CN102439188A - High manganese nitrogen-containing steel sheet having high strength and high ductility and method for manufacturing same - Google Patents
High manganese nitrogen-containing steel sheet having high strength and high ductility and method for manufacturing same Download PDFInfo
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- CN102439188A CN102439188A CN2010800190970A CN201080019097A CN102439188A CN 102439188 A CN102439188 A CN 102439188A CN 2010800190970 A CN2010800190970 A CN 2010800190970A CN 201080019097 A CN201080019097 A CN 201080019097A CN 102439188 A CN102439188 A CN 102439188A
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 174
- 239000010959 steel Substances 0.000 title claims abstract description 174
- RBVYPNHAAJQXIW-UHFFFAOYSA-N azanylidynemanganese Chemical compound [N].[Mn] RBVYPNHAAJQXIW-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims description 50
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 126
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 65
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 39
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 36
- 239000011651 chromium Substances 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 32
- 239000012535 impurity Substances 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 40
- 239000011572 manganese Substances 0.000 claims description 40
- 229910052748 manganese Inorganic materials 0.000 claims description 40
- 238000002844 melting Methods 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000005098 hot rolling Methods 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- PWKWDCOTNGQLID-UHFFFAOYSA-N [N].[Ar] Chemical compound [N].[Ar] PWKWDCOTNGQLID-UHFFFAOYSA-N 0.000 claims description 11
- 229910052758 niobium Inorganic materials 0.000 claims description 11
- 239000010955 niobium Substances 0.000 claims description 11
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 229910052720 vanadium Inorganic materials 0.000 claims description 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 9
- 238000005097 cold rolling Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims 3
- 239000012300 argon atmosphere Substances 0.000 claims 1
- 238000005096 rolling process Methods 0.000 claims 1
- 229910001566 austenite Inorganic materials 0.000 abstract description 28
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 9
- 238000005482 strain hardening Methods 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 16
- 229910000734 martensite Inorganic materials 0.000 description 16
- 230000001939 inductive effect Effects 0.000 description 15
- 239000004411 aluminium Substances 0.000 description 12
- 230000002950 deficient Effects 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910000794 TRIP steel Inorganic materials 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000006104 solid solution Substances 0.000 description 6
- 238000007669 thermal treatment Methods 0.000 description 6
- 229910000885 Dual-phase steel Inorganic materials 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- 238000005728 strengthening Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000014509 gene expression Effects 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 229910000617 Mangalloy Inorganic materials 0.000 description 2
- 229910000937 TWIP steel Inorganic materials 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000797 Ultra-high-strength steel Inorganic materials 0.000 description 1
- 238000010314 arc-melting process Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000003450 growing effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
-
- 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
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
-
- 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
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- 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
- C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/001—Austenite
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/004—Dispersions; Precipitations
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- Materials Engineering (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Heat Treatment Of Sheet Steel (AREA)
Abstract
The invention provides a high manganese nitrogen steel plate. The high manganese nitrogen steel sheet of the present invention comprises: 0.5 to 1.0 weight percent of carbon, 10 to 20 weight percent of manganese, 0.02 to 0.3 weight percent of nitrogen, and the balance of iron and unavoidable impurities. The high manganese nitrogen-containing steel sheet of the present invention forms an austenite structure at normal temperature, in which the stacking fault energy is effectively adjusted by adding chromium and nitrogen. Thus, the high manganese-nitrogen steel sheet of the present invention generates mechanical twins during plastic deformation, thereby achieving a high work hardening rate and tensile strength as well as excellent workability.
Description
Technical field
The present invention relates to have the high manganese nitrogen steel plate of HS and high ductibility, relate in more detail and can have the automotive sheet of higher formability and high manganese nitrogen steel plate and the method for manufacture thereof that looks like the impact absorbing material of automotive bumper reinforcing member and so on as requiring.
Background technology
The higher formability of steel plate basic need that is used for body of a motor car etc.In order to address that need, used mostly in the past that tensile strength is low to be merely about 200～300Mpa, but the good ultra low-carbon steel of formability is as autobody sheet.But, to the concern of environmental problems such as topsoil, the method for a lot of raising automobile fuel efficiency has been proposed along with recently.Particularly,, require autobody sheet not only to have higher formability, also have higher intensity along with the lightweight of paying attention to automobile in order to improve fuel efficiency.
