CN104046917B - Superhigh intensity ferritic steel and the manufacture method thereof of rich Cu nanocluster strengthening - Google Patents
Superhigh intensity ferritic steel and the manufacture method thereof of rich Cu nanocluster strengthening Download PDFInfo
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- CN104046917B CN104046917B CN201310081053.6A CN201310081053A CN104046917B CN 104046917 B CN104046917 B CN 104046917B CN 201310081053 A CN201310081053 A CN 201310081053A CN 104046917 B CN104046917 B CN 104046917B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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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
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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- 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
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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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
Abstract
Superhigh intensity ferritic steel and the manufacture method thereof of rich Cu nanocluster strengthening, its component is as follows by weight percentage: C is 0～0.2%; Cu is 0.5～5%; Ni is 0.01～4%; Mn is 0.01～4%; Al is 0.001～2%; Cr is 0～12%; Mo is that 0～3%, W is that 0～3%, Mo+W is not less than 0.05%; V is that 0～0.5%, Ti is that 0～0.5%, Nb is that 0～0.5%, V+Ti+Nb is not less than 0.01%; Si is 0～1%; B is 0.0005～0.05%; P is not higher than 0.04%; S is not higher than 0.04%; N is not higher than 0.04%; O is not higher than 0.05%; Surplus is Fe and inevitable impurity, carries out solid solution and Ageing Treatment after melting, casting and forging rolling, makes the ferritic steel taking nanocluster strengthening as main and combined with fine-grained, solid solution and dislocation strengthening, obtains excellent obdurability, weldability and corrosion resistance.
Description
Technical field
The present invention relates to a kind of superhigh intensity ferritic steel and manufacture method thereof, be specifically related to a kind of rich CuSuperhigh intensity ferritic steel and the manufacture method thereof of nanocluster strengthening.
Background technology
Along with resource, environmental pressure strengthen day by day, environmental protection, the energy-conservation attention that is more and more subject to steel and iron industry.Develop the unimach of energy-conservation, material-saving and excellent performance, meet the 26S Proteasome Structure and Function of each applicationRequirement is the important channel of realizing sustainable development of iron and steel industry.
Tradition unimach, as lonneal martensitic structure or lower bainite build up low-alloySteel, high tempering alloy carbide precipitate, post-curing build up unimach, intermetallicCompound precipitation strength Maraging steel etc., have reached the requirement of superhigh intensity to a certain extent, but high-carbon,High alloy and heat treatment change and require the characteristics such as rapid cooling to make it still have welding performance and plasticity and toughness are poor, becomeThe problem such as this height, scantling are limited.
Along with the development of nanosecond science and technology, utilize nanometer precipitated phase Strengthening and Toughening mechanism to improve unimachCombination property has become the important channel of development of new unimach, particularly with the traditional horse of employingFamily name's body matrix phase ratio utilizes strengthened nano precipitated phase mechanism development of new on ferrite structure basisUnimach has great technique and cost advantage. Recently, researcher analyses at Cu nanoclusterGo out to strengthen steel aspect and carried out Primary Study. Cu is face-centred cubic structure element, in body-centered cubic structureIn ferrite matrix, solid solubility is very little, can from ferrite matrix, separate out through suitable heat treatment Cu,Form Cu nanocluster precipitated phase, produce the intensity of precipitation strength effect raising steel, and research shows to receiveRice cluster size is less, the amount of separating out is more, separate out spacing less, distribute more even, precipitation strengthEffect is better. But at present the Cu particle size in Cu precipitation strength steel is mostly more than 50nm,And the amount of separating out is few, precipitate particle spacing is large, distribution of particles is uneven, makes the invigoration effect of Cu particleLimited, the intensity of gained Cu precipitation strength steel is mostly below 1000MPa, as patent CNThe precipitation hardened chrome ferritic stainless steel of a kind of nanoscale Cu is disclosed in 101328561A, whereinCu precipitate particle is of a size of 50～200nm, the reinforced ferrite that utilizes Cu phase precipitation strength effect to obtainSteel yield strength is not less than that 300MPa, tensile strength are not less than 450MPa, percentage elongation is not less than 25%.
The present invention, by kind and content and the Technology for Heating Processing of Reasonable Regulation And Control alloying element, optimizes CuThe nucleation and growth process of nanocluster, so optimize nanocluster separate out size, quantity and distribution,Form concentration high, be evenly distributed, rich Cu nanocluster that size is tiny, farthest performance is richThe invigoration effect of Cu nanocluster, combined with fine-grained strengthening, solution strengthening and dislocation strengthening etc. are multiple simultaneouslySchedule of reinforcement is realized complex intensifying, makes the rich Cu nanoclusters of low-carbon (LC), low cost, excellent combination propertyThe superhigh intensity ferritic steel of bunch strengthening.
Summary of the invention
An object of the present invention is to provide a kind of superhigh intensity ferritic steel of rich Cu nanocluster strengthening,Wherein taking high concentration, be uniformly distributed, rich Cu nanocluster that size is tiny strengthens as main, combination simultaneouslyRefined crystalline strengthening, solution strengthening and dislocation strengthening various ways are realized complex intensifying, make and have ultra-high strength and toughnessThe novel low-cost superhigh intensity ferritic steel of property, superior weldability energy and decay resistance.
Another object of the present invention is to provide a kind of superhigh intensity of manufacturing above-mentioned rich Cu nanocluster strengtheningThe method of ferritic steel.
On the one hand, the invention provides a kind of superhigh intensity ferritic steel of rich Cu nanocluster strengthening, pressWeight percent meter, its chemical constituent is as follows: C is 0～0.2%; Cu is 0.5～5%; Ni is 0.01～4%;Mn is 0.01～4%; Al is 0.001～2%; Cr is 0～12%; Mo is that 0～3%, W is 0～3%,Mo+W is not less than 0.05%; V is that 0～0.5%, Ti is that 0～0.5%, Nb is 0～0.5%, V+Ti+NbBe not less than 0.01%; Si is 0～1%; B is 0.0005～0.05%; P is not higher than 0.04%; S not higher than0.04%; N is not higher than 0.04%; O is not higher than 0.05%; Surplus is Fe and inevitable impurity.
In one embodiment of the invention, the component of described rich Cu nanocluster be Cu, Ni,Mn、Al。
In another embodiment of the invention, the average-size of described rich Cu nanocluster is 3nm,Average headway is 2～10nm, and every cu μ m nanoclusters number of clusters is not less than 10,000.
In another embodiment of the invention, the superhigh intensity iron of described rich Cu nanocluster strengtheningIn element body steel, also comprise composite Nano carbide (V, Ti, Nb) C, described nano-carbide is of a size of 5～100nm。
In another embodiment of the invention, the superhigh intensity iron of described rich Cu nanocluster strengtheningThe matrix of element body steel is ferrite, and described ferritic average grain size is 1～20 μ m.
In another embodiment of the invention, the superhigh intensity iron of described rich Cu nanocluster strengtheningThe yield strength of element body steel is 900～1200MPa, and hot strength is 1200～1500MPa, and percentage elongation is10～20%, the contraction percentage of area is 50%～80%.
On the other hand, the present invention also provides a kind of superhigh intensity of manufacturing described rich Cu nanocluster strengtheningThe method of ferritic steel, its step is as follows:
(1) chemical constituent of the superhigh intensity ferritic steel of described rich Cu nanocluster strengthening is formedFeedstock composition carries out melting, casting and forging rolling successively;
(2) carry out solution treatment, be then cooled to room temperature;
(3) carry out Ageing Treatment, be then cooled to room temperature.
In a kind of embodiment of the inventive method, described solution treatment is 800～1300 DEG C of scopesInside carry out.
In the another kind of embodiment of the inventive method, described solution treatment is carried out at 900 DEG C.
In the another kind of embodiment of the inventive method, described solution treatment is carried out 0.1～3 hour.
In the another kind of embodiment of the inventive method, described solution treatment is carried out 0.5 hour.
In the another kind of embodiment of the inventive method, described Ageing Treatment is within the scope of 400～600 DEG CCarry out.
In the another kind of embodiment of the inventive method, described Ageing Treatment is carried out at 550 DEG C.
In the another kind of embodiment of the inventive method, described Ageing Treatment is carried out 0.1～20 hour.
In the another kind of embodiment of the inventive method, described Ageing Treatment is carried out 2 hours.
The present invention, by Reasonable Regulation And Control alloying element kind and content and Technology for Heating Processing, obtains concentrationHigh, be evenly distributed, rich Cu nanocluster that size is tiny, effectively brought into play separating out of nanocluster strongTurn use into, and the various ways such as combined with fine-grained strengthening, solution strengthening and dislocation strengthening carries out complex intensifying,Obtain excellent obdurability, wherein taking rich Cu nanocluster as main hardening constituent, done with its precipitation strengthWith being topmost schedule of reinforcement, reducing the carbon content in steel, thereby also there is good welding performanceAnd plasticity and toughness, add in addition appropriate Cr and Al element, can form stable chromium oxide and aluminium oxideDiaphragm, Cu also plays the effect that improves steel corrosion resistance in atmosphere and seawater, thereby comprehensively improvesAnti-oxidant and the decay resistance of steel. Complex optimum of the present invention nanocluster strengthening, refined crystalline strengthening,Alloying element kind and the content of solution strengthening, use minimum, the most rational alloying element, and withExisting super-strength martensitic steel is compared, can be without after superhigh intensity ferritic steel of the present invention heat treatmentQuenchings etc. are process for cooling fast, and production size is larger, and is suitable for continuous casting and rolling production, and production costLow.
