider soft, high tension fracture shrink characteristics, the cold-workability of wire rod is difficult in fact.
In patent documentation 12, put down in writing low Ni system, contained the good high strength two phase stainless steel of nitrogen, relaxation more than 0.05%., put down in writing the steel of the nitrogen of the raising intensity that contains more than 0.13% in an embodiment, do not considered soft, high tension fracture shrink characteristics, the cold-workability of wire rod is difficult in fact.
In patent documentation 13, put down in writing the two phase stainless steel that low Ni is, contains nitrogen, ductility and excellent in deep drawing characteristics more than 0.05%., put down in writing in an embodiment to improving the steel that the deep drawing quality of steel plate contains the nitrogen of the raising intensity more than 0.08% by improving extensibility, do not considered soft, high tension fracture shrink characteristics, the cold-workability of wire rod is difficult in fact.
More than, in the former stainless steel, have necessary soft, the high fracture shrinkage character of the cold-workability of wire rod and cheap and show that the stainless steel of high anti-corrosion, magnetizability does not also have.
Patent documentation 1: Japanese kokai publication hei 9-314276 communique
Patent documentation 2: TOHKEMY 2005-179718 communique
Patent documentation 3: TOHKEMY 2006-274295 communique
Patent documentation 4: international open WO2005/073422 communique
Patent documentation 5: No. 3271262 communique of Japanese Patent
Patent documentation 6:EP0337846 specification sheets
Patent documentation 7: No. 2906445 communique of Japanese Patent
Patent documentation 8: No. 2817266 communique of Japanese Patent
Patent documentation 9: TOHKEMY 2006-16665 communique
Patent documentation 10: Japanese kokai publication sho 62-47461 communique
Patent documentation 11: Japanese kokai publication sho 61-56267 communique
Patent documentation 12: Japanese kokai publication hei 2-305940 communique
Patent documentation 13: TOHKEMY 2006-169622 communique
Summary of the invention
The objective of the invention is to, it is two-phase steel wire rod, steel wire and bolt and manufacture method thereof with austenite-ferrite that cheap high strength, high anti-corrosion bolt is provided, control by tissue, composition, material, give the high strength of cold forging and bolt goods the high anti-corrosion duplex stainless steel of cheapness.
The objective of the invention is to, the two phase stainless steel wire rod of cold-workability and solidity to corrosion cheapness good, that have magnetic is provided, the manufacturing cost of the cold-worked article of austenite stainless steel wire rod is in the past descended significantly, and give magnetizability.
Present inventors have carried out multiple research for solving above-mentioned problem, found that: the Ni content that in the anti-corrosion two phase stainless steel of height, reduces high price, make by the composition adjustment simultaneously and organize stabilization (low M value), the volume fraction of ferritic phase is controlled at a high position, and by thermal treatment and Wire Drawing the tensile strength of wire rod, steel wire is suitably changed, can be taken into account the high strength of cold forging and bolt goods at an easy rate.
In addition, present inventors find: by the high anti-corrosion two phase stainless steel based on ferritic phase+austenite phase with magnetic, reduce the Ni of high price, simultaneously by composition adjustment control tissue (control of M value), and change inhibition work hardening with low (C+N), can give extremely excellent cold-workability to the two phase stainless steel wire rod of the high anti-corrosion of cheapness.
The present invention is based on above-mentioned opinion and finishes, local as follows as its main idea.
That is to say that first kind of mode of the present invention is that a kind of austenite-ferrite is the two-phase steel wire rod, wherein,
In quality %, contain:
C:0.005~0.05%、
Si:0.1~1.0%、
Mn:0.1~10.0%、
Ni:1.0~6.0%、
Cr:19.0~30.0%、
Cu:0.05~3.0%、
N:0.005~0.20%,
Surplus by Fe and in fact unavoidable impurities constitute, C+N is below 0.20%, the M value of formula (a) is below 60, the F value of formula (b) is 45~85, tensile strength is 550~750N/mm 2
M=551-462(C+N)-9.2Si-8.1Mn
-29(Ni+Cu)-13.7Cr-18.5Mo (a)
F=5.6Cr-7.1Ni+2.4Mo+15Si-3.1Mn-300C
-134N-26.6 (b)
The second way of the present invention is on the basis of first kind of mode, can also contain below the Mo:1.0% in quality %.