And; Be directly connected to passenger's safety as the auto parts machinery of impact absorbing material in automotive bumper reinforcing member or the car door and so on; Thereby the significantly increase of the commercialization necessity of ultrahigh-strength steel, for example be necessary to use to have the steel plate that has higher unit elongation when tensile strength is generally the superstrength more than the 780Mpa.
This automobile high-strength steel for example has two-phase (DP:Dual Phase) steel, phase-change induced plastic (TRIP:TRansformation Induced Plasticity) steel, twin induced plastic (TWIP:Twin Induced Plasticity) steel etc.
At first; Dual phase steel obtains through following method: after steel is carried out hot rolling, be cooled in the process of normal temperature; Make final cooling temperature be lower than Ms (martensite start) point (Ms) and make an austenitic part change martensite into, thereby have the two-phase that constitutes by martensite and this two-phase structure of ferritic of austenitic transformation by at normal temperatures.This dual phase steel (DP steel) can obtain various mechanical propertys through regulating martensite and ferritic molar ratio.
Transformation induced plasticity steel (TRIP steel) shows excellent workability, and obtains in the following manner: after local organization becomes residual austenite, in the accessory moulding process, make austenite to martensitic transformation.Significant work hardening has the high advantage of intensity to this TRIP steel because of martensitic transformation causes, but has the low excessively defective of unit elongation.
Promptly; The Work-hardening Mechanism of dual phase steel and transformation induced plasticity steel is mainly utilized the martensitic stucture as hard phase; But this martensite demonstrates higher work hardening increment rate in plastic history, therefore, though can produce high-intensity hot-rolled steel sheet; But because the ductility extreme difference, thereby has the defective that is difficult to guarantee the unit elongation more than 30%.
On the other hand, twin inducing plasticity steel (TWIP steel) contains a large amount of manganese and has stable austenite one phase at normal temperatures, in the accessory course of processing, in its austenite structure, forms mechanical twin and increases the work hardening degree.That is, the standard weave of twin inducing plasticity steel is an austenite, is not ferritic, and in plastic history, constantly forms the motion that mechanical twin hinders dislocation at the austenite crystal intragranular, thereby extraly obtains drawing hardening effect and have good unit elongation.And twin inducing plasticity steel can cause the mechanical twin of the work hardening of height owing to forming, thereby not only can obtain higher unit elongation, can also obtain higher draw tensile strength.Particularly, the unit elongation of twin inducing plasticity steel is higher by 50% than dual phase steel or transformation induced plasticity steel in the past, thereby is preferably used as automotive sheet.
Yet; The twin inducing plasticity steel of being developed so far since the content of the manganese that is used to guarantee stabilization of austenite and regulate stacking fault energy up to about 18-30%; And except manganese, also need add a large amount of aluminium or silicon etc., thereby has the defective that causes materials cost or manufacturing expense significantly to increase.And, also have because of the volatilization of manganese in steel making working procedure or continuous casting working procedure or temperature reduction etc. cause the bigger defective of appending the manufacturing expense burden, thereby the requirement that is proposing to develop the twin inducing plasticity steel that reduces manganese content.And; Aspect from mechanical property; The ys that the twin inducing plasticity steel of being developed so far has only is about 300Mpa, and tensile strength also is no more than the defective of 1GPa, thereby need provide a kind of when keeping unit elongation and then improve the steel plate of intensity.
Summary of the invention
Technical problem
Thus, the objective of the invention is to, a kind of steel plate that can remedy the defective that dual phase steel, transformation induced plasticity steel and twin inducing plasticity steel had in the past is provided.
Specifically, the objective of the invention is to, a kind of content that can reduce manganese is provided, and have the steel plate of HS and high ductibility simultaneously.
In addition, the objective of the invention is to, provide a kind of usefulness cheap element substitution manganese, it is higher that intensity and ductility are compared the steel plate that contains a large amount of manganese, and the steel plate of processing more easily.
And, the objective of the invention is to, a kind of method of manufacture that can improve the high manganese nitrogen steel plate of nitrogen content is provided.
The means of dealing with problems
To achieve these goals; The present invention provides a kind of high manganese nitrogen steel plate; It is characterized in that, comprise: the carbon of 0.5 weight percent to 1.0 weight percent, the manganese of 10 weight percent to 20 weight percents; 0.02 the nitrogen of weight percent to 0.2 weight percent, the iron of surplus and unavoidable impurities.
Perhaps, to achieve these goals, the present invention provides a kind of high manganese nitrogen steel plate; It is characterized in that; Comprise: the carbon of 0.5 weight percent to 1.0 weight percent, the chromium below the manganese of 10 weight percent to 20 weight percents, 4.0 weight percents; 0.02 the nitrogen of weight percent to 0.3 weight percent, the iron of surplus and unavoidable impurities.
Perhaps; To achieve these goals, the present invention provides a kind of high manganese nitrogen steel plate, it is characterized in that; Comprise: the carbon of 0.5 weight percent to 1.0 weight percent; Chromium below the manganese of 10 weight percent to 20 weight percents, 4.0 weight percents, the nitrogen of 0.02 weight percent to 0.3 weight percent; Less than the silicon of 4 weight percents, less than the aluminium of 3 weight percents, less than the niobium of 0.30 weight percent, less than the titanium of 0.30 weight percent and at least a less than in the vanadium of 0.30 weight percent, the iron of surplus and unavoidable impurities.
In this case, at least a portion of above-mentioned nitrogen can be comprised in the above-mentioned steel plate through arc-melting (arc-melting) method.
In above-mentioned high manganese nitrogen steel plate, the product of tensile strength and breaking elongation (TS * El) can be more than the 50000MPa%.
And, can comprise the manganese of 15 weight percent to 18 weight percents.
And, can comprise the nitrogen of 0.10 weight percent to 0.3 weight percent.
And above-mentioned steel plate can be a hot-rolled steel sheet.
Perhaps, above-mentioned steel plate can be cold rolled annealed steel plate.
To achieve these goals, the present invention provides a kind of method of manufacture of high manganese nitrogen steel plate, it is characterized in that, comprises following step: the step that electrolytic iron, electrolytic manganese and carbon dust is disposed at the inside of treatment chamber; Step with the above-mentioned treatment chamber of argon-nitrogen gas atmosphere filling; And the step of above-mentioned electrolytic iron, electrolytic manganese and carbon dust being carried out arc-melting.
And, can repeatedly carry out above-mentioned arc-melting repeatedly.
And the ratio of the nitrogen in above-mentioned nitrogen-argon atmospher can be 0.2 to 0.8.
And aforesaid method also can comprise following step: under the temperature more than 900 ℃, above-mentioned high nitrogen steel plate is carried out the hot rolled step; And the step of the above-mentioned steel plate after the hot rolling being carried out air cooling or forced air-cooling.
And aforesaid method also can comprise following step: with the draft more than 50% cooled above-mentioned steel plate is carried out cold rolling step at normal temperatures; Under the temperature more than 800 ℃ to the heat treated step of annealing of the above-mentioned steel plate after cold rolling; And the step of the above-mentioned steel plate of annealing after the thermal treatment being carried out air cooling or forced air-cooling.
And; The steel plate that forms through aforesaid method can comprise: the carbon of 0.5 weight percent to 1.0 weight percent; The manganese of 10 weight percent to 20 weight percents, the nitrogen of 0.02 weight percent to 0.2 weight percent, the iron of surplus and unavoidable impurities.
And the raw material that in aforesaid method, is disposed at the inside of above-mentioned treatment chamber also can comprise chromium.
In this case; The steel plate that forms through aforesaid method can comprise: the carbon of 0.5 weight percent to 1.0 weight percent; The manganese of 10 weight percent to 20 weight percents; 4.0 the chromium below the weight percent, the nitrogen of 0.02 weight percent to 0.2 weight percent, the iron of surplus and unavoidable impurities.
And the raw material that in aforesaid method, is disposed at the inside of above-mentioned treatment chamber also can comprise chromium, and can comprise at least a in silicon, aluminium, niobium, titanium and the vanadium.
In this case; The steel plate that forms through aforesaid method can comprise: the carbon of 0.5 weight percent to 1.0 weight percent; The manganese of 10 weight percent to 20 weight percents; 4.0 the chromium below the weight percent; 0.02 the nitrogen of weight percent to 0.3 weight percent is less than the silicon of 4 weight percents, less than the aluminium of 3 weight percents, less than the niobium of 0.30 weight percent, less than the titanium of 0.30 weight percent and at least a less than in the vanadium of 0.30 weight percent, the iron of surplus and unavoidable impurities.