In sum, according to the superhigh intensity ferritic steel of rich Cu nanocluster strengthening of the present invention, withDescribed rich Cu nanocluster strengthening is main, and combining nano carbide refined crystalline strengthening, other solid solution alloiesThe various ways such as element solid solution strengthening and dislocation strengthening are realized complex intensifying, thereby obtain obdurability couplingSplendid performance, and it is low to have good weldability, corrosion resistance and cost, can be widely used in automobile,Naval vessel, bridge, pipeline, the energy, power station, ocean engineering, building structure, pressure vessel, engineering machineThe fields such as tool, container and defence equipment.
Brief description of the drawings
By reference to the accompanying drawings with reference to following detailed description those skilled in the art will understand better of the present invention onAddress many other feature and advantage, wherein:
Fig. 1 is in the matrix of the superhigh intensity ferritic steel NSF104 that manufactures according to the embodiment of the present invention 1The high-resolution-ration transmission electric-lens photo of rich Cu nanocluster;
Fig. 2 is in the matrix of the superhigh intensity ferritic steel NSF104 that manufactures according to the embodiment of the present invention 1The high-resolution-ration transmission electric-lens photo of nano-carbide;
Fig. 3 is micro-group of the superhigh intensity ferritic steel NSF104 that manufactures according to the embodiment of the present invention 1Knit pattern stereoscan photograph;
Fig. 4 is superhigh intensity ferritic steel NSF108 and the compared steel of manufacturing according to the embodiment of the present invention 1The tensile stress strain curve of T24.
Detailed description of the invention
According to specific embodiment, technical scheme of the present invention is described further below. Protection of the present inventionScope is not limited to following examples, enumerates these examples and only limits never in any form for exemplary purposeThe present invention processed.
The invention provides a kind of superhigh intensity ferritic steel of rich Cu nanocluster strengthening, percentage by weightThan meter, its chemical constituent is as follows, and: C is 0～0.2%; Cu is 0.5～5%; Ni is 0.01～4%; MnBe 0.01～4%; Al is 0.001～2%; Cr is 0～12%; Mo is that 0～3%, W is 0～3%, Mo+WBe not less than 0.05%; V is that 0～0.5%, Ti is that 0～0.5%, Nb is that 0～0.5%, V+Ti+Nb is not lowIn 0.01%; Si is 0～1%; B is 0.0005～0.05%; P is not higher than 0.04%; S is not higher than 0.04%;N is not higher than 0.04%; O is not higher than 0.05%; Surplus is Fe and inevitable impurity.
Below to each chemical constituent content in the superhigh intensity ferritic steel of described rich Cu nanocluster strengtheningThe restriction reason of scope describes:
C: form stable nano-carbide with V, Ti and Nb, can produce precipitation strength effect,Effectively refinement ferrite crystal grain, produces refined crystalline strengthening effect, thereby improves the intensity of steel, at thisIn bright, in order to ensure superior weldability energy and the toughness of steel, only use low carbon content, therefore the present invention willThe content of C is limited to 0～0.2%;
Cu: the main component of nanocluster is also the most important of nanocluster strengthening in the present inventionElement, utilizing lower-cost Cu to form nanocluster can efficient hardening ferritic steel, reduces carbideThe application of strengthening, and then can reduce the phosphorus content in steel, contribute to improve welding performance and the toughness of steel,In addition Cu also has the effect that improves steel corrosion resistance in atmosphere and seawater, when Cu content is lower than 0.5%Time, strengthening effect is not obvious, and in the time of Cu too high levels, can produce red brittleness, to processing characteristics notProfit, therefore the present invention is limited to 0.5～5% by Cu content;
Ni: one of component of nanocluster, participates in nanocluster precipitation strength effect, and can hinderNanocluster is grown up, and contributes to refinement nanocluster, and Ni also contributes to improve the toughness of steel, but NiFor austenite former, when its too high levels, in steel, meeting retained austenite, causes tissue odds even,And can increase production cost, therefore the present invention is limited to 0.01～4% by Ni content;
Mn: one of component of nanocluster, participate in nanocluster precipitation strength effect, Mn is difficult to understandFamily name's body forming element, has and postpones the effect of austenite to ferritic transformation, is conducive to refinement ferrite crystalline substanceGrain, improves intensity and toughness, but when Mn too high levels, can retained austenite in steel, cause tissueInhomogeneous, and high Mn content can cause steel billet segregation, toughness variation and solderability to reduce, thereforeThe present invention is limited to 0.01～4% by Mn content;