The third mode of the present invention is on the basis of first kind of mode, can also contain below the B:0.01% in quality %.
The 4th kind of mode of the present invention is on the basis of first kind of mode, in quality % can also contain in the following element more than a kind:
Below the Al:0.1%,
Below the Mg:0.01%,
Below the Ca:0.01%.
The 5th kind of mode of the present invention is on the basis of first kind of mode, in quality % can also contain in the following element more than a kind:
Below the Nb:1.0%,
Below the Ti:0.5%,
Below the V:1.0%,
Below the Zr:1.0%.
The 6th kind of mode of the present invention is that each and the tensile strength that comprise in five kinds of modes of above-mentioned first kind of mode to the are 700~1000N/mm 2Austenite-ferrite be the two-phase steel wire.
The 7th kind of mode of the present invention is that each and the tensile strength that comprise in five kinds of modes of above-mentioned first kind of mode to the are 700~1200N/mm 2High strength, high anti-corrosion bolt.
The 8th kind of mode of the present invention is that each and the tensile strength that will comprise in five kinds of modes of above-mentioned first kind of mode to the are 700~1000N/mm 2Austenite-ferrite be after the cold shaping of two-phase steel wire becomes bolt, implement down 1~100 minute aging heat treatment high strength, the manufacture method of high anti-corrosion bolt at 300~600 ℃.
The 9th kind of mode of the present invention is a kind of soft two phase stainless steel wire rod with magnetizability, wherein,
In quality %, contain:
C:0.005~0.05%、
Si:0.1~1.0%、
Mn:0.1~10.0%、
Ni:1.6~6.0%、
Cr:19.0~30.0%、
Cu:0.05~3.0%、
N:0.005% is above and be lower than 0.06%,
Surplus by Fe and in fact unavoidable impurities constitute, C+N is below 0.09%, the M value of formula (a) is below 60, tensile strength is 700N/mm 2Below, the tension fracture shrinking percentage is more than 70%.
M=551-462(C+N)-9.2Si-8.1Mn-29(Ni+Cu)
-13.7Cr-18.5Mo (a)
The of the present invention ten kind of mode is that % also contains below the Mo:3.0% in quality on the basis of the 9th kind of mode.
The 11 kind of mode of the present invention is that % also contains below the B:0.01% in quality on the basis of the 9th kind of mode.
The 12 kind of mode of the present invention is on the basis of the 9th kind of mode, in quality % also contain in the following element more than a kind:
Below the Al:0.1%,
Below the Mg:0.01%,
Below the Ca:0.01%.
The 13 kind of mode of the present invention is on the basis of the 9th kind of mode, in quality % also contain in the following element more than a kind:
Below the Nb:1.0%,
Below the Ti:0.5%,
Below the V:1.0%,
Below the Zr:1.0%.
Although the high strength of excellent in cold forging property of the present invention, high anti-corrosion bolt less contain the Ni of high price with the two phase stainless steel wire rod, but still can guarantee good cold forging, and can give equal above high anti-corrosion and high strength, have the effect that cheapness provides high strength, high anti-corrosion bolt with SUS304.
The soft two phase stainless steel wire rod that cold-workability of the present invention is good, although less contain the Ni of high price, but still can give extremely excellent cold-workability, magnetizability and with the equal solidity to corrosion of austenite stainless steels such as SUS304, SUS316, have the unusual effect that the high anti-corrosion goods with magnetizability can be provided at an easy rate.
Description of drawings
Fig. 1 is the figure of relation of volume fraction of the ferritic phase of expression F value and wire fabrication.
Fig. 2 is the working modulus (%) and compression set stress (N/mm of the expression steel wire (15% stretching wire rod) corresponding with the F value 2) the figure of relation.
Embodiment
Qualification reason to first kind of mode of the present invention~the 8th kind of mode describes below.
In order to ensure the intensity of bolt goods, contain the C more than 0.005%., surpass 0.05%, then not only make the solidity to corrosion deterioration because of generating the Cr carbonitride if contain, and also deterioration of cold forging, therefore it is limited to below 0.05%.Be preferably below 0.03%.
In order to guarantee the intensity of bolt goods by solution strengthening and age hardening, contain the N more than 0.005%., surpass 0.20% if contain, then therefore the obvious deterioration of cold forging is defined as 0.20% with the upper limit.Preferred range is to be lower than 0.05%.
Consider that from the reason of above-mentioned cold forging C+N is limited to below 0.20%.Be preferably below 0.10%.
For deoxidation, contain the Si more than 0.1%., surpass 1.0% if contain, then the cold forging deterioration.Therefore, the upper limit is defined as 1.0%.Preferred range is 0.2~0.6%.
As for deoxidation reaches the adjustment of carrying out in order to obtain stable austenite structure, contain the Mn more than 0.1%., surpass 10.0% if contain, then resistance to rust and ferrite volume fraction reduce, and tensile strength rises, the cold forging deterioration.Therefore, the upper limit is defined as 10.0%.Preferred range is 0.5~5.0%.
In order to make the austenite structure stabilization, to guarantee cold forging, contain the Ni more than 1.0%., surpass 6.0% even contain, its effect is also saturated, on the contrary the volume fraction of ferritic phase is become below 45%, cold forging (life tools) deterioration not only, and make the economy deterioration at high price because of Ni.Therefore, the upper limit is defined as 6.0%.Preferred range is above 3.0% and below 5.0%.
In order to ensure the volume fraction of solidity to corrosion, increase ferritic phase and by making the austenite structure stabilization guarantee cold forging, contain the Cr more than 19.0%.But, surpassing 30.0% even contain, its effect is also saturated, also makes the volume fraction of ferritic phase surpass 85% on the contrary, thereby the strength degradation of bolt goods.Therefore, the upper limit is defined as 30.0%.Preferred range is 22.0~26.0%.
Cu is effective for making the austenite structure stabilization, suppressing work hardening, promote the age hardening of ferritic phase and make bolt goods high strength when improving cold forging and the ageing treatment behind cold forging.Therefore, contain more than 0.05%., surpass 3.0% if contain, then surpass the solid solubility of Cu, therefore the obvious deterioration of raw-material hot manufacturing, is defined as 3.0% with the upper limit.Preferred range is more than 0.2% and is lower than 1.0%.
The M value of following formula (a) helps the stability of austenite phase, is " iron と Steel ", the index of record in 63 (1977), 772 pages, if the M value increases, then generates the martensitic phase that the processing of hard causes.When the cold forging of two phase stainless steel, if the M value surpasses 60, then when cold forging, generate the martensitic phase that the processing of hard causes, make the obvious deterioration of cold forging (life tools, the cold forging crackle took place deterioration).Therefore, the M value is defined as below 60.Preferred range is below 40.
M=551-462(C+N)-9.2Si-8.1Mn-29(Ni+Cu)
-13.7Cr-18.5Mo (a)
The F value of following formula (b) helps the volume fraction of ferritic phase, is the index of putting down in writing in the special fair 7-74416 communique of Japan, if the F value increases, then ferritic phase increases.Fig. 1 shows the investigation result of volume fraction of the ferritic phase of F value and two phase stainless steel wire fabrication.If the F value reaches more than 45, then the volume fraction of ferritic phase just reaches more than the 45vol.%, demonstrates high endurance, low work hardening characteristic (Fig. 2), can make intensity (tensile strength of the bolt axial region) high strength to 700~1200N/mm of goods 2, and can guarantee the cold forging of head.Therefore, the F value is limited to more than 45.The working modulus corresponding (%) of Fig. 2 and compression set stress (N/mm with the F value 2) relation show that be lower than at 45 o'clock in the F value, work hardening is big, cold forging (forge crack, instrument damage) is deterioration significantly.On the other hand, if the F value surpasses 85, then soft ferritic phase surpasses 85%, and the austenite that intensity is high reduces mutually, so the intensity of bolt goods reduces on the contrary.Therefore, the upper limit is defined as 85.Preferred range is 50~80.
F=5.6Cr-7.1Ni+2.4Mo+15Si-3.1Mn-300C
-134N-26.6 (b)
The tensile strength of wire rod helps cold forging very much, is lower than 550N/mm in the tensile strength of wire rod 2The time, the intensity of steel wire such as bolt is low, as the value reduction of high strength goods.Therefore, undergage is decided to be 550N/mm 2On the other hand, if the tensile strength of wire rod surpasses 750N/mm 2, the obvious deterioration of cold forging (life tools deterioration, the cold forging crackle takes place) then.Therefore, the upper limit is defined as 750N/mm 2Preferred range is 600~700N/mm 2
Mo is for improving the solidity to corrosion effective elements, can stably obtaining effect by adding more than 0.1%., surpass 1.0% if contain, then not only the cost of material rises, and the material hardization, the cold forging deterioration.Therefore, the upper limit is defined as 1.0%.Preferred range is more than 0.2% and is lower than 0.5%.
B is for improving the hot workability effective elements, can stably obtaining effect by adding more than 0.001%., surpass 0.01%, then generate boride, make solidity to corrosion and cold forging deterioration if contain.Therefore, the upper limit is defined as 0.01%.Preferred range is 0.002%~0.006%.
Al, Mg, Ca are effectively for deoxidation, and therefore Al:0.005% is above by adding, Mg:0.001% is above, Ca:0.001% more than one in above, can stably obtain effect., even make Al surpass 0.1% respectively, make Mg surpass 0.01%, make Ca surpass 0.01% ground to contain, its effect is also saturated, also produces thick oxide compound (inclusion) on the contrary, produces the cold forging crackle.Therefore, respectively the upper limit is defined as Al:0.1%, Mg:0.01%, Ca:0.01%.Preferred range is to contain in Al:0.01%~0.06%, Mg:0.002~0.005%, Ca:0.002~0.005% more than one.
Nb, Ti, V, Zr guarantee that for the generation that suppresses the Cr carbonitride solidity to corrosion is effectively, by in adding more than the Nb:0.05%, more than the Ti:0.02%, more than the V:0.05%, more than the Zr:0.05% more than one, can stably obtain effect., even make Nb surpass 1.0%, make Ti surpass 0.5%, make V surpass 1.0%, make Zr surpass 1.0% ground to contain, its effect is also saturated, also produces thick precipitate on the contrary, produces the cold forging crackle.Therefore, stipulate the upper limit of each element.Preferred range is to contain in Nb:0.1%~0.6%, Ti:0.05~0.5%, V:0.1~0.6%, Zr:0.1~0.6% more than one.
Usually, as unavoidable impurities, in manufacturing process, steel contains aerobic, but under situation of the present invention, as unavoidable impurities, preferably oxygen is defined as below 0.01%.
Though the wire rod Wire Drawing is formed the drawing steel wire, and the tensile strength of steel wire helps cold forging and bolt product strength very much, be lower than 700N/mm in the tensile strength of steel wire 2The time, the intensity of bolt goods is low, as the value reduction of high strength goods.Therefore, undergage is decided to be 700N/mm 2On the other hand, if the tensile strength of steel wire surpasses 1000N/mm 2, the obvious deterioration of cold forging (life tools deterioration, the cold forging crackle takes place) then.Therefore, the upper limit is defined as 1000N/mm 2Preferred range is 750~900N/mm 2
High strength is carried out in the timeliness thermal treatment of the tensile strength of high strength bolt of the present invention after by Wire Drawing and cold forging.At this moment, the tensile strength at the bolt goods is lower than 700N/mm 2The time, low as the value of high strength bolt goods, on the other hand, if the tensile strength of bolt goods reaches 1200N/mm 2More than, cold forging crackle and instrument damage etc., the obvious deterioration of cold forging cost then take place.Therefore, the upper limit with the tensile strength of bolt goods is defined as 1200N/mm 2The preferable range of bringing into play effect economically is 800~1000N/mm 2
After steel wire of the present invention being shaped as bolt,,, then be resultful if be implemented in the timeliness thermal treatment that keeps more than 300 ℃ more than 1 minute in order to improve the tensile strength of bolt goods effectively by cold forging.On the other hand, if surpass 600 ℃ then effects that obsolesce, thereby make the tensile strength decline of bolt goods.Therefore, the upper limit is defined as 600 ℃.Preferred temperature range is 400~550 ℃.In addition, if the hold-time surpasses 100 minutes, then not only the effect of age hardening is saturated, and according to circumstances makes the tensile strength of bolt goods reduce because of overaging.Therefore, the upper limit with the hold-time is defined as 100 minutes.The scope of preferred hold-time is 5~60 minutes.
Qualification reason to the 9th kind of mode~the 13 kind of mode of the present invention describes below.
In order to ensure the intensity of steel, add the C more than 0.005%., if add to surpass 0.05%, cold-workability deterioration not only then, and make also deterioration of solidity to corrosion because of generating the Cr carbide.Therefore, the upper limit is defined as below 0.05%.Preferred range is 0.01~0.03%.
In order to guarantee the intensity of cold working parts by solution strengthening, add the N more than 0.005%., if add more than 0.06%, then tensile strength rises, the cold-workability deterioration.Therefore, the upper limit is defined as is lower than 0.06%.In common two phase stainless steel, add N more than 0.06% for the use of the alloying element that reduces high price, but under the situation of steel of the present invention, it is characterized in that: by control tissue and become balance-dividing and N content is suppressed at low-level, thereby with soft state the cold-workability of wire rod is improved.Preferred range is more than 0.02% and is lower than 0.05%.
Consider that from the reason of above-mentioned cold-workability C+N is limited to below 0.09%.Be preferably below 0.07%.
For deoxidation, add the Si more than 0.1%., if add to surpass 1.0%, then make the cold-workability deterioration because of hardization.Therefore, the upper limit is defined as 1.0%.Preferred range is 0.2~0.6%.
As for deoxidation and in order to obtain ferrite+austenitic two phase constitutions and to make the austenite structure stabilization and the adjustment carried out, add the Mn more than 0.1%., if add to surpass 10.0%, then, solidity to corrosion and intensity makes the cold-workability deterioration because of rising.Therefore, the upper limit is defined as 10.0%.Preferred range is 0.5~5.0%.
Obtain ferrite+austenitic two phase constitutions in order to reduce the M value and make the austenite structure stabilization and guarantee cold-workability, add 1.6% Ni., even add to surpass 6.0%, its effect is also saturated, and because of Ni be that high valence elements makes the economy deterioration.Therefore, the upper limit is defined as 6.0%.Preferred range is 2.0~5.0%.
In order to ensure solidity to corrosion and obtain ferrite+austenitic two phase constitutions and make the austenite structure stabilization guarantee cold-workability, add the Cr more than 19.0%., surpass 30.0% even add, its effect is also saturated, opposite cold-workability deterioration.Therefore, the upper limit is defined as 30.0%.Preferred range is 20.0~26.0%.
Obtain ferrite+austenitic two phase constitutions in order to reduce the M value and make the austenite structure stabilization, suppress work hardening and cold-workability is improved, contain the Cu more than 0.05%., surpass 3.0%, then surpass the solid solubility of Cu, make the obvious deterioration of raw-material hot manufacturing therefore, the upper limit to be defined as 3.0% if contain.Preferred range is to be lower than 1.0%.
The M value of following formula (a) helps the stability of austenite phase, is " iron と Steel ", the index of record in 63 (1977), 772 pages, if the M value increases, then generates the martensitic phase that the processing of hard causes.When the cold forging of two phase stainless steel, if the M value, then generates the martensitic phase that the processing of hard causes, the obvious deterioration of cold-workability above 60 when cold working.Therefore, the M value is defined as below 60.Preferred range is below 40.
M=551-462(C+N)-9.2Si-8.1Mn-29(Ni+Cu)
-13.7Cr-18.5Mo (a)
The tensile strength of wire rod helps the cold-workability of wire rod very much, if the tensile strength of wire rod surpasses 700N/mm 2, then cold-workability significantly reduces.Therefore, the upper limit is defined as 700N/mm 2On the other hand, the tensile strength at wire rod is lower than 500N/mm 2The time, the intensity of cold-worked article is low excessively, as the value reduction of goods.Therefore, preferably undergage is decided to be 500N/mm 2Preferred range is 500~650N/mm 2
The tension fracture shrinking percentage of wire rod helps the cold-workability of wire rod very much, is lower than at 70% o'clock in the tension fracture shrinking percentage of wire rod, cold-workability deteriorations such as the processing of cold drawn silk, cold forging.Therefore, the upper limit is defined as more than 70%.Preferred range is more than 75%.
Magnetizability is the function that does not have in the austenite stainless steel, when linking operation, fastening piece utilize magnetizability to improve operation to Magnetic tools, under the situation in the food of sneaking into that comes off by wire netting, sieve aperture (particularly travelling belt of using of food etc.) generating material, utilize Magnetic Sensor to prevent to sneak into etc., very big in the function of industrial magnetizability.Therefore, limit magnetizability among the present invention.Be preferably more than 3.0 by specific permeability.
Mo is for improving the solidity to corrosion effective elements, by adding more than 0.1%, can stably obtaining effect., if add to surpass 3%, material hardization not only then, and separate out the σ phase makes the obvious deterioration of cold-workability.Therefore, the upper limit is defined as 3%.Preferred range is 0.3~1.0%.
B is for improving the hot workability effective elements, by adding more than 0.001%, can stably obtaining effect.,, then generate boride, make solidity to corrosion and cold-workability deterioration if add to surpass 0.01%.Therefore, the upper limit is defined as 0.01%.Preferred range is 0.002%~0.006%.
Al, Mg, Ca are effectively for deoxidation, therefore, by in adding more than the Al:0.005%, more than the Mg:0.001%, more than the Ca:0.001% more than one, can stably obtain effect., even make Al surpass 0.1% respectively, make Mg surpass 0.01%, make Ca surpass 0.01% ground to contain, its effect is also saturated, produces thick oxide compound (inclusion) on the contrary, the cold-workability deterioration.Therefore, respectively the upper limit is defined as Al:0.1%, Mg:0.01%, Ca:0.01%.Preferred range is to contain in Al:0.008%~0.06%, Mg:0.001~0.005%, Ca:0.001~0.005% more than one.
Nb, Ti, V, Zr guarantee that for the generation that suppresses the Cr carbonitride solidity to corrosion is effectively, by in adding more than the Nb:0.01%, more than the Ti:0.01%, more than the V:0.01%, more than the Zr:0.01% more than one, can stably obtain effect., even make Nb surpass 1.0%, make Ti surpass 0.5%, make V surpass 1.0%, make Zr surpass 1.0% ground to contain, its effect is also saturated, produces thick precipitate on the contrary, the cold-workability deterioration.Therefore, stipulate the upper limit of each element.Preferred range is to contain in Nb:0.05%~0.6%, Ti:0.05~0.5%, V:0.1~0.6%, Zr:0.05~0.6% more than one.
Usually, as unavoidable impurities, in manufacturing process, steel contains aerobic, but under situation of the present invention, as unavoidable impurities, preferably oxygen is defined as below 0.01%.
Embodiment 1
Below embodiments of the invention 1 are described.
The chemical constitution of the steel of embodiment 1 shown in table 1~4.
Figure GPA00001081188500131
Figure GPA00001081188500151
Figure GPA00001081188500161
With the steel fusing of the vacuum melting stove of 300kg with above-mentioned chemical constitution, be cast as the strand of φ 180mm, by wire rolling this strand is rolled down to φ 5.5~6.5mm, finish hot rolling at 1050 ℃, then be implemented in 1050 ℃ of melt processing of maintenance 5 minutes, water-cooled down by online thermal treatment, then, carry out pickling, make wire fabrication.Then, implement the oxalic acid epithelium and handle, light cold drawn silk is worked into φ 5.2mm, is finish-machined to the steel wire that cold forging is used.
Then, process into about 5000 hexagon bolts by cold forging and rolling.Then, its part is implemented 300~650 ℃, kept 3~200 minutes ageing treatment.Then, whole bolts are finish-machined to the hexagon bolt goods by cylinder grinding, cleaning.
Evaluation is that volume fraction, cold forging (crackle has or not, the damaged of instrument have or not), the tensile strength of bolt goods, the solidity to corrosion of the ferritic phase of tensile strength, steel wire to steel wire estimated.Its evaluation result is shown in table 5~8.
Figure GPA00001081188500181
Figure GPA00001081188500201
Figure GPA00001081188500211
Mechanical properties is to estimate according to tensile strength in the tension test of JIS Z 2241 and fracture shrinking percentage.In the steel wire of example of the present invention, all at 650~1000N/mm 2Scope in, in the bolt goods of example of the present invention, all at 700~1200N/mm 2Scope in, high strength is good.
Volume fraction about the ferritic phase of steel wire carries out mirror ultrafinish by the vertical section to steel wire, makes ferritic phase painted with reagent in the village, calculates area occupation ratio by image analysis and obtains volume fraction.The ferrite of the steel wire of example of the present invention divides rate in the scope of 45~85vol.%.
About cold forging, by implementing to forge processing, make 5000 hex hds with 3 sections upsetting machines, the damage that has or not with instrument of forge crack is estimated.Not the damage of generation instrument the time be chosen as life tools zero, be chosen as when the generation instrument is damaged life tools *.Cold crack does not take place in the wire rod of example of the present invention, is life tools zero, excellent in cold forging property.
About the solidity to corrosion of bolt goods,,, estimated and whether got rusty each 10 spray testings of implementing 100 hours of each bolt goods according to the salt spray testing of JIS Z 2371.So long as the level of not getting rusty and more only getting rusty just is evaluated as zero with solidity to corrosion, under the situation that the stream rust takes place, get rusty comprehensively, solidity to corrosion is evaluated as *.The resistance to rust of the bolt goods of example of the present invention all is zero.
On the other hand, comparative example No.38~61 outside scope of the present invention, deteriorations such as the intensity of cold forging, bolt goods, solidity to corrosion, dominance of the present invention is obvious.
Embodiment 2
Below embodiments of the invention 2 are described.
The chemical constitution (quality) of the steel that adopts among the embodiment 2 shown in the table 9,10 (for the examination material).
Figure GPA00001081188500231
With the steel fusing of the vacuum melting stove of 150kg with above-mentioned chemical constitution, be cast as the strand of φ 180mm, by wire rolling this strand is rolled down to φ 5.5mm, finish hot rolling at 1050 ℃, with this state, be implemented in 1050 ℃ of continuous heat treatment of maintenance 5 minutes, water-cooled down, carry out pickling then, make wire rod.Then, be worked into φ 2.0mm, this steel wire be cold worked into the wire netting of the mesh-like that travelling belt uses by bending machining with the strong cold drawn silk of common technology.
Estimate: tensile strength, tension fracture shrinking percentage, cold-workability, solidity to corrosion, magnetizability to wire rod are estimated.Its evaluation result sees Table 11,12.
Table 11
Figure GPA00001081188500261
Table 12
The tensile strength of wire rod and tension fracture shrinking percentage are to estimate according to tensile strength in the tension test of JIS Z 2241 and fracture shrinking percentage.In the wire rod of example of the present invention, all tensile strength is 500~700N/mm 2, the fracture shrinking percentage is 〉=70% scope.
Cold-workability is to estimate according to cold drawn silk processing and wire netting processibility thereafter.With do not have broken string, cold formability when being shaped as wire netting is evaluated as zero with losing, will be because of broken string, lose in the time of can not being shaped as wire netting be evaluated as *.In the wire rod of example of the present invention, not have broken string, lose, cold-workability is good.
About solidity to corrosion,, estimated and whether got rusty will after grind with #500 on the top layer of the wire rod of overpickling,, implementing 100 hours spray testing according to the salt spray testing of JIS Z2371.So long as the level of not getting rusty and more only getting rusty just is evaluated as zero with solidity to corrosion, the stream rust is taking place, when getting rusty solidity to corrosion is being evaluated as comprehensively *.The resistance to rust of example of the present invention all is zero.
About magnetizability, measured specific permeability by ferrite meter (simple and easy permeameter) with wire netting.Have magnetizability if specific permeability for can clearly confirm more than 3.0 of magnetizability, is evaluated as, will be lower than 3.0 average evaluation is no magnetizability.
On the other hand, comparative example No.86~107 are outside scope of the present invention, and in aspect deteriorations such as cold-workability, solidity to corrosion, cost, magnetizabilities, dominance of the present invention is obvious.
Each above embodiment shows, the duplex stainless steel that less contains the high anti-corrosion of Ni at high price of the present invention has good cold forging, and can carry out the high strength of bolt goods, high strength, high anti-corrosion bolt can be provided at an easy rate, and, also can in nut, use, industrial be very useful.
Each above embodiment shows, according to the present invention, can make the two phase stainless steel wire rod of soft, as to have magnetizability cheapness, can give very excellent cold-workability and with the equal solidity to corrosion of austenite stainless steels such as SUS304, SUS316, the high anti-corrosion cold-worked article that can provide screw, pin, wire netting, steel wire, wirerope, spring etc. to have magnetizability at an easy rate, industrial be very useful.

Claims (13)

1. the high strength of an excellent in cold forging property, high anti-corrosion bolt are the two-phase steel wire rod with austenite-ferrite, and it contains in quality %:
C:0.005~0.05%、
Si:0.1~1.0%、
Mn:0.1~10.0%、
Ni:1.0~6.0%、
Cr:19.0~30.0%、
Cu:0.05~3.0%、
N:0.005~0.20%,
Surplus by Fe and in fact unavoidable impurities constitute, C+N is below 0.20%, the M value of formula (a) is below 60, the F value of formula (b) is 45~85, tensile strength is 550~750N/mm 2,
M=551-462(C+N)-9.2Si-8.1Mn
-29(Ni+Cu)-13.7Cr-18.5Mo (a)
F=5.6Cr-7.1Ni+2.4Mo+15Si-3.1Mn-300C
-134N-26.6 (b)。
2. the high strength of excellent in cold forging property according to claim 1, high anti-corrosion bolt are the two-phase steel wire rod with austenite-ferrite, and wherein, % contains below the Mo:1.0% in quality.
3. the high strength of excellent in cold forging property according to claim 1 and 2, high anti-corrosion bolt are the two-phase steel wire rod with austenite-ferrite, and wherein, % contains below the B:0.01% in quality.
4. be the two-phase steel wire rod according to the high strength of each described excellent in cold forging property in the claim 1~3, high anti-corrosion bolt with austenite-ferrite, wherein, in quality % contain in the following element more than a kind:
Below the Al:0.1%,
Below the Mg:0.01%,
Below the Ca:0.01%.
5. be the two-phase steel wire rod according to the high strength of each described excellent in cold forging property in the claim 1~4, high anti-corrosion bolt with austenite-ferrite, wherein, in quality % contain in the following element more than a kind:
Below the Nb:1.0%,
Below the Ti:0.5%,
Below the V:1.0%,
Below the Zr:1.0%.
6. the high strength of an excellent in cold forging property, high anti-corrosion bolt are the two-phase steel wire with austenite-ferrite, and it has the chemical constitution of each record in the claim 1~5, and tensile strength is 700~1000N/mm 2
7. a high strength, high anti-corrosion bolt, it has the chemical constitution of each record in the claim 1~5, and tensile strength is 700~1200N/mm 2
8. the manufacture method of a high strength, high anti-corrosion bolt, wherein, the chemical constitution that will have each record in the claim 1~5, tensile strength is 700~1000N/mm 2Austenite-ferrite be after the cold-forming of two-phase steel wire becomes bolt, 300~600 ℃ of timeliness thermal treatments of implementing down 1~100 minute.
9. soft two phase stainless steel wire rod that cold-workability is good with magnetizability, it contains in quality %:
C:0.005~0.05%、
Si:0.1~1.0%、
Mn:0.1~10.0%、
Ni:1.6~6.0%、
Cr:19.0~30.0%、
Cu:0.05~3.0%、
N:0.005% is above and be lower than 0.06%,
Surplus by Fe and in fact unavoidable impurities constitute, C+N is below 0.09%, the M value of formula (a) is below 60, tensile strength is 700N/mm 2Below, the tension fracture shrinking percentage is more than 70%,
M=551-462(C+N)-9.2Si-8.1Mn-29(Ni+Cu)
-13.7Cr-18.5Mo (a)。
10. the soft two phase stainless steel wire rod with magnetizability that cold-workability according to claim 9 is good, wherein, % contains below the Mo:3.0% in quality.
11. according to claim 9 or the good soft two phase stainless steel wire rod with magnetizability of 10 described cold-workabilities, wherein, % contains below the B:0.01% in quality.
12. the soft two phase stainless steel wire rod with magnetizability good according to each described cold-workability in the claim 9~11, wherein, in quality % contain in the following element more than a kind:
Below the Al:0.1%,
Below the Mg:0.01%,
Below the Ca:0.01%.
13. the soft two phase stainless steel wire rod with magnetizability good according to each described cold-workability in the claim 9~12, wherein, in quality % contain in the following element more than a kind:
Below the Nb:1.0%,
Below the Ti:0.5%,
Below the V:1.0%,
Below the Zr:1.0%.
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