The effect of invention
According to exemplary embodiment of the present invention, high manganese nitrogen steel plate of the present invention forms austenite structure at normal temperatures, and comes to regulate effectively stacking fault energy through adding chromium and nitrogen.Thus, in the plastic history of this steel plate, produce mechanical twin and obtain higher work hardening and tensile strength and good workability.Promptly; In the high manganese nitrogen steel plate of exemplary embodiment of the present invention, the product of tensile strength and breaking elongation (TS *, compare with twin inducing plasticity steel in the past El) up to more than the 50000MPa%; Not only the product of tensile strength and breaking elongation is significantly bigger, and manufacturing cost is also cheaper.
And the high manganese nitrogen steel plate of exemplary embodiment of the present invention can use with various forms such as hot-rolled steel sheet and cold rolled annealed steel plate.
Description of drawings
Fig. 1 is the electron micrograph of the high manganese nitrogen steel plate of one embodiment of the invention.
Fig. 2 is the figure of expression through the tensile strength curve of the steel of experimental example 9 formation.
Embodiment
Below, will describe with reference to the exemplary embodiment of accompanying drawing high manganese nitrogen steel plate of the present invention and method of manufacture thereof.
Compare with twin induced plastic (TWIP) steel in the past of the manganese that comprises 20 weight percents, exemplary embodiment of the present invention reduces to 10～20% with the content of manganese, and adds carbon and nitrogen and obtain the austenite one phase tissue at normal temperatures.Particularly, nitrogen also influences stacking fault energy except influencing solid solution strengthening effect, thereby can induce the formation of mechanical twin.
Thus; The high manganese nitrogen steel plate of exemplary embodiment of the present invention can be through comprising above-mentioned alloying element; Make content be lower than twin inducing plasticity steel in the past such as high price alloying elements such as manganese or aluminium; And unit elongation is reached more than 50%, have higher ys and the tensile strength of comparing in the past of twin inducing plasticity steel simultaneously.
At first; The high manganese nitrogen steel plate of the first embodiment of the present invention comprises: the carbon of 0.5 weight percent to 1.0 weight percent; The manganese of 10 weight percent to 20 weight percents, the nitrogen of 0.02 weight percent to 0.3 weight percent, the iron of surplus and unavoidable impurities.
Specifically, the high manganese nitrogen steel plate of the first embodiment of the present invention comprises the manganese of 10 weight percent to 20 weight percents.That is,, thereby importantly, in iron-carbon phase diagram, make the pyritous austenite region be expanded to the austenite region of normal temperature because twin inducing plasticity steel forms mechanical twin in the austenitic matrix of normal temperature in plastic history.Present embodiment utilizes manganese as the austenite stabilizer element that is used to realize this result.
And in the steel plate of present embodiment, the content of manganese is 15 weight percent to 18 weight percents more preferably.Content at manganese reaches under the situation of 15 weight percents, owing to can guarantee stabilization of austenite, and reduce the generation that stacking fault energy promotes mechanical twin in the plastic history effectively, and thereby tensile strength * unit elongation is long-pending very high.
On the other hand, if the content of manganese less than 10 weight percents, then the stability because of the austenite phase significantly reduces, and causes in the process of hot rolling postcooling in austenite region, producing ferritic or martensitic phase.And, if the content of manganese is less than 10 weight percents, then because of the stacking fault energy of the austenite phase too high defective that is difficult to form mechanical twin that exists that becomes.
And, if the content of manganese greater than 20 weight percents, then because of the stacking fault energy too high viscous deformation that does not form twin and the austenite phase takes place that becomes, causes the mechanical property variation.
And the high manganese nitrogen steel plate of present embodiment comprises the carbon of 0.5 weight percent to 1.0 weight percent.That is, the content of manganese is that the iron-manganese binary alloy below 20 weight percents can't obtain the austenite one phase tissue at normal temperatures, and some forms ε martensite or α ' martensite.Thus, in the present embodiment, in order to obtain the austenite one phase tissue at normal temperatures, added not only cheap but also as the carbon of strong austenite stabilizer element.
On the other hand; If the content of carbon is less than 0.5 weight percent; Then because austenitic stability still fully is difficult to obtain austenite one phase inadequately in the process of hot rolling postcooling; Even perhaps obtained austenite one phase at normal temperatures, also become transformation induced plasticity steel (TRIP steel), thereby can not obtain required twin inducing plasticity steel (TWIP steel) owing to undergoing phase transition to martensite from austenite when the viscous deformation.
And, if the content of carbon greater than 1.0 weight percents, though then can obtain stable austenite at normal temperatures, reduces unit elongation or reduces weldableness owing to separating out of cementite taken place.And, if the content of carbon greater than 1.0 weight percents, then because stacking fault energy becomes too high, and has the defective that is difficult in deformation process, generate mechanical twin.
And the high manganese nitrogen steel plate of first embodiment comprises the nitrogen of 0.02 weight percent to 0.30 weight percent.Specifically, nitrogen is as making the interstitial element of austenite phase stabilization, if increase the addition of nitrogen, and just as the carbon that kind can obtain to improve stabilization of austenite, and the effect of gaining in strength through solution strengthening.And,, can not improve stacking fault energy yet, thereby can easily generate mechanical twin even the content of nitrogen increases.
On the other hand, according to present embodiment, be 0.10 weight percent when above at the content of nitrogen, the solid solution strengthening effect grow, thus the beneficial effect that makes that the ys of steel plate significantly improves is provided.
And; The content of nitrogen only reaches the content degree of when forming general steel plate, introducing as impurity less than the situation of 0.02 weight percent; Thereby have and be difficult to improve austenitic stability; Might under normal temperature, form ferritic or martensitic phase after the hot rolling, and be difficult to obtain the defective of the function that is used to regulate stacking fault energy.On the other hand; The technology that under not adding as the situation of the additional elements of chromium and so on, improves nitrogen content belongs to a highly difficult technology; But according to the present invention; Particularly can the content of nitrogen be brought up to more than 0.1 weight percent, more preferably more than 0.2 weight percent through utilizing the following arc-melting method that will explain.
Then; The high manganese nitrogen steel plate of the second embodiment of the present invention comprises: the carbon of 0.5 weight percent to 1.0 weight percent; Chromium below the manganese of 10 weight percent to 20 weight percents, 4.0 weight percents, the nitrogen of 0.02 weight percent to 0.3 weight percent; Chromium below 4 weight percents, the iron of surplus and unavoidable impurities.
At first, chromium not only can improve the solidity to corrosion of steel, can also improve the solid solubility of nitrogen.And chromium also makes the stacking fault energy that increases along with the interpolation of carbon reduce, and promotes the formation of mechanical twin thus.But chromium is as ferrite stabilizer, if addition greater than 4.0 weight percents, then can generate a part of ferritic in course of hot rolling.And chromium exists under situation about too much using and causes the too high defective of manufacturing cost as advanced material, thereby, can the content of chromium be controlled at below 4 weight percents.
And, under the situation of content greater than 0.30 weight percent of nitrogen,, also need increase the addition of chromium in order to make nitrogen in the inner a large amount of solid solutions of steel plate, this will cause manufacturing expense to increase, because of rather than optimal way.
And the reason of the content range of control other compositions in addition is with identical in the reason of first embodiment explanation, and the Therefore, omited specifies.
Then; The high manganese nitrogen steel plate of the third embodiment of the present invention comprises: the carbon of 0.5 weight percent to 1.0 weight percent; The manganese of 10 weight percent to 20 weight percents; 4.0 the chromium below the weight percent; 0.02 the nitrogen of weight percent to 0.3 weight percent is less than the silicon of 4 weight percents, less than the aluminium of 3 weight percents, less than the niobium of 0.30 weight percent, less than the titanium of 0.30 weight percent and at least a less than in the vanadium of 0.30 weight percent, the iron of surplus and unavoidable impurities.
Specifically, under the situation of adding the silicon below 4 weight percents, can reduce grain fineness number, finally increase ys and improve intensity through the solid solution strengthening effect that silicon plays.And the interpolation of silicon causes the stacking fault energy of steel to reduce, thereby makes the generation of the mechanical twin in the plastic history more smooth.
But, under the situation of addition greater than 4 weight percents of silicon, form silicon oxide layer and reduce hot dip property at surface of steel plate.And, under the situation that causes stabilization of austenite to descend because of the stacking fault energy that too reduces steel, can promote the martensitic generation of ε, thereby, can the content of silicon be controlled at below 4 weight percents.
And, under the situation of adding the aluminium below 3 weight percents, can access deoxidation effect.And aluminium improves stacking fault energy at slip plane and suppresses the martensitic generation of ε, thereby improves ductility.Moreover, under the little situation of the addition of manganese, aluminium can also suppress the martensitic generation of ε, thereby the content of manganese is minimized and improves workability.
But, under the situation of content greater than 3 weight percents of aluminium,, and when continuous casting, reduce castibility owing to the become generation of too high inhibition twin crystal of stacking fault energy reduces ductility.And, when hot rolling, descend owing to surface oxidation seriously causes surface quality of products.
And niobium, titanium and vanadium are the strong carbide forming elements that combines to form carbide with carbon, and the carbide that form this moment stops crystal grain-growth effectively to promote the grain fineness number miniaturization, and can obtain precipitating reinforcing effect through the formation of precipitated phase.But, if the addition of niobium, titanium or vanadium greater than 0.30 weight percent, then because of niobium, titanium, vanadium grain boundary segregation cause embrittlement of grain boundaries or because of precipitated phase too thickization reduce the grain growing effect.Thus, the addition of niobium, titanium or vanadium can be below 0.30 weight percent.
And the reason of the content range of control other compositions in addition is with identical in the reason of first embodiment and second embodiment explanation, and the Therefore, omited specifies.
Then, the method for manufacture to the high manganese nitrogen steel plate of exemplary embodiment of the present describes.
The method of manufacture of the steel plate of exemplary embodiment of the present is following.At first, electrolytic iron, electrolytic manganese, carbon dust are disposed at the inside of treatment chamber.At this moment, the amount of putting into each material of inner treatment chamber through adjusting is regulated the composition as the steel plate of finished product.Then, inner treatment chamber is become after the vacuum, with argon gas and nitrogen filling, to form the argon-nitrogen gas atmosphere therein.This moment, argon-nitrogen gas atmosphere integral body was 1 normal atmosphere, and wherein the dividing potential drop of nitrogen can be in 0.2～0.8 barometric pressure range.If the ratio of nitrogen, then adds the addition of the nitrogen in the steel to less than 20 weight percents when carrying out arc-melting very few and cause arc-melting efficient to reduce.And, if greater than 80 weight percents, then there is following defective in the ratio of nitrogen:, cause the inner treatment chamber severe contamination owing to the hypotony as the argon of rare gas element causes the serious dense smoke that is caused by manganese.And, if the ratio of nitrogen is too high, then have following defective: the fusion of tungsten electrode bar cause raw-material disperse serious, thereby cause that the surface of steel plate becomes very coarse state behind arc-melting.Then, utilize electrode bar that the material of inner treatment chamber is carried out arc-melting,, required steel plate is provided thus with the postcooling reasonable time.And, though above-mentioned arc-melting-disposable completion of process of cooling ability is preferably repeatedly and carries out several times.And along with the number of times that carries out above-mentioned arc-melting-process of cooling repeatedly increases, it is high more that the content of nitrogen becomes.
Particularly; Forming through usual way under the situation of twin inducing plasticity steel; The content of nitrogen is merely 0.02 weight percent to 0.1 weight percent; If do not add element, just be difficult to form the high manganese nitrogen steel plate of composition with above-mentioned first embodiment as the solid solution that can promote nitrogen of chromium and so on.But; As stated; Under the situation of carrying out arc-melting formation steel plate under the argon-nitrogen gas atmosphere; Even do not add high valence elements, also compare the more nitrogen of situation that forms steel plate through usual way, thereby especially can form the high manganese nitrogen steel plate of composition with above-mentioned first embodiment owing to introducing as chromium and so on.But, utilize the method for above-mentioned arc-melting to be not limited to the situation of the steel plate that forms composition with above-mentioned first embodiment, also can be used in and form steel plate with other various compositions.
Utilizing after above-mentioned arc-melting forms high manganese nitrogen steel plate, under the temperature more than 900 ℃, above-mentioned steel plate is carried out hot rolling, carry out air cooling or forced air-cooling subsequently.
And; More preferably; With the draft more than 50% hot rolling and cooled above-mentioned steel plate are carried out at normal temperatures cold rolling, subsequently under the temperature more than 800 ℃ to the thermal treatment of annealing of the steel plate after cold rolling, and the steel plate after the annealing thermal treatment carried out air cooling or forced air-cooling.
Perhaps, utilize usual way also can produce high manganese nitrogen steel plate of the present invention.
Specifically; Utilize the step of pdps manufactured steel plate to comprise: the steel plate of required composition is heated to more than 1100 ℃; Under the temperature more than 900 ℃ the above-mentioned steel plate after the heating is being carried out hot rolling so that steel plate to be provided, and the above-mentioned steel plate after the hot rolling is being carried out air cooling or forced air-cooling.And; This method also can comprise following step: carry out cold rolling with the draft more than 50% to cooled above-mentioned steel plate; Under the temperature more than 800 ℃ to the thermal treatment of annealing of the steel plate after cold rolling, and the steel plate after the annealing thermal treatment carried out air cooling or forced air-cooling.
The mode that is used for embodiment of the present invention
The steel that experimental example 1 to experimental example 6 and comparative example 1 to comparative example 6 will have chemical ingredients as shown in table 1 respectively is heated to more than 1100 ℃; And under the temperature more than 900 ℃, carry out hot rolling and form the plate that thickness is 3mm; Carry out air cooling afterwards, thereby process test piece.And experimental example 4 is the cold rolling one-tenth of the hot-rolled steel sheet 1.5mm of 3mm with the thickness of experimental example 3 especially, and cold rolled annealed test piece is made in the annealing thermal treatment of then under 800 ℃ of temperature, carrying out 10 minutes.
Table 1
Then, utilize and measure intensity and unit elongation through the test piece of above-mentioned operation manufacturing, its result is as shown in table 2 below.
Table 2
As shown in table 2, the ys of the steel plate of experimental example 1 to experimental example 4 (YS) is greater than 300Mpa, and tensile strength (TS) is also up to more than the 880Mpa.And the breaking elongation of the steel plate of experimental example 1 to experimental example 4 (EL) is about 60%, and the product of tensile strength and unit elongation (TS * EL) up to 50000MPa%.That is, when comparing, unit elongation is suitable with twin inducing plasticity steel (comparative example 2, comparative example 3) in the past for the steel of foregoing invention example, but ys and tensile strength are higher.Particularly, shown in experimental example 3, under the situation of content greater than 0.2 weight percent of nitrogen, the solid solution strengthening effect of nitrogen makes ys and tensile strength values very high.That is, the tensile strength of the steel plate of experimental example 3 is higher than 1GPa, and has the unit elongation near 60%, thus the product of tensile strength and unit elongation (TS * EL) also greater than 60000MPa%.And experimental example 4 is the cold rolled annealed steel plates after the hot-rolled steel sheet to experimental example 3 carries out cold rolled annealed processing, confirms that its tensile strength and unit elongation have all obtained increase.
The formation of above-mentioned mechanical twin can obtain confirming through Fig. 1.Particularly, Fig. 1 is the electron micrograph of the high manganese nitrogen steel plate of one embodiment of the invention (being experimental example 3), and is as shown in Figure 1, in the steel plate of experimental example 3, is formed with mechanical twin.
In addition; Compare with the steel plate of experimental example 1 to experimental example 4, at the experimental example that has also added aluminium and silicon 5 and also added in the steel plate of experimental example 6 of aluminium, though the content of chromium significantly reduces; But comprise a large amount of nitrogen, its ys and tensile strength values are also good thus.
On the contrary, the steel plate of the comparative example that forms through previous methods is compared with the present invention, and tensile strength or unit elongation are lower.At first, good as the tensile strength of the comparative example 1 of phase-change induced plastic steel plate, be 928.7MPa, but the total elongation rate variance is merely 15.5%.And; Under the situation of the twin induced plastic steel plate (comparative example 2, comparative example 3) for preparing according to the method in the past that does not contain nitrogen; Breaking elongation is good, reach more than 60%, but tensile strength is relatively poor relatively; For about 700MPa, the result causes the product (TS * EL) also be merely about 40000MPa% of tensile strength and unit elongation.And comparative example 4 to the comparative example 6 of the content through having increased carbon can confirm that unit elongation increases along with carbon content and sharply descends.
Then, 9 expressions of experimental example 7 to experimental example utilize the arc-melting method to form the situation of steel plate.That is, with electrolytic iron, electrolytic manganese, carbon dust with the ratio arrangement of regulation in inner treatment chamber, and treatment chamber is in after the vacuum state, make at inner treatment chamber formation argon-nitrogen gas atmosphere with argon gas and nitrogen filling.At this moment, advantageously, argon-nitrogen gas atmosphere integral body is 1 normal atmosphere, and wherein the branch of nitrogen is pressed in 0.2～0.8 barometric pressure range.In this experiment, be under the condition of 400A at electric current, make the arc electrodes rod carry out 30 minutes arc-meltings to starting material isolating under the state of 2～5cm the progressive mode, with postcooling 30 minutes with test piece.And, carry out three above-mentioned arc-meltings and process of cooling repeatedly.
Then, the steel plate of experimental example 10 is after except electrolytic iron, electrolytic manganese, carbon dust, also the raw material of chromium being disposed at inner treatment chamber, to carry out arc-melting and the steel plate that forms.Other conditions of the steel plate formation method of experimental example 10 are identical with the situation of experimental example 1 to experimental example 3.
Then, the steel plate of comparative example 7 representes not carry out abideing by the arc-melting of aforesaid method, and under nitrogen atmosphere, fuses the situation that raw material forms steel.
The concrete composition of experimental example 7 to the experimental example 10 that forms through aforesaid method and the high manganese steel sheet of comparative example 7 is following.
Table 3
As experimental example 7 to experimental example 10, under the argon-nitrogen gas atmosphere, the steel that does not comprise chromium is carried out arc-melting, can form high manganese steel sheet.And, as experimental example 4, under the argon-nitrogen gas atmosphere, the steel that comprises chromium is carried out arc-melting, can form the higher steel of nitrogen content.
On the other hand, comparative example is represented to comprise chromium and under nitrogen atmosphere, is passed through the situation that fusion forms steel according to common method for making steel.Even as comparative example, comprise chromium and under nitrogen atmosphere, fuse, the nitrogen content in the steel also is less than the nitrogen content in the steel plate of this experimental example.Promptly; As comparative example; Under through the situation of fusing the steel that forms the chromium that comprises 1.73 weight percents; The content of nitrogen is 0.086 weight percent, compares with the nitrogen content that reaches 0.141 weight percent of the experimental example 10 of the chromium that comprises roughly the same amount, and the nitrogen content in the steel plate of this comparative example is wanted much less.
Fig. 2 is the figure of expression according to the tensile strength curve of the steel of experimental example 9 formation.As shown in Figure 2, the intensity of the steel of experimental example 9 and unit elongation show as 985Mpa, 56% respectively, show very goodly.The product of intensity and unit elongation is about 55000MPa%; This value is apparently higher than comprising the manganese below 20 weight percents and not comprising the high mangaenese steel of chromium; With contain greater than the manganese of 20 weight percents or also to comprise the high mangaenese steel of high-valency metal of picture chromium and so on approximate, so very useful.
More than, some embodiments of the invention are specified.But, be to be understood that and under situation without departing from the spirit and scope of the present invention, carry out various corrections and distortion the foregoing description for the those of ordinary skill of technical field under the present invention.Thus, the present invention's scope of requiring to protect is only limited appended claims and equivalent way thereof.
Claims (19)
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| KR10-2009-0036963 | 2009-04-28 | ||
| KR1020090036963A KR101140931B1 (en) | 2009-04-28 | 2009-04-28 | Nitrogen-added high manganese steel having high strength and large ductility and method for manufacturing the same |
| KR1020100026584A KR101193718B1 (en) | 2010-03-25 | 2010-03-25 | Nitrogen-added high manganese steel having high strength and large ductility and method for manufacturing the same |
| KR10-2010-0026584 | 2010-03-25 | ||
| PCT/KR2010/002625 WO2010126268A2 (en) | 2009-04-28 | 2010-04-27 | High manganese nitrogen-containing steel sheet having high strength and high ductility, and method for manufacturing same |
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| US (1) | US20120045358A1 (en) |
| EP (1) | EP2431492B1 (en) |
| JP (1) | JP5437482B2 (en) |
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| CN111850422A (en) * | 2020-04-30 | 2020-10-30 | 中科益安医疗科技（北京）股份有限公司 | High-nitrogen nickel-free austenitic stainless steel seamless thin-walled tube and preparation method thereof |
| CN111850422B (en) * | 2020-04-30 | 2022-01-11 | 中科益安医疗科技（北京）股份有限公司 | High-nitrogen nickel-free austenitic stainless steel seamless thin-walled tube and preparation method thereof |
| CN112708823A (en) * | 2020-11-24 | 2021-04-27 | 河钢股份有限公司 | High-manganese and high-aluminum TWIP steel with high thermoplasticity and production method thereof |
| CN118272735A (en) * | 2024-04-07 | 2024-07-02 | 燕山大学 | Fe-Mn-Cr-C-N high manganese steel and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010126268A2 (en) | 2010-11-04 |
| WO2010126268A3 (en) | 2011-03-03 |
| JP2012525500A (en) | 2012-10-22 |
| JP5437482B2 (en) | 2014-03-12 |
| EP2431492A2 (en) | 2012-03-21 |
| EP2431492B1 (en) | 2015-09-30 |
| EP2431492A4 (en) | 2014-01-22 |
| US20120045358A1 (en) | 2012-02-23 |
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