Al: one of component of nanocluster, participate in nanocluster precipitation strength effect, Al still refinesDeoxidier in steel process, has the effect of cleaning molten steel, but when Al too high levels, can bring smeltingThe difficulty of casting, therefore the present invention is limited to 0.001～2% by Al content;
Cr: anti-oxidant and anticorrosive element can improve the anti-oxidant and decay resistance of steel, still simultaneouslyFerrite former, can increase and the ferritic structure of stabilized steel, but Cr too high levels can reduceThe toughness of steel, and can increase production cost, therefore the present invention is limited to 0～12% by Cr content;
Mo and W: ferrite former, the ferritic structure of stabilized steel, can also play solution strengtheningEffect, but Mo and W interpolation are too much, matrix can be separated out Fe2Mo and Fe2W fragility phase, makes steelToughness drop, therefore the present invention is all limited to 0～3% by the content of Mo and W, and Mo and W's is totalAmount is not less than 0.05%;
V, Ti and Nb: strong carbon compound forming element, with the MC type of C formation face-centred cubic structureCarbide (M:V, Ti or Nb), has the advantages that size is little, heat endurance is high, can effectively hinder crystalline substanceGrain length is large, and the effect of performance refined crystalline strengthening and precipitation strength, in the present invention in order to ensure the good weldering of steelConnect performance and toughness, only use low carbon content, V, the Ti of interpolation 0.5% or Nb can make solid carbon effectFruit reaches capacity, and therefore the present invention is all limited to 0～0.5% by the content of V, Ti and Nb, and V, TiBe not less than 0.01% with the total amount of Nb;
Si: improve carbon and distribute, prevent the formation of cementite, ferritic structure that can also stabilized steel, playsSolution strengthening effect, but Si adds when too much, can reduce the toughness of steel, therefore the present invention contains SiAmount is limited to 0～1%;
B: can significantly purify crystal boundary, improve intensity and the toughness of steel, but when B too high levels, crystal boundaryCan separate out too much boride, reduce the toughness of steel, therefore the present invention is limited to B content0.0005～0.05%；
P and S: inevitable impurity element in steel, when content is high, can form frangible compounds with Cu,Toughness and the welding performance of harm steel, therefore the content of P and S is all controlled at below 0.04%;
N and O: inevitable impurity element in steel, toughness and the welding performance of harm steel, therefore NBe controlled at respectively below 0.04% and 0.05% with the content of O;
Composition beyond above-mentioned is Fe and other inevitable impurity, do not damaging effect of the present inventionIn scope, do not get rid of and also contain above-mentioned composition in addition.
The present invention also provides a kind of superhigh intensity ferritic steel of manufacturing described rich Cu nanocluster strengtheningMethod, its step is as follows:
(1) chemical constituent of the superhigh intensity ferritic steel of described rich Cu nanocluster strengthening is formedFeedstock composition carries out melting, casting and forging rolling successively;
(2) carry out solution treatment, be then cooled to room temperature;
(3) carry out Ageing Treatment, be then cooled to room temperature.
The method according to this invention can be smelted in electric arc furnaces, converter, induction furnace, then can adoptProduce strand or adopt die casting mode to produce ingot casting by continuous casting mode, described strand or ingot casting have goodHot and cold processing characteristics, then can carry out cold rolling, warm-rolling or forge within the scope of 800～1300 DEG COr hot rolling, sheet material is carried out within the scope of 800～1300 DEG C to solution treatment through rolling or after forging, when processingBetween be 0.1～3 hour, cooling subsequently, the type of cooling can be air cooling, air-cooled, oil quenching or shrend, can be coldBut to room temperature or be directly cooled to aging temp and carry out Ageing Treatment, Ageing Treatment is 400～600 DEG C of scopesInside carry out, the processing time is 0.1～20 hour, cooling subsequently, the type of cooling can be equally air cooling, air-cooled,Oil quenching or shrend, finally obtain the superhigh intensity ferritic steel that rich Cu nanocluster of the present invention is strengthened.
