CN105734437A - Nanoscale rodlike copper precipitated phase strengthening and toughening marine steel plate and preparation method thereof - Google Patents
Nanoscale rodlike copper precipitated phase strengthening and toughening marine steel plate and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
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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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
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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
- 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
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
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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
- 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
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0231—Warm rolling
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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
- 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
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0273—Final recrystallisation annealing
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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
- C22C38/02—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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- 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
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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
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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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
- C22C38/14—Ferrous alloys, e.g. steel alloys containing 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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/001—Austenite
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
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Abstract
The invention discloses a nanoscale rodlike copper precipitated phase strengthening and toughening marine steel plate and belongs to the technical field of metallurgy materials.The steel plate is prepared from C, Cu, Mn, Al, Si, Mo, Ti and the balance Fe and unavoidable impurities.The preparation method comprises the first step of ingot casting, the second step of hot rolling, the third step of warm rolling and the fourth step of heat treatment.In the second step of hot rolling, heat treatment is carried out on a cast ingot, 4-10 passes of hot rolling is carried out, the temperature is rapidly decreased and kept for a period of time, then water cooling is carried out to reach the normal temperature, and a hot-rolled steel plate is obtained; in the third step of warm rolling, 6-10 passes of warm rolling is carried out on the hot-rolled steel plate, and annealing treatment is carried out before each time of warm rolling; in the fourth step of heat treatment, the temperature of the warm-rolled steel plate is rapidly increased to 800-850 DEG C and kept, then, the temperature is rapidly decreased to 380-420 DEG C and kept, and therefore the product is obtained.According to the steel plate, the tensile strength is 1700-1850 MPa, the yield strength is 650-730 MPa, and the stretch rate is 32-38%.The steel material with nanoscale rodlike Cu educt, a submicron austenite betten structure and small ferrite grains is prepared and has the quite high strength and plasticity, and the corrosion resistance of steel is improved.
Description
Technical field
The invention belongs to metallurgical material technical field, particularly to a kind of nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate and preparation method thereof.
Background technology
Steel are a kind of at field purposes materials the most widely such as aviation, nuclear energy, naval vessel, petrochemical industry;High-intensity high-tenacity is the main development direction of ferrous materials;The subject matter run at present is how to keep good toughness improving its intensity while;At present, China's environmental problem has a strong impact on health and the orthobiosis of people;Promote automotive light weight technology by improving the intensity of ferrous materials, be reduction energy consumption, reduce and pollute the effective measures reducing carbon emission.It addition, China on the Nansha Islands, the dispute of region, the East Sea and surrounding countries is growing more intense.Wherein, the Nansha Islands have highly important strategic position in geopolitics and military security, the important straits such as the maritime traffic throat of Pacific and Indian oceans is gripped in the Nansha Islands and marine site thereof, nearly Malacca, ground, are the nearest air routes sailing for the Indian Ocean, the Middle East, Europe from Asia.Can living in island or the shoal reef of people at more than 50, the South Sea, have that half is many to be occupied by Vietnam, China's Mainland is only actual controls 8, and China's ocean vivosphere from now on has been buried factor leading to social instability by this present situation.China to complete South Sea deployment in recent years, strives for favourable international environment, controls to belong to the territory of the Chinese nation, needs emphasis badly and build a collection of large-scale ships and relevant ocean work platforms thereof, coordinate the maritime sovereignty safeguarding China.Therefore, the research and development of marine steel are one of China's national defense industry important directions sending out exhibition.In order to promote the sustainable development of Shipbuilding of China, National Development and Reform Committee it is proposed that to make the first shipbuilding state in 2015.Obviously, along with China prepares manufacturing flourish, the demand of high-quality steel plate will be continued to increase.
The core theory of " Iron & Steel Material of New Generation " or " super-steel " and technology are to realize the super-refinement of steel interior tissue, the matrix of current fine-grained steel are refined to micron number magnitude so that it is intensity significantly improves.Its strengthening approach is totally different from traditional strengthening approach being added to main maneuver with alloying element, but have employed and reduce alloying component content as far as possible so that it is carbon equivalent maintains in the level of mild steel, relies on grain ultrafining to improve intensity.The project of Ultra-Grade Steels have employed crystal grain micronization, composition alloy or the approach without alloying element, it is possible to obtain is prone to the steel with ferrite for principal phase tissue of welding.This is the plan formulated on theoretical breakthrough basis for the first period and come into effect, and the development of following high-quality special steel is had directive significance.
In order to ensure to meet high-end equipment manufacturing demand and dependability, in order to enable successfully to build the large ship of military service function admirable when modern production, it is necessary to structural steel possesses every good performance.(1) enough intensity: means of transport bears down bigger dead load and alternate load in working order, especially in the severe ocean conditions such as stormy waves, its dead load born is bigger, and alternate load is increasingly complex.It is therefore necessary to ensure structural member has necessary strength.(2) good plasticity: vehicle structure component, through various forms of bendings, punching press ability molding.Bending have cold rectify, roll bending, mold pressing, crimping, the cold-working such as flanging bending, have again the hot-working such as hot bending, hot moulding, flame forming plate and fairing by flame.In order to ensure steel can successfully machine-shaping, and in steel stretcher strain situation, do not cause excessive hardening, and cause hydraulic performance decline, even crack.Steel should possess the stretcher strain ability of abundance, namely adapts to the plasticity of stretcher strain.The stretcher strain when plasticity of the steel after molding still can ensure steel plate redeformation-possess good plasticity.(3) good fatigue performance: means of transport such as boats and ships etc. rise and fall along with wave in ocean, and Ship Structure is subject to the effect of tension and compression stress alternation.It will result in a certain position of hull and produces fatigue crack, and fatigue crack can become again the formation of crack of brittle break.Therefore for making hull steel, requiring again the resistance to low cycle fatigue property that it must possess, the experimental results proves that the fatigue behaviour of metal material is directly proportional to its intensity, and therefore, improving intensity is improve the effective measures of its fatigue behaviour.(4) good decay resistance: means of transport is at wet environment, particularly in rivers,lakes and seas, or offshore production platform high-quality special steel is in marine environment for a long time, they to be unavoidably subject to the erosion of big gas and water and aquatic organism, cause that corrosion of component is thinning, even bore a hole, reduce service life, thus increasing the repairing number of times updating steel plate.Therefore, decay resistance is also a critically important requirement.High tough weather resisting steel is the developing focus of recent domestic, and China coastline is longer, coastal area mostly is again developed area, steel construction makes consumption big, sea atmosphere corrosion becomes outstanding problem, it is necessary to more researcheres are engaged in the research and development of the novel weathering resistant steel that height is tough, corrosion resisting property is higher.
On engineer applied, in order to strengthening material adopts crystal grain thinning method, utilizing a large amount of crystal boundary existed to improve the intensity of material in restriction or anchoring dislocation motion, its principle can by Hall-Petch relation (σ=σ0+kd-1/2) describe.Grain refinement makes grain boundary area total in unit volume increase, it is thus achieved that higher intensity, the yield strength of most metals material and hardness number show the trend of increase with the reduction of crystallite dimension;Yield strength (the σ that common coarse crystal steel (crystallite dimension is about 100 μm) at room temperature stretchesy) it being only 90MPa, ultra-fine grain micro-alloy steel (crystallite dimension is about 6 μm) at room temperature stretches, its yield strength σy~310MPa.It addition, the schedule of reinforcement of material includes precipitation hardening, refined crystalline strengthening, phase transformation strengthening, solution strengthening (displacement strengthening and gap strengthening), dislocation and subgrain strengthening etc..The impact of the strength of materials can be represented with the Hall-Petch formula revised: σy=σ0+σss+σint+σp+σtr+σdis+Kyd-1/2;σ in formula0Lattice friction (hinders power and the lattice resistance of dislocation motion);σssDisplacement strengthening increment;σimGap strengthening increment;σpPrecipitation strength increment;σtrPhase transformation strengthening increment;σdisDislocation and substructure strengthening increment;KyThe intercrystalline strengthening factor;D crystal grain diameter.Wherein, the intensity increment that precipitate causes can with famous Orowan mechanism estimation: σp=0.8MGb/ λ, wherein M is the Taylor factor, and G is modulus of shearing, b Bai Geshi vector, and λ is adjacent precipitate spacing;Visible precipitated phase density improves and size reduction is all conducive to improving precipitating reinforcing effect.
Novel TRIP590 (Fe-1.4Mn-0.3Si-0.03Al-0.07C) steel prepared by Anshan iron and steel plant is applied in auto industry, its crystallite dimension is about 20 μm, when room temperature tensile, its yield strength is 450MPa, tensile strength is the 860MPa (development of novel TRIP590 and the TRIP780 of Anshan iron and steel plant, 7th China Steel nd Annual Meeting collection, rolls up 4,137-140 (2009));Although the material prepared by the method has higher yield strength and tensile strength, but its extensibility is relatively low, is only 27%.The Fe-1.45Mn-1.22Si-0.03Al-0.12Ni-0.12CTRIP590 steel that Jia Shujun et al. is prepared, average grain size is about 5.7 μm, its yield strength is 430MPa, tensile strength is about 600MPa, extensibility 23% (the two-phase section annealing temperature impact on TRIP590 structure of steel and performance, material heat treatment journal, rolls up 34,110-114 (2013));Its yield strength is close with the present invention, but tensile strength and plasticity are relatively low, high intensity and high tenacity are required, and higher application is not met by requirement, and its higher Si content, easily cause the surface defect in industrial processes, make follow-up zinc-plated operation encounter difficulties.Although, for the problems referred to above, Shen Yongfeng et al. adopts quenching-partition Technology for Heating Processing to make the tensile strength of TRIP590 steel reach 1000MPa, elongation percentage up to 50% (Y.F.Shen, L.N.Qiu, X.Sun, L.Zuo, P.K.Liaw, D.Raabe, Effectsofretainedaustenitevolumefraction, morphology, andcarboncontentonstrengthandductilityofnanostructuredTR IP-assistedsteels, Mater.Sci.Eng.A, Vol.636,551-564 (2015)), prepared for Korea S Huh et al. TRIP590 steel (J.Y.HuhH.Huh, C.S.Lee, Effectofstrainrateonplasticanisotropyofadvancedhighstren gthsteelsheets, JInt.Plast., Vol.44,23-46 (2013)), tensile strength can reach 850MPa, but still with marine steel needed for superhigh intensity value have bigger gap, and plasticity is also relatively low, extensibility is only 20%.
Summary of the invention
For the combination property above shortcomings of existing TRIP Steel material, the present invention provides a kind of nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate and preparation method thereof.The method is by quickly heating and controls bainite isothermal transformation temperature and temperature retention time, obtain the bar shaped austenite of rod-like nano yardstick Cu precipitated phase, submicron-scale, in deformation process, On Dislocation Motion has inhibition, austenite structure is progressively changed into the process of martensitic phase, improves toughness while reinforced metal.
The nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate of the present invention, composition is by weight percentage: C:0.56 ± 0.03%, Cu:0.5 ± 0.1%, Mn:1.5 ± 0.2%, Al:1.5 ± 0.1%, Si:0.5 ± 0.1%, Mo:0.2 ± 0.02%, Ti:0.1 ± 0.02%, surplus is Fe and inevitable impurity, and steel plate thickness is 1.5~3.0mm.
The nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate of the present invention, its tensile strength is 1700~1850MPa, and yield strength is 650~730MPa, and extensibility is 32~38%.
The nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate of the present invention, its microstructure is made up of the ferrite crystal grain of isometry, the particle diameter of crystal grain is at 1~12 μm, bar shaped austenite in ferrite grain boundaries region accounts for the 20~30% of the crystal grain gross area, the austenitic width of bar shaped is 100~300nm, and length is 2~10 μm;The length of the bar-shaped Cu precipitate of nanoscale is 30~100nm, and width is 10~50nm, and Dispersed precipitate is in bar shaped austenite.
The preparation method of the nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate of the present invention, comprises the following steps:
Step 1, ingot casting:
By the composition proportion of steel plate, under noble gas or nitrogen atmosphere are protected, smelt and pour into ingot casting;
Step 2, hot rolling:
(1) by ingot casting, heat to 1150~1230 DEG C of insulation 2~3h;
(2) by the ingot casting after insulation, carrying out hot rolling, start rolling temperature is 1150~1250 DEG C, and finishing temperature is 950~1050 DEG C, and hot rolling overall reduction is 60~90%;
(3) by the steel plate after hot rolling, it is cooled to 750~850 DEG C with the speed of 40~60 DEG C/s, is incubated 0.5~1h, then water-cooled is to room temperature, it is thus achieved that hot rolled steel plate;
Step 3, warm-rolling:
By hot rolled steel plate, carrying out 6~10 passage warm-rollings, before every time warm-rolling, be annealed processing, until warm-rolling overall reduction is 60~75%, air cooling is to room temperature, it is thus achieved that warm-rolling steel plate;Wherein, annealing temperature is 720~780 DEG C, and annealing time is 30min;
Step 4, heat treatment (partition-microalloy element is redistributed):
(1) by warm-rolling steel plate, heat to 800~850 DEG C with the speed of 100~200 DEG C/s, be incubated 120~180s;
(2) then, it is quickly cooled to 380~420 DEG C with the speed of 80~100 DEG C/s, is incubated 4~6min, obtains nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate.
In described step 1, smelting the raw material selected is metallic iron, manganese metal, metallic aluminium, metallic silicon, metallic copper, metal molybdenum, Titanium.
In described step 1, smelting temperature is 1620~1680 DEG C.
In described step 1, noble gas or nitrogen atmosphere protection refer to: by smelting equipment, be evacuated to vacuum≤100Pa, pass into noble gas or nitrogen to normal pressure, then smelt;Described noble gas is argon.
In described step 2 (3), carry out 4~10 passage hot rollings.
In described step 3, holding furnace is adopted to be annealed processing.
Described step 4, the equipment of employing is electric pole type salt bath furnace.
In described step 4 (1), adding thermal medium is NaCl.
In described step 4 (2), adding thermal medium is KNO3And NaNO2, KNO3And NaNO2Mass ratio be 55: 45.
Copper can improve the atmospheric corrosion resistance ability of low-alloy steel.In rustless steel, copper can improve the corrosion resistance to 2-cyclopenten-2,3-diol-1-one., and makes steel have good deep drawing quality, and copper also has precipitation-hardening effect.Steel are in corrosion process, and copper plays a part activated cathode, promote anodic passivity thus slowing down corrosion.It addition, copper can form close thin copper oxide intermediate layer between the corrosion layer of steel and measuring copper layer, form double-deck rusty scale, be close to the internal layer of steel matrix, can slow down inside corrosive medium corrosion steel plate.The nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate of the present invention, is thermally treated resulting in different tissue morphologies through different process.Adopt transmission electron microscope that the microstructure after cupric TRIP steel partition heat treatment is observed, find that the bar-shaped Cu of nanoscale of diffusion-precipitation distribution in partition process precipitates out and submicron austenite lath, and along with the rising of partition temperature, the bar-shaped Cu precipitate of nanoscale increases;Conservative control partition temperature and temperature retention time, to obtain the fine austenite tissue of nanoscale bar-shaped Cu precipitate and stable submicron-scale;Si in tissue postpones the formation of carbide, makes carbon content in austenite increase, is solid-solution in the intensity and hardness that can improve steel in austenite;C, Mn, Al can suppress transformation of austenite to martensite, play the effect of stable austenite;Cu is enriched with into little granule at interior rusty scale, promotes the formation of dense barrier layer, stops matrix to corrode further.Obtained rod-like nano yardstick Cu precipitated phase, the bar shaped austenite of submicron-scale, in deformation process, On Dislocation Motion has set direction inhibition, austenite structure is progressively changed into the process of martensitic phase simultaneously, improves toughness while reinforced metal.
Principles of the invention is: under quickly heating, condition of fast cooling, makes steel plate obtain the fine austenite lath of the bar-shaped Cu precipitate of nanoscale and submicron-scale, obtains fine ferrite crystal grain simultaneously;The bainite isothermal transformation temperature of conservative control cold-rolled steel sheet and temperature retention time, to obtain stable residual austenite soma and to prevent cementite from precipitating out in isothermal transformation, make the austenite structure formed in steel plate can retain to room temperature;Si in tissue postpones the formation of carbide, makes carbon content in austenite increase, easily retains to room temperature, be solid-solution in the intensity and hardness that can improve steel in austenite;C, Mn, Al can suppress transformation of austenite to martensite, play the effect of stable austenite;The bar-shaped Cu precipitate Dispersed precipitate of obtained nanoscale is in the bar shaped austenite of submicron-scale, bar shaped austenite at deformation process sub-micron yardstick is progressively changed into martensite, precipitate and the lath martensite On Dislocation Motion being deformed into mutually have extremely strong inhibition, make metal be strengthened;Simultaneously the bar shaped austenite of submicron-scale is progressively changed into the process of martensite and makes toughness improve, the Cu of the nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate of the present invention contributes to copper and improves the atmospheric corrosion resistance ability of steel, improve the corrosion resistance to 2-cyclopenten-2,3-diol-1-one., and make steel have good deep drawing quality.
Nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate of the present invention and preparation method thereof, compared with prior art, has the advantage that
1. by melting, continuous rolling combination quickly heating, fast cooling technology, set rational technical process and technological parameter prepares the Steel material with the bar-shaped Cu precipitate of nanoscale, submicron austenite lath and fine ferrite crystal grain, there is very high intensity and plasticity, be significantly higher than prepare by traditional method chemistry similar composition, crystallite dimension steel sample;
2. owing to high strength steel plate has the bar shaped austenitic structure of the bar-shaped Cu precipitate of nanoscale and submicron order, this composite construction On Dislocation Motion in deformation process has very strong inhibition, submicron order bar shaped austenite structure is progressively changed into martensite, by the strong plasticity of phase change induction, and make hardening increase mutually, this material is made to have very high tensile strength, good plasticity and superior anti-wear performance, Cu in steel is favorably improved corrosion resistance, the steel plate that this height is tough is to Yu Haiyang large ship, engineering platform demand, the development of the new technical field such as a new generation's lightweight automobile has important value;
3. existing process conditions only need to be carried out simple modifications by the preparation method of the present invention, suitably adjust for chemical composition, add a small amount of Cu, control the parameter such as heat treatment and cooling and can obtain this high-strength corrosion-resistant erosion steel plate.
Accompanying drawing explanation
The scanning electron micrograph figure of the nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate of Fig. 1 embodiment of the present invention 1 preparation;Wherein, A is austenite, and B is martensite, and C is ferrite;
The low power transmission electron micrograph figure of the nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate of Fig. 2 embodiment of the present invention 1 preparation;Wherein, A is austenite, and B is martensite, and C is ferrite, and D is that copper precipitates out;
The high power transmission electron micrograph figure of the nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate of Fig. 3 embodiment of the present invention 1 preparation;Wherein, A is austenite, and E is nano twin crystal, and D is that copper precipitates out;
The true stress-true strain curve chart of nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate prepared by Fig. 4 embodiment of the present invention;Wherein, 1-correspondence embodiment 1,2-correspondence embodiment 2,3-correspondence embodiment 3,4 is the product in comparative example.
Detailed description of the invention
The metallic iron selected in following example is by weight percentage containing C0.002~0.008%, Mn0.1~0.2%, Al0.05~0.08%, Si0.03~0.06%, and surplus is Fe and inevitable impurity.
The manganese metal selected in following example is by weight percentage containing C0.07~0.09%, Fe1.1~2.2%, Si0.03~0.04%, and surplus is Mn and inevitable impurity.
The metallic aluminium selected in following example is by weight percentage containing Fe0.1~0.2%, Si0.02~0.05%, Mn0.001~0.002%, and surplus is Al and inevitable impurity.
The metallic silicon selected in following example is by weight percentage containing Fe0.1~0.3%, Al0.1~0.3%, and surplus is Si and inevitable impurity.
The metallic copper selected in following example is by weight percentage containing Fe0.01~0.03%, Ni0.01~0.02%, and surplus is Cu and inevitable impurity.
The metal molybdenum selected in following example is by weight percentage containing Fe0.02~0.03%, Co0.03~0.05%, and surplus is Mo and inevitable impurity.
The Titanium selected in following example is by weight percentage containing Fe0.03~0.05%, Si0.02%, Mn0.01%, and surplus is Ti and inevitable impurity.
The device that quickly cooling adopts in following example is Northeastern University's rolling technique and the Ultrafast cooling device of National Key Laboratory of tandem rolling automatization exploitation.
Following example are smelted under noble gas or nitrogen atmosphere are protected, refers to and smelting equipment is evacuated to vacuum≤100Pa, then pass to noble gas or nitrogen to normal pressure, then smelt;Noble gas selects argon.
The equipment smelting employing in following example is vaccum sensitive stove.
The cold-rolling equipment adopted in step 3 in following example is the double; two unidirectional asynchronous rolling machine of roller of Φ 450 type.
In following example, the quickly heating of step 4 light plate and the firing equipment of insulation employing are electric pole type salt bath furnace;Wherein heating to 800~850 DEG C of heating Jie adopted when being incubated is NaCl, and the thermal mediums that add adopted when cooling to 380~420 DEG C of insulations are KNO3And NaNO2, KNO3And NaNO2Mass ratio be 55: 45.
The equipment testing the employing of sheet metal mechanical property in following example is AG-Xplus100kN type electronic universal tester.
Embodiment 1
Nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate, composition is by weight percentage: C:0.56%, Mn:1.5%, Al:1.5%, Si:0.5%, Cu:0.5%, Mo:0.2%, Ti:0.1%, and surplus is Fe and inevitable impurity;Steel plate thickness is 1.5mm.
The preparation method of nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate, comprises the following steps:
Step 1, ingot casting:
By the composition proportion of steel plate, selecting metallic iron, manganese metal, metallic aluminium, metallic silicon, metallic copper, metal molybdenum, Titanium is raw material;
In a nitrogen atmosphere, 1620 DEG C of smeltings, ingot casting is poured into;
Step 2, hot rolling:
(1) by ingot casting, heat to 1200 DEG C of insulation 2h;
(2) by the ingot casting after insulation, carrying out 4 passage hot rollings, start rolling temperature is 1080 DEG C, and finishing temperature is 1030 DEG C, and overall reduction is 60%;
(3) by the steel plate after hot rolling, it is cooled to 800 DEG C with the speed of 50 DEG C/s, is incubated 0.5h, then water-cooled is to room temperature, it is thus achieved that hot rolled steel plate;
Step 3, warm-rolling:
By hot rolled steel plate, carrying out 8 passage warm-rollings, before every time warm-rolling, be annealed processing, until warm-rolling overall reduction is 75%, air cooling is to room temperature, it is thus achieved that thickness is 1.5mm warm-rolling steel plate;Wherein, annealing temperature is 750 DEG C, and annealing time is 30min;
Step 4, heat treatment:
(1) by warm-rolling steel plate, heat to 820 DEG C with the speed of 120 DEG C/s, be incubated 180s;
(2) then, with the speed ultra-rapid cooling of 90 DEG C/s to 400 DEG C, it is incubated 5min, obtains nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate.
Nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate prepared by the present embodiment, its tensile strength is 1850MPa, and yield strength is 700MPa, and extensibility is 37%;Its microstructure is made up of the ferrite crystal grain of isometry, and the particle diameter of crystal grain is at 1~5 μm, and the bar shaped austenite in crystal grain adjacent area accounts for the 30% of the crystal grain gross area, and the austenitic mean breadth of bar shaped is 100nm, length 2~3 μm;The nano bar-shape Cu having a large amount of Dispersed precipitate in bar shaped austenite precipitates out, and mean breadth is 20nm, length 50nm;The nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate of the present embodiment, the scanning electron micrograph of its microstructure is as shown in Figure 1;As shown in Figure 2 and Figure 3, Fig. 3 discloses pattern and the distribution of the bar-shaped Cu precipitate of the nanoscale in submicron order bar shaped austenite to projection electron microphotograph;The true stress-true strain curve of stretcher strain is such as shown in Fig. 4 curve 1;
The nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate of the present embodiment, yield strength is 7 times of common coarse crystal micro alloyed steel (crystallite dimension about 100 μm), yield strength height~400MPa than superfine steel alloy (crystallite dimension about 6 μm),~250MPa higher than the yield strength of novel TRIP590 steel, yield strength and Tensile strength data are superior to the performance through the heat treated TRIP590 steel (without Cu) of same process, shown in the curve 4 in true stress-true strain curve such as Fig. 4 of the stretcher strain of TRIP590 steel.
Embodiment 2
Nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate, composition is by weight percentage: C:0.53%, Mn:1.3%, Al:1.4%, Si:0.4%, Cu:0.4%, Mo:0.18%, Ti:0.08%, and surplus is Fe and inevitable impurity;Steel plate thickness is 1.5mm.
The preparation method of nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate, comprises the following steps:
Step 1, ingot casting:
By the composition proportion of steel plate, selecting metallic iron, manganese metal, metallic aluminium, metallic silicon, metallic copper, metal molybdenum, Titanium is raw material;
In a nitrogen atmosphere, 1640 DEG C of smeltings, ingot casting is poured into;
Step 2, hot rolling:
(1) by ingot casting, heat to 1250 DEG C of insulation 2h;
(2) by the ingot casting after insulation, carrying out 6 passage hot rollings, start rolling temperature is 1250 DEG C, and finishing temperature is 1050 DEG C, and overall reduction is 70%;
(3) by the steel plate after hot rolling, it is cooled to 750 DEG C with the speed of 40 DEG C/s, is incubated 1h, then water-cooled is to room temperature, it is thus achieved that hot rolled steel plate;
Step 3, warm-rolling:
By hot rolled steel plate, carrying out 6 passage warm-rollings, before every time warm-rolling, be annealed processing, until warm-rolling overall reduction is 60%, air cooling is to room temperature, it is thus achieved that thickness is 1.5mm warm-rolling steel plate;Wherein, annealing temperature is 720 DEG C, and annealing time is 30min;
Step 4, heat treatment:
(1) by warm-rolling steel plate, heat to 800 DEG C with the speed of 100 DEG C/s, be incubated 180s;
(2) then, with the speed ultra-rapid cooling of 80 DEG C/s to 380 DEG C, it is incubated 6min, obtains nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate.
Nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate prepared by the present embodiment, its tensile strength is 1848MPa, and yield strength is 710MPa, and extensibility is 35%;Its microstructure is made up of the ferrite crystal grain of isometry, and the particle diameter of crystal grain is at 1~5 μm, and the bar shaped austenite in crystal grain adjacent area accounts for the 20% of the crystal grain gross area, and the austenitic mean breadth of bar shaped is 150nm, length 5~8 μm;The nano bar-shape Cu having a large amount of Dispersed precipitate in bar shaped austenite precipitates out, and mean breadth is 15nm, length 40nm.
Embodiment 3
Nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate, composition is by weight percentage: C:0.56%, Mn:1.7%, Al:1.6%, Si:0.6%, Cu:0.6%, Mo:0.22%, Ti:0.12%, and surplus is Fe and inevitable impurity;Steel plate thickness is 3.0mm.
The preparation method of nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate, comprises the following steps:
Step 1, ingot casting:
By the composition proportion of steel plate, selecting metallic iron, manganese metal, metallic aluminium, metallic silicon, metallic copper, metal molybdenum, Titanium is raw material;
In a nitrogen atmosphere, 1660 DEG C of smeltings, ingot casting is poured into;
Step 2, hot rolling:
(1) by ingot casting, heat to 1150 DEG C of insulation 3h;
(2) by the ingot casting after insulation, carrying out 10 passage hot rollings, start rolling temperature is 1150 DEG C, and finishing temperature is 950 DEG C, and overall reduction is 90%;
(3) by the steel plate after hot rolling, it is cooled to 850 DEG C with the speed of 60 DEG C/s, is incubated 0.5h, then water-cooled is to room temperature, it is thus achieved that hot rolled steel plate;
Step 3, warm-rolling:
By hot rolled steel plate, carrying out 10 passage warm-rollings, before every time warm-rolling, be annealed processing, until warm-rolling overall reduction is 75%, air cooling is to room temperature, it is thus achieved that thickness is 3.0mm warm-rolling steel plate;Wherein, annealing temperature is 780 DEG C, and annealing time is 30min;
Step 4, heat treatment:
(1) by warm-rolling steel plate, heat to 850 DEG C with the speed of 200 DEG C/s, be incubated 120s;
(2) then, with the speed ultra-rapid cooling of 100 DEG C/s to 420 DEG C, it is incubated 4min, obtains nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate.
Nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate prepared by the present embodiment, its tensile strength is 1756MPa, and yield strength is 680MPa, and extensibility is 32%;Its microstructure is made up of the ferrite crystal grain of isometry, and the particle diameter of crystal grain is at 1~5 μm, and the bar shaped austenite in crystal grain adjacent area accounts for the 30% of the crystal grain gross area, and the austenitic mean breadth of bar shaped is 300nm, length 2~6 μm;The nano bar-shape Cu having a large amount of Dispersed precipitate in bar shaped austenite precipitates out, and mean breadth is 40nm, length 58nm.
Embodiment 4
Nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate, composition is by weight percentage: C:0.59%, Mn:1.6%, Al:1.4%, Si:0.6%, Cu:0.6%, Mo:0.2%, Ti:0.1%, and surplus is Fe and inevitable impurity;Steel plate thickness is 2.0mm.
The preparation method of nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate, comprises the following steps:
Step 1, ingot casting:
By the composition proportion of steel plate, selecting metallic iron, manganese metal, metallic aluminium, metallic silicon, metallic copper, metal molybdenum, Titanium is raw material;
Under an argon atmosphere, 1680 DEG C of smeltings, ingot casting is poured into;
Step 2, hot rolling:
(1) by ingot casting, heat to 1150 DEG C of insulation 1h;
(2) by the ingot casting after insulation, carrying out 8 passage hot rollings, start rolling temperature is 1150 DEG C, and finishing temperature is 1000 DEG C, and overall reduction is 80%;
(3) by the steel plate after hot rolling, it is cooled to 800 DEG C with the speed of 60 DEG C/s, is incubated 0.8h, then water-cooled is to room temperature, it is thus achieved that hot rolled steel plate;
Step 3, warm-rolling:
By hot rolled steel plate, carrying out 7 passage warm-rollings, before every time warm-rolling, be annealed processing, until warm-rolling overall reduction is 65%, air cooling is to room temperature, it is thus achieved that thickness is the warm-rolling steel plate of 2mm;Wherein, annealing temperature is 750 DEG C, and annealing time is 30min;
Step 4, heat treatment:
(1) by warm-rolling steel plate, heat to 820 DEG C with the speed of 100 DEG C/s, be incubated 180s;
(2) then, it is cooled to 420 DEG C with the speed of 100 DEG C/s, is incubated 5min, obtains nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate.
The nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate of the present embodiment, its tensile strength is 1800MPa, and yield strength is 730MPa, and extensibility is 32%;Its microstructure is made up of the ferrite crystal grain of isometry, and the particle diameter of crystal grain is at 2~10 μm, and the bar shaped austenite in crystal grain adjacent area accounts for the 25% of the gross area, and the austenitic mean breadth of bar shaped is 150nm, length 3~5 μm;The nano bar-shape Cu having a large amount of Dispersed precipitate in bar shaped austenite precipitates out, and mean breadth is 30nm, length 80nm;Its true stress-true strain curve is such as shown in Fig. 4 curve 2;
Average grain size is about the Fe-1.45Mn-1.22Si-0.03Al-0.12Ni-0.12CTRIP590 steel of 5.7 μm, and its yield strength is 430MPa, and tensile strength is about 600MPa, extensibility 23%;Close with the present embodiment steel plate composition, yield strength, tensile strength and plasticity are relatively low, and high intensity and high tenacity requiring, higher application is not met by requirement, and its higher Si content, easily cause the surface defect in industrial processes, cause that follow-up zinc-plated operation encounters difficulties.
Embodiment 5
Nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate, composition is by weight percentage: C:0.53%, Mn:1.4%, Al:1.6%, Si:0.4%, Cu:0.4%, Mo:0.2%, Ti:0.1%, and surplus is Fe and inevitable impurity;Steel plate thickness is 3mm.
The preparation method of nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate, comprises the following steps:
Step 1, ingot casting:
By the composition proportion of steel plate, selecting metallic iron, manganese metal, metallic aluminium, metallic silicon, metallic copper, metal molybdenum, Titanium is raw material;
In a nitrogen atmosphere, 1250 DEG C of smeltings, ingot casting is poured into;
Step 2, hot rolling:
(1) by ingot casting, heat to 1150 DEG C of insulation 1h;
(2) by the ingot casting after insulation, carrying out 5 passage hot rollings, start rolling temperature is 1150 DEG C, and finishing temperature is 1050 DEG C, and overall reduction is 60%;
(3) by the steel plate after hot rolling, it is cooled to 850 DEG C with the speed of 60 DEG C/s, is incubated 1h, then water-cooled is to room temperature, it is thus achieved that hot rolled steel plate;
Step 3, warm-rolling:
By hot rolled steel plate, carrying out 6 passage warm-rollings, before every time warm-rolling, be annealed processing, until warm-rolling overall reduction is 60%, air cooling is to room temperature, it is thus achieved that warm-rolling steel plate;Wherein, annealing temperature is 750 DEG C, and annealing time is 30min;
Step 4, heat treatment:
(1) by warm-rolling steel plate, heat to 820 DEG C with the speed of 100 DEG C/s, be incubated 180s;
(2) then, it is cooled to 380 DEG C with the speed of 100 DEG C/s, is incubated 5min, obtains nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate.
The nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate of the present embodiment, its tensile strength is 1760MPa, and yield strength is 650MPa, and extensibility is 38%;Its microstructure is made up of the ferrite crystal grain of isometry, and the particle diameter of crystal grain is at 5~12 μm, and the bar shaped austenite in crystal grain adjacent area accounts for the 20% of the gross area, and the austenitic mean breadth of bar shaped is 200nm, length 5~10 μm;The nano bar-shape Cu having a large amount of Dispersed precipitate in bar shaped austenite precipitates out, and mean breadth is 50nm, length 100nm;Its true stress-true strain curve is such as shown in Fig. 4 curve 3.
The TRIP590 steel tensile strength 850MPa of Korea S, plasticity ratio is relatively low, and extensibility is only 20%;To intensity, plasