CN104513933A - Inexpensive non-magnetic stainless steel and manufacturing method thereof - Google Patents
Inexpensive non-magnetic stainless steel and manufacturing method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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Abstract
The invention relates to an inexpensive non-magnetic austenite stainless steel and a manufacturing method thereof. The components comprise, by weight, 0.05-0.12% of C, 0.2-1.0% of Si, 14.0-18.0% of Mn, 16.0-19.0% of Cr, 0-2.0% of Ni, 1.0-3.0% of Cu, 0.1-0.3% of N, 0.001-0.004% of B, and the balance of Fe and unavoidable impurities. According to the present invention, the finished product can maintain the non-magnetic state after 80% of the finished product is subjected to cold rolling reduction; low nickel pig iron with a nickel content of 1-2 wt% and produced by using inexpensive laterite-nickel ore can be adopted as the nickel resource raw material without application of other nickel-containing resources, such that the consumption of the high nickel iron or pure nickel can be substantially saved, and the low cost characteristic is provided; and the inexpensive non-magnetic austenite stainless steel of the present invention has characteristics of no magnetism, high strength, and excellent cold processing performance, and can be widely used in the industries of electrical devices, electronics, instrumentations, springs, zippers and the like.
Description
Technical field
The present invention relates to stainless material field, particularly one still non-magnetic cheap magnetism-free stainless steel and manufacture method thereof after heavy reduction distortion.
Background technology
The industries such as electrical equipment, electronics, instrument need a large amount of non-magnetic material, as hard disk, pointer, automobile instrument panel, medical facilities, spring members etc.The intensity of part industry to material also proposes high requirement.
At present, the conventional magnetism-free stainless steel trade mark comprises 301,304 and 305 etc.Problems existing mainly contains:
(1) many industries particularly electronic instrument industry requirement material still have nonmagnetic after certain shaping.And 301 and 304 belong to metastable austenite stainless steel, this kind of material easily produces strain-induced martensite tissue after the modes such as punching press, bending or reaming are out of shape, and causes this material to have certain magnetic.This kind of material needs high temperature annealing and cleanup acid treatment toward contact after being shaped, and this often extends life cycle of the product, brings energy consumption and environmental pollution simultaneously;
(2) although 305 stainless steels do not exist the problems referred to above substantially, because its nickel content reaches 10.5 ~ 13.0%, expensive, be only limited to high-end product, apply limited.
(3) due to nickel resources in recent years, the prices fluctuate much, uses the higher stainless material (as 304 and 305) of nickel content to bring huge cost pressure and risk control difficulty to enterprise.Therefore, produce can meet distortion after without the need to thermal treatment just with or without magnetic characteristic, while to have again cheap and stable stainless steel product necessary.
Chinese patent CN101311290A discloses a kind of without magnetic strength malleableize stainless steel and manufacture method thereof.The chemical composition of described nonmagnetic Strength-toughen stainless steel is: C≤0.12%, Si≤1.50%, Mn:14.5 ~ 16.5%, S≤0.010%, P≤0.03%, Cr:15.1 ~ 16.0%, Ni≤0.90%, Mo≤0.70%, Nb≤0.35%, N:0.25 ~ 0.50%, all the other are Fe and inevitable impurity.This invention, mainly for the manufacture of oil non-magnetic drill collar, because N content is higher, can only adopt die casting and forging process.Simultaneously because Ni content is low, and do not add Cu, cold-forming property is poor.
Chinese patent CN101538689B discloses a kind of non-magnetic stainless steel with high strength and toughness, its manufacture method and application.This stainless chemical component weight per-cent: C≤0.04, Si:0.35-0.65, Mn:17.0-22.0, Cr:13.0-17.0, Mo:0.30-0.50, Ni:0.15-0.45, N:0.30-0.80, P≤0.03, S≤0.005, all the other are Fe and inevitable impurity.This steel grade is mainly applied on oil drilling tools, has nonmagnetic preferably.But its Mn and N content high, it is large to smelt difficulty, and the method for continuous casting and hot rolling can not be adopted to produce.
Chinese patent CN101781740A discloses a kind of nonmagnetic corrosion-resistant stainless steel, and its composition is C≤0.03%, Si≤0.3%, P≤0.03%, S≤0.01%, Ni:12.0-12.5%, Cr:17.0 ~ 18.0%, Mo:2.0-2.5%, N:0.16-0.18%, Mn≤2.0%, surplus is Fe.This steel grade erosion resistance and nonmagnetic effect better, but employ higher Ni content, and cost of alloy is very high.
Chinese patent CN101386962A discloses a kind of non-magnetic high-strength stainless steel and manufacture method thereof.Its composition is: C0.05 ~ 0.20%, Si≤1.0%, Mn11 ~ 15%, S≤0.03%, P≤0.035%, Cr15 ~ 20%, Ni≤5.0%, Mo0.5 ~ 1.0%, N0.2 ~ 0.4%, and trace element≤0.50%, surplus is Fe.Although this invention magnetic is low, intensity is high, and its Ni content is high, less economical.Its manufacture method relates to non-vacuum induction furnace, electroslag heavily melts simultaneously, is not suitable for scale operation.
Chinese patent CN101435058B discloses a kind of austenitic stainless steel and production technique thereof, its composition is: C≤0.10%, Cr:12.5-15.0%, Mn:12.0-15.0%, Ni:0.5-1.5%, Cu:0.4 ~ 0.8%, N:0.08-0.16%, Si:0.4-0.8%, P≤0.035%, S≤0.02%, RE:0.08 ~ 0.18%, surplus is Fe and inevitable impurity.This steel grade Theoretical Calculation Md
30/50temperature value >-20 DEG C, therefore, can produce magnetic under certain deformation conditions.Simultaneously because Cr content is low, therefore solidity to corrosion is poor.In addition, itself Ni and Cu total amount is low, and cold-workability is poor.
Chinese patent CN101921969A discloses a kind of high-intensity non-magnetic rustproof spring steel, and its composition is: C:0.10-0.12%, Si:0.4-0.5%, P≤0.06%, S≤0.02%, Ni:1.2-1.4%, Cr:15.0-15.5%, Cu:1.5 ~ 1.7%, Mn:12.3-12.6%, clout is Fe.This steel grade carbon content is high, and Cr content is low, and erosion resistance is general.The not mentioned N content of this steel grade simultaneously, its theoretical Md
30/50>0 DEG C, can production magnetic after cold working.
Chinese patent CN101560634A and CN102560286A discloses a kind of non-magnetic high-strength austenitic stainless steel, but its Ni content is all more than 3.5%, and cost is higher.
Chinese patent CN102199738A and CN102002642A discloses a kind of non-magnetic high-strength stainless steel, but its N content is very high, and all more than 0.4%, be difficult to adopt continuous casting mode to produce, cost of alloy is high simultaneously.
Generally speaking, above published related invention patent all well can not take into account still non-magnetic requirement after gross distortion, and several key factor such as cost of alloy is low and manufacture difficulty is low.
Summary of the invention
The object of the present invention is to provide a kind of cheap magnetism-free stainless steel and manufacture method thereof, its Md
30/50temperature is lower than-70 DEG C, and the cold rolling draft of normal temperature does not have magnetic after reaching 80%, normal temperature relative magnetic permeability≤1.005; Simultaneously because the Ni resource in steel is from laterite or low nickel steel scrap, the cost of alloy of Ni can be ignored, and therefore price advantage is obvious; And after gross distortion without the need to anneal and nonmagnetic, cost performance is high, price steadiness, be applicable to scale operation and difficulty low (as applicable continuous casting, hot continuous rolling).
For achieving the above object, technical scheme of the present invention is:
A kind of cheap magnetism-free stainless steel of the present invention, its composition by weight percent is: C:0.05 ~ 0.12%, Si:0.2 ~ 1.0%, Mn:14.0 ~ 18.0%, Cr:16.0 ~ 18.5%, Ni:0 ~ 2.0%, Cu:1.0 ~ 3.0%, N:0.1 ~ 0.3%, B:0.001 ~ 0.004%, all the other are Fe and inevitable impurity; This stainless Md30/50 temperature lower than-70 DEG C, and does not have magnetic, normal temperature relative magnetic permeability≤1.005 after 80% under normal temperature cold rolling.
In present component design:
Carbon (C), C is strong formation, the element stablizing and expand austenitic area, and C plays an important role to forming austenite structure under room temperature.But C content is too high can reduce stainless plasticity, and unfavorable to stainless solidity to corrosion, and so C will have suitable percentage composition, therefore, controlling C content in steel of the present invention is 0.05-0.12%.
Silicon (Si), Si is that ferrite is formed and stable element.Si is for deoxidation in fusion process, and Si can improve the hot strength of ferritic phase simultaneously, therefore contains the Si of more than 0.2% in general stainless steel.But will the solubleness of N be reduced during Si too high levels, and accelerate the precipitation of intermetallic phase.Therefore, in steel of the present invention, control Si content is 0.2-1.0%.
Manganese (Mn), Mn is more weak austenite former, but is strong austenite structure stable element in stainless steel, and can improve the solubleness of N in steel.In low nickle type austenitic stainless steel, in Mn and steel, the elements compounding effect such as C, N, replaces part Ni, guarantees that stainless steel is at room temperature austenite structure.The interpolation of Mn also can reduce Md in addition
30/50temperature, often adds 1%Mn, can make Md
30/50temperature reduces by 8 DEG C.For guaranteeing the stability of austenite structure, and save the usage quantity of Ni, the present invention's control Mn content is 14-18%.
Chromium (Cr), Cr is the most important element that steel obtains corrosion resistance nature.Because Cr is the element significantly strengthening corrosion resistance nature, for ensureing good solidity to corrosion, in steel of the present invention, Cr content controls more than 16.0%.But Cr is main ferrite former, too high Cr will cause occurring ferritic phase in material, obtain completely without the austenite of magnetic, therefore need corresponding higher nickel equivalent to coordinate with it under can not ensureing room temperature state, to ensure to obtain room temperature austenite structure.Therefore, in steel of the present invention, Cr content controls at 16.0-18.5%.
Nickel (Ni), Ni forms element mutually most important with stable austenite, and can strengthen the ability of stainless steel resistance to reduction acid and improve processing characteristics, but in order to reduce costs, the present invention reduces the content of Ni greatly, restriction Ni content≤2.0%.
Copper (Cu), Cu is a kind of austenite former, can improve stainless steel cold-forming property and improve the corrosion resistance in reductive acid.But along with the raising of Cu content, stainless hot workability is deteriorated, and therefore the present invention adds the Cu of 1.0 ~ 3.0% weight.
Nitrogen (N), N is the element forming, stablize and expand austenitic area very consumingly in stainless steel.The present invention reduces Md by adding N
30/50temperature, effectively suppresses the formation of magnetic martensitic phase in strain path.N except substituting noble metal as except Ni, can also significantly improve the intensity of material, can also improve stainless rustless property, solidity to corrosion and delay the precipitation etc. of carbide in stainless steel under the prerequisite of not obvious reduction material plasticity and toughness.But because the solubleness of N in stainless steel is limited, when N content is too high, raising smelted and hot worked difficulty, especially the raising of N content will cause serious hot-rolling edge cracking, make it be difficult to produce on existing product line.Therefore, in steel of the present invention, N content controls at 0.1-0.3%.
Boron (B), the B of trace can improve stainless hot workability, but too much add B and also can play negative effect.Therefore in steel of the present invention, B content controls at 0.001-0.004%.
In order to increase the stability of the stainless austenite structure of the present invention, namely preventing from occurring martensite Magnetic Phase in material deformation process, needing alloying element proportioning reasonable in design.Generally use Md
30/50temperature evaluates the trend that austenite phase transition is deformation martensite phase, when its implication is strain 50%, produces the temperature that martensitic phase content reaches 30%.In other words, when material is out of shape 50% at such a temperature, martensitic phase content can reach 30%.Md
30/50temperature is higher, represents austenite in this material more unstable mutually, and the trend of material generation strain induced martensite transformation is more obvious.Md can be calculated by following experimental formula
30/50temperature (wherein each element all gets mass percent):
Md
30/50＝413-9.5Ni%-13.7Cr%-8.1Mn%-9.2Si%-462(C%+N%)
The Md of 304 steel is calculated according to this experimental formula
30/50=40 DEG C, higher.Therefore 304 stainless steels are at normal temperatures after certain strain, can produce strain-induced martensite and cause material to be magnetic.
The manufacture method of the cheap magnetism-free stainless steel of the present invention, comprises the steps:
1) smelt, cast
Smelt by mentioned component, wherein, the molten iron of blast fumance or not nickeliferous steel scrap are added as mother liquor after electric furnace, the Ni in mother liquor from the Ni content utilizing red soil nickel ore to produce be the low ferronickel water of 1.0 ~ 2.0wt% or its cool the low nickel pig made; Mother liquor enters argon oxygen decarburizing furnace, ladle refining furnace is smelted, and then molten steel is cast into slab, casting superheating temperature 20 ~ 60 DEG C, pulling rate 0.5 ~ 2.0m/min;
2) hot rolling
By heating of plate blank to 1100 ~ 1250 DEG C, batch after being then hot-rolled down to target thickness;
3) cold rolling or cold forging
Annealed at the temperature of 1000 ~ 1150 DEG C in continuous furnace by hot rolled coil, then pickling cold rolling, cold rolling draft scope is 0 ~ 80%, or Cold Forging is to required thickness, and the steel plate of acquisition does not produce magnetic.
Further, when without nickel content >=0.4wt% in magnetic austenitic stainless steel, the nickel raw material of employing from: the nickel content utilizing red soil nickel ore to produce be the low ferronickel water of 1.0 ~ 2.0wt% or its cool the low nickel pig made; When without nickel content < 0.4wt% in magnetic austenitic stainless steel, adopt and do not add nickel-bearing raw material or adopt nickel remaining in steel scrap to produce.
The present invention is the economy of the raw material that smelting uses and batching thereof improving the measure in product economy.Its raw material adopted comprises: low ferronickel water or the low nickel pig iron, ferrochrome, ferrosilicon, manganese metal, electrolytic copper, steel scrap etc.Nickel-bearing raw material wherein cools from: the low ferronickel water that blast furnace directly utilizes red soil nickel ore to produce or its low nickel pig (Ni content is 1.0 ~ 2.0wt%) made, and does not add Ni content at the ferronickel of more than 10wt% and pure nickel raw material.When this kind that adds different ratios low ferronickel water or the low nickel pig iron, the magnetism-free stainless steel that the present invention that can smelt Ni content >=0.4wt% mentions.If do not add any low ferronickel water or the low nickel pig iron and other ferronickel resources, the magnetism-free stainless steel that the present invention that can smelt Ni content < 0.4wt% mentions, Ni is wherein from Ni remaining in steel scrap.
The advantage of the more existing magnetism-free stainless steel of the present invention is:
(1) Composition Control is reasonable, easily accomplishes scale production.Nitrogen content as design is moderate, easily controls in steel-making, continuous casting and course of hot rolling, and nitrogen can solid solution in continuously cast bloom, does not produce bubble, does not produce limit in the hot rolling and split; And the steel grade of other nitrogen contents more than 0.3% is difficult to realize continuous casting, and in the hot rolling easily produce limit split;
(2) save expensive nickel resources, cost of alloy is low.Adopt novel batching pattern according to composition characteristic, nickel element wherein adopts the nickel resources from red soil nickel ore, and the ferronickel of Ni content that need not be expensive more than 10% and pure nickel resource;
(3) Md
30/50temperature value is low, after cold rolling large pressure, still nonmagnetic, easy cold working;
(4) chromium content is high, and solidity to corrosion is better.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Of the present invention as follows without magnetic austenitic stainless steel manufacturing process: blast furnace/electrosmelting → argon oxygen decarburizing furnace smelting → external refining → continuous casting/die casting → hot rolling → heat is moved back pickling → cold rolling or cold forging → cold and moved back pickling.
The embodiment of the present invention adopts the two-step approach of electric furnace, argon oxygen decarburizing furnace (AOD) to smelt, melt after the raw materials such as the low nickel pig iron, ferrochrome, ferrosilicon, manganese metal, electrolytic copper, steel scrap being added electric furnace according to certain proportioning in smelting process, molten steel is poured into AOD furnace after melting down, the blowing of de-C, de-S and increasing N, control N is carried out in AOD furnace, after smelting composition is qualified, molten steel is cast.It should be noted that: do not add Ni content in smelting process in the ferronickel of more than 10wt% and pure nickel resource.After casting, strand is heated to 1100-1250 DEG C, Hot Rolling Mill is rolled down to desired thickness, then carry out annealing and pickling; Afterwards, it is cold rolling on cold rolling mill heat to be moved back acid-cleaning plate, and draft scope is 0 ~ 80%, final obtain after heavy reduction distortion still non-magnetic without nickel or few nickel cheapness austenitic stainless steel.The intensity of concrete thickness required for user and hardness are determined.
The composition of various embodiments of the present invention and Md
30/50be worth as shown in table 1.
The composition of table 1 embodiment of the present invention and Md
30/50value
Each embodiment, after cold rolling different draught, have detected the content of magnetic martensitic phase in material with magnetic tester.Get the cold-reduced sheet of respective thickness, be processed into the mechanical stretch sample of JIS13B standard, carry out intensity and hardness determination, result is as shown in table 2 simultaneously.
The magnetic of table 2 embodiment of the present invention and mechanical property
From table 1 and table 2, the Md of various embodiments of the present invention Theoretical Calculation
30/50temperature value is all less than-70 DEG C.Each embodiment after about 80%, does not all detect magnetic with magnetic tester under cold rolling, therefore to meet after heavy reduction distortion still non-magnetic feature.And in smelting process, do not use expensive high ferronickel (nickel content is at more than 10wt%) raw material, there is good economy.Therefore, the present invention can be widely used in electrical equipment, electronics, instrument, spring, slide fastener etc. and require after material deformation still non-magnetic stainless material application industry, has wide market application foreground.
Claims (3)
1. a cheapness is without magnetic austenitic stainless steel, its composition by weight percent is: C:0.05 ~ 0.12%, Si:0.2 ~ 1.0%, Mn:14.0 ~ 18.0%, Cr:16.0 ~ 18.5%, Ni:0 ~ 2.0%, Cu:1.0 ~ 3.0%, N:0.1 ~ 0.3%, B:0.001 ~ 0.004%, all the other are Fe and inevitable impurity; This stainless Md
30/50temperature lower than-70 DEG C, and does not have magnetic, normal temperature relative magnetic permeability≤1.005 after 80% under normal temperature cold rolling.
2. the manufacture method of cheap magnetism-free stainless steel as claimed in claim 1, comprises the steps:
1) smelt, cast
Smelt by mentioned component, wherein, the molten iron of blast fumance or not nickeliferous steel scrap are added as mother liquor after electric furnace, the Ni in mother liquor from the Ni content utilizing red soil nickel ore to produce be the low ferronickel water of 1.0 ~ 2.0wt% or its cool the low nickel pig made; Mother liquor enters argon oxygen decarburizing furnace, ladle refining furnace is smelted, and then molten steel is cast into slab, casting superheating temperature 20 ~ 60 DEG C, pulling rate 0.5 ~ 2.0m/min;
2) hot rolling
By heating of plate blank to 1100 ~ 1250 DEG C, batch after being then hot-rolled down to target thickness;
3) cold rolling or cold forging
Annealed at the temperature of 1000 ~ 1150 DEG C in continuous furnace by hot rolled coil, then pickling cold rolling, cold rolling draft scope is 0 ~ 80%, or Cold Forging is to required thickness, and the steel plate of acquisition does not produce magnetic.
3. the manufacture method of cheap magnetism-free stainless steel as claimed in claim 2, it is characterized in that, as described nickel content >=0.4wt% without in magnetic austenitic stainless steel, the nickel raw material of employing from: the nickel content utilizing red soil nickel ore to produce be the low ferronickel water of 1.0 ~ 2.0wt% or its cool the low nickel pig made; When without nickel content < 0.4wt% in magnetic austenitic stainless steel, adopt and do not add nickel-bearing raw material or adopt nickel remaining in steel scrap to produce.
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| CN105839022A (en) * | 2016-03-31 | 2016-08-10 | 宝钢不锈钢有限公司 | High-hardness non-magnetic nickelless stainless steel and manufacturing method thereof |
| CN105908100A (en) * | 2016-04-27 | 2016-08-31 | 无锡环宇精密铸造有限公司 | Production method of nonmagnetic stainless steel casting |
| CN106868423A (en) * | 2017-01-20 | 2017-06-20 | 宁波市博祥新材料科技有限公司 | The manufacture method and its product of a kind of low nickel magnetism-free stainless steel of high manganese and high nitrogen |
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| CN111020406A (en) * | 2019-12-13 | 2020-04-17 | 浦项(张家港)不锈钢股份有限公司 | Low-nickel all-austenite nonmagnetic stainless steel and manufacturing method and application thereof |
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| CN105839022A (en) * | 2016-03-31 | 2016-08-10 | 宝钢不锈钢有限公司 | High-hardness non-magnetic nickelless stainless steel and manufacturing method thereof |
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| CN108637032A (en) * | 2018-04-18 | 2018-10-12 | 苏州启航不锈钢制品有限公司 | Zero magnet spring essence line of one kind and its production and processing technology |
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