The present invention is by cold and hot deformation techniques such as forging rollings, can crystal grain thinning, also can introduce a large amount of dislocations and skyThe defects such as position, for highly concentrated nano cluster nucleation provides good condition, also can realize dislocation strengthening. SubsequentlyHeat-treat according to the present invention, under specified temp, successively carry out certain time length solution treatment and timeEffect is processed, and obtains ferrite supersaturated solid solution through solution treatment, by reasonable control aging temp andAging time is effectively controlled separating out of nanocluster and is grown up. With regard to solution treatment, Cu element is at faceIn the austenite of heart cubic structure, there is very large solid solubility, carry out solid solution according to the present invention at 800～1300 DEG CProcess, can ensure added Cu element completely solid solution among matrix, and excess Temperature crystal grainSeriously alligatoring, the intensity of steel and toughness all can decline. With regard to Ageing Treatment, Cu element is at ironThe solid solubility of element in body is very low, and solid solubility can decline with the decline of temperature, if adopt when too highEffect temperature, nanocluster will alligatoring, if adopt too low aging temp, nanocluster is separated out deficiency.According to the present invention after above-mentioned solution treatment again after 400～600 DEG C are carried out Ageing Treatment, through high scoreDistinguish that transmission electron microscope photo confirms, in ferrite matrix coherence separated out concentration high, be evenly distributed, size is thinLittle rich Cu nanocluster. According to strengthened nano precipitated phase mechanism, dislocation and precipitated phase reciprocation,Precipitated phase effectively hinders dislocation and moves, thus realize strengthening, many in precipitated phase quantity, size is little, distributionIn situation, can obtain maximum strengthening effect uniformly. The present invention is by Reasonable Regulation And Control alloy element and heatTreatment process obtain concentration high, be evenly distributed, rich Cu nanocluster that size is tiny, to greatest extentBring into play the invigoration effect of rich Cu nanocluster. In addition in the present invention, except Cu element, also have,Other element (Ni, Mn and Al) is also the important composition of nanocluster, not only affects nanoclusterNucleation, and can hinder nanocluster and grow up, contribute to refinement nanocluster.
In addition, in the superhigh intensity ferritic steel of rich Cu nanocluster strengthening of the present invention, also comprise carbonizationThing forming element (V, Ti and Nb) and trace carbon element (C), after above-mentioned heat treatment, at ferrite baseIn body, separate out a small amount of composite Nano carbide with interface emission form, do not endangering welding performance and toughnessSituation under, the nano-carbide that these are tiny, heat endurance is high has played refined crystalline strengthening effect. WithTime the present invention by optimizing various alloying element kinds and content, (for example actively brought into play alloying elementMo and W) solution strengthening effect, and by rational cold and hot distortion and Technology for Heating Processing, realizeDislocation strengthening, thereby reach taking the strengthening of rich Cu nanocluster as main and combined with fine-grained strengthening, solid solutionStrengthening and dislocation strengthening realize the effect of complex intensifying.
Unless be separately construed as limiting, term used herein is the implication that those skilled in the art understand conventionally.
Below in conjunction with accompanying drawing, by embodiment, the present invention is described in further detail.
Embodiment 1
According to the present invention, the compositing range of the superhigh intensity ferritic steel of rich Cu nanocluster strengthening, smelts9 kinds of invention steel NSF101～109, smelted the T24 steel of power plant application as a comparison simultaneously. According toThe alloying component composition of NSF101～109 shown in table 1 and T24, in arc-melting furnace, smelts withCasting, is rolled processing by the ingot casting making with each 5～10% drafts, obtains total deformation and isThe sheet material of 70% left and right. Sheet material after rolling is carried out at 900 DEG C to solution treatment in 0.5 hour, subsequently withArgon gas quenching mode is cooled to room temperature, then at 550 DEG C, carries out 2 hours Ageing Treatment, same subsequentlyBe cooled to room temperature in argon gas quenching mode, thereby make invention steel NSF101～109 and compared steel T24.
The alloying component composition of table 1. invention steel NSF101～109 and compared steel T24
Embodiment 2
According to the alloying component composition of NSF104 in table 1, in arc-melting furnace, smelt and cast,The ingot casting making is rolled to processing with each 5～10% drafts, and obtaining total deformation is 70% left sideRight sheet material. Sheet material after rolling is carried out at 850 DEG C to solution treatment in 0.5 hour, subsequently with shrendMode is cooled to room temperature, then at 550 DEG C, carries out 2 hours Ageing Treatment, cold in air cooling mode subsequentlyBut to room temperature. Thereby make invention steel NSF104 '.
Embodiment 3
According to the alloying component composition of NSF104 in table 1, in arc-melting furnace, smelt and cast,The ingot casting making is rolled to processing with each 5～10% drafts, and obtaining total deformation is 70% left sideRight sheet material. Sheet material after rolling is carried out at 1200 DEG C to solution treatment in 0.5 hour, subsequently with shrendMode is cooled to room temperature, then at 550 DEG C, carries out 2 hours Ageing Treatment, cold in air cooling mode subsequentlyBut to room temperature. Thereby make invention steel NSF104 ".
Test example 1
Carry out compared steel T24 after utilizing transmission electron microscope to above-mentioned heat treatment and invention steel NSF101～109Analysis. As shown in Table 1, in compared steel T24 composition, do not contain nanocluster forming element, transmission electron microscopeIn result display comparison steel T24, there is not nanocluster, and found in invention steel NSF101～109The rich Cu nanocluster that concentration is high, be evenly distributed, size is tiny. Fig. 1 is invention steel NSF104 baseThe high-resolution-ration transmission electric-lens photo of nanocluster in body, wherein the average-size of nanocluster is about 3nm,Be evenly distributed, average headway is about 4nm, and every cu μ m nanoclusters number of clusters is no less than 10,000,Determine by transmission electron microscope energy spectrum analysis, nanocluster mainly comprises Cu, Ni, Mn and Al element.As can be seen here, according to shape in rich Cu nanocluster strengthening low cost superhigh intensity ferritic steel of the present inventionBecome concentration high, be evenly distributed, rich Cu nanocluster that size is tiny, according to strengthened nano precipitated phaseMechanism, the rich Cu nanocluster that these concentration are high, size is little effectively hinders dislocation motion, can be remarkableStrengthen the intensity of ferritic steel.
In addition, utilize transmission electron microscope also to observe some nano-carbides, Fig. 2 is invention steel NSF104The high-resolution-ration transmission electric-lens photo of the nano-carbide of separating out in matrix, true by transmission electron microscope energy spectrum analysisFixed, described nano-carbide is composite Nano carbide (V, Ti) C, is of a size of about 20nm. Nano silicon carbideThing has the advantages that size is little, heat endurance is high, has effectively hindered grain growth, plays refined crystalline strengthening and doesWith. In addition,, compared with simple carbide, double carbide has slower coarsening behavior, thereby hasBetter heat endurance. Fig. 3 is the stereoscan photograph of invention steel NSF104 displaing micro tissue topography, asShown in figure, wherein matrix is fine ferrite grain, even grain size, tiny, and average grain size is1.5 μ m, the above-mentioned nanometer precipitated phase of separating out in visible matrix has effectively played the effect of crystal grain thinning, rootKnown according to Hall-Petch relational expression, by refining grain size, can improve the strength of materials, simultaneously brilliantParticle size is less, and plasticity is better, and toughness index is higher.
Test example 2
Cut tensile sample is processed into in invention steel NSF101～109 and compared steel T24 by line,On MTS testing machine, carry out tensile test at room temperature, yield strength, hot strength, the contraction percentage of area and elongationRate the results are shown in table 2. Fig. 4 is invention steel NSF108 constructed in accordance and compared steel T24'sTensile stress strain curve. From table 2 and Fig. 4, compared steel T24 is through identical smelting and heat treatmentAfter technique, its yield strength is 347MPa, and hot strength is 586MPa, with the document phase of deliveringSymbol, and invention steel NSF101～109 constructed in accordance, yield strength is 900～1200MPa,Hot strength is 1200～1500MPa, and compared with T24 steel, yield strength and hot strength are all obviously carriedHeight, and the contraction percentage of area remains on 50%～80%, and percentage elongation remains on 10～20%, obdurability couplingGood. As can be seen here, the present invention passes through to adjust nanocluster strengthening, refined crystalline strengthening and solution strengthening element,And take suitable Technology for Heating Processing, significantly improve the intensity of steel.
The room temperature tensile mechanical property of table 2. invention steel NSF101～109 and compared steel T24
| Numbering | Yield strength (MPa) | Hot strength (MPa) | The contraction percentage of area (%) | Percentage elongation (%) |
| NSF101 | 942 | 1201 | 68 | 13.2 |
| NSF102 | 1124 | 1264 | 64 | 13.7 |
| NSF103 | 1062 | 1357 | 60 | 13.6 |
| NSF104 | 1042 | 1261 | 66 | 14.2 |
| NSF105 | 1057 | 1354 | 59 | 10.7 |
| NSF106 | 1124 | 1245 | 62 | 13.5 |
| NSF107 | 972 | 1210 | 72 | 16.6 |
| NSF108 | 1119 | 1448 | 55 | 13.5 |
| NSF109 | 1141 | 1266 | 61 | 13.1 |
| T24 | 347 | 586 | 89 | 22.9 |
Test example 3
Cut the invention steel NSF104 ' making in embodiment 2 is processed into tensile sample by line,On MTS testing machine, carry out tensile test at room temperature, recording yield strength is 1082MPa, and hot strength is1240MPa, the contraction percentage of area is 67%, percentage elongation is 12.4%.
As described in Example 2, invention steel NSF104 ' forms and heat treatment with the alloying component of NSF104Technique is identical, and difference is, invention steel NSF104 ' carries out solution treatment at 850 DEG C. Pass throughReduce solid solution temperature, can prevent that crystal grain from growing up fast, obtain fine grained texture. Thereby, by above-mentioned chamberThe mechanical property that temperature stretching experiment records is known, carries out the rich Cu that solution treatment makes at described temperatureThe superhigh intensity ferritic steel of nanocluster strengthening has the intensity of superelevation and good plasticity and toughness equally.
Test example 4
Cut the invention steel NSF104 making in embodiment 3 by line " be processed into tensile sample,On MTS testing machine, carry out tensile test at room temperature, recording yield strength is 944MPa, and hot strength is1207MPa, the contraction percentage of area is 62%, percentage elongation is 12.7%.
As described in Example 3, invention steel NSF104 is " with alloying component composition and the heat treatment of NSF104Technique is identical, and difference is, invention steel NSF104 " carries out solution treatment at 1200 DEG C. Pass throughImprove solid solution temperature, make the abundant solid solution of alloying element, cooling rear alloying element is in ferrite matrixTo there is larger degree of supersaturation, thereby increase the nucleation rate of nanometer precipitated phase, and then in the time of Ageing TreatmentCan produce more nano-strengthening phase. Thereby the mechanical property being recorded by above-mentioned tensile tests at room canKnow, at described temperature, carry out the superhigh intensity iron element of the rich Cu nanocluster strengthening that solution treatment makesBody steel has the intensity of superelevation and good plasticity and toughness equally.
In sum, one aspect of the present invention, from thermodynamics optimal design alloying component, is rationally adjusted faceThe proportioning of the heart cube element, C element and other alloying elements, farthest increases nanometer precipitated phaseVolume fraction, and control Precipitation Temperature simultaneously and separate out the time, bring up a large amount of nucleation sites, make all solidFused gold element is evenly separated out, and controls growing up of nanometer precipitated phase while separating out in position, obtain concentration high,The rich Cu nanocluster be evenly distributed, size being tiny, to realizing the superhigh intensity of novel ultra-high strength steelPlay the effect of most critical. In addition the effective crystal grain thinning of nano-carbide, optimized alloy element producesThe effect of raw solution strengthening, cold and hot distortion produces crystal grain thinning and dislocation strengthening effect. Therefore, the present inventionThe superhigh intensity ferritic steel of rich Cu nanocluster strengthening be taking nanocluster strengthening as main, thin brilliant strongNEW TYPE OF COMPOSITE reinforced low-carbon, low cost that the various ways such as change, solution strengthening and dislocation strengthening combine are superHigh strength steel, has superhigh intensity and good welding performance, plasticity and toughness, corrosion resistance, comprehensiveCan be excellent, can be widely used in automobile, naval vessel, bridge, pipeline, the energy, power station, ocean engineering,The fields such as building structure, pressure vessel, engineering machinery, container and defence equipment.
Those skilled in the art it should be noted in the discussion above that embodiment described in the invention is only exemplary, can make within the scope of the invention various other replacements, changes and improvements. Thereby the present invention is notBe limited to above-mentioned embodiment, and be only defined by the claims.
Claims (18)
1. a superhigh intensity ferritic steel for rich Cu nanocluster strengthening, by weight percentage, its changeComponent is as follows:
C is 0～0.2%; Cu is 1.5～5%; Ni is 0.01～2.5%; Mn is 0.75～4%; Al is0.001～2%; Cr is 0～12%; Mo is that 0～3%, W is that 0～3%, Mo+W is not less than 0.05%;V is that 0～0.5%, Ti is that 0～0.5%, Nb is that 0～0.5%, V+Ti+Nb is not less than 0.01%; Si is0～1%; B is 0.0005～0.05%; P is not higher than 0.04%; S is not higher than 0.04%; N is not higher than 0.04%;O is not higher than 0.05%; Surplus is Fe and inevitable impurity.
2. according to the superhigh intensity ferritic steel of the rich Cu nanocluster strengthening of claim 1, described richnessThe component of Cu nanocluster is Cu, Ni, Mn, Al.
3. according to the superhigh intensity ferritic steel of the rich Cu nanocluster strengthening of claim 1, described richnessThe average-size of Cu nanocluster is 3nm, and spacing is 2～10nm, and every cu μ m nanoclusters number of clusters is notBe less than 10,000.
4. according to the superhigh intensity ferritic steel of the rich Cu nanocluster strengthening of claim 1, wherein also wrapContaining composite Nano carbide (V, Ti, Nb) C, described composite Nano carbide (V, Ti, Nb) C is of a size of5～100nm。
5. according to the superhigh intensity ferritic steel of the rich Cu nanocluster strengthening of claim 1, its matrix groupBe woven to ferrite, described ferritic average grain size is 1～20 μ m.
6. according to the superhigh intensity ferrite of the rich Cu nanocluster strengthening of any one in claim 1 to 5Steel, its yield strength is 900～1200MPa.
7. according to the superhigh intensity ferrite of the rich Cu nanocluster strengthening of any one in claim 1 to 5Steel, its hot strength is 1200～1500MPa.
8. according to the superhigh intensity ferrite of the rich Cu nanocluster strengthening of any one in claim 1 to 5Steel, its percentage elongation is 10～20%.
9. according to the superhigh intensity ferrite of the rich Cu nanocluster strengthening of any one in claim 1 to 5Steel, its contraction percentage of area is 50%～80%.
10. manufacture the superhigh intensity iron element of the rich Cu nanocluster strengthening of aforementioned any one claim for one kindThe method of body steel, its step is as follows:
(1) what make that the chemical constituent of the superhigh intensity ferritic steel of described rich Cu nanocluster strengthening forms is formerFeed composition carries out melting, casting and forging rolling successively;
(2) carry out solution treatment, be then cooled to room temperature;
(3) carry out Ageing Treatment, be then cooled to room temperature.
11. according to the method for claim 10, and wherein said solution treatment is entered within the scope of 800～1300 DEG COK.
12. according to the method for claim 11, and wherein said solution treatment is carried out at 900 DEG C.
13. according to the method for claim 11 or 12, and wherein said solution treatment is carried out 0.1～3 hour.
14. according to the method for claim 13, and wherein said solution treatment is carried out 0.5 hour.
15. according to the method for claim 10, and wherein said Ageing Treatment is entered within the scope of 400～600 DEG COK.
16. according to the method for claim 15, and wherein said Ageing Treatment is carried out at 550 DEG C.
17. according to the method for claim 15 or 16, and wherein said Ageing Treatment is carried out 0.1～20 hour.
18. according to the method for claim 17, and wherein said Ageing Treatment is carried out 2 hours.
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| PCT/CN2014/073406 WO2014139453A1 (en) | 2013-03-13 | 2014-03-13 | Ultrahigh strength ferritic steel strengthened by using cu-rich nanoclusters, and manufacturing thereof |
| JP2015561927A JP6584961B2 (en) | 2013-03-13 | 2014-03-13 | Copper-rich nanocluster reinforced ultra high strength ferritic steel and method for producing the same |
| JP2019011574A JP6794479B2 (en) | 2013-03-13 | 2019-01-25 | Copper-rich nanocluster reinforced ultra-high-strength ferritic steel and its manufacturing method |
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| CN109504903B (en) * | 2016-08-18 | 2021-01-29 | 江苏鼎泰工程材料有限公司 | Low-alloy ultrahigh-strength steel |
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| CN106636909A (en) * | 2017-01-13 | 2017-05-10 | 南京理工大学 | Corrosion-resistant soft magnetic ferrite stainless steel |
| JP6969222B2 (en) * | 2017-08-23 | 2021-11-24 | 日本製鉄株式会社 | Cu-added steel sheet |
| KR102168829B1 (en) * | 2018-12-10 | 2020-10-22 | 주식회사 포스코 | LOW-Cr FERRITIC STAINLESS STEEL WITH EXCELLENT FORMABILITY AND HIGH TEMPERATURE PROPERTIES AND MANUFACTURING METHOD THEREOF |
| US20220154301A1 (en) * | 2019-02-28 | 2022-05-19 | Jfe Steel Corporation | Steel sheet and member, and methods for manufacturing same |
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| CN111326217B (en) * | 2020-01-22 | 2023-03-21 | 北京化工大学 | Metal nanocluster structure optimization method |
| JP7278476B2 (en) * | 2020-04-15 | 2023-05-19 | 日鉄ステンレス株式会社 | Ferritic stainless steel material and manufacturing method thereof |
| CN112795844B (en) * | 2020-12-29 | 2021-12-03 | 钢铁研究总院 | Low-carbon Cr-Ni series high-strength corrosion-resistant steel and preparation method thereof |
| CN113755760B (en) * | 2021-09-10 | 2022-08-19 | 北京科技大学 | In-situ nano reinforced and toughened steel for crankshafts |
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| CN114540708B (en) * | 2022-02-14 | 2023-03-17 | 厦门大学 | Co-rich nanoparticle reinforced ferrite stainless steel and preparation method thereof |
| CN114807774B (en) * | 2022-06-21 | 2023-05-30 | 育材堂（苏州）材料科技有限公司 | Hot work die steel, heat treatment method thereof and hot work die |
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| CN116493883B (en) * | 2023-06-07 | 2024-01-19 | 徐州徐工基础工程机械有限公司 | Method for manufacturing housing of mechanical equipment power component and housing |
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| WO2014139453A1 (en) | 2014-09-18 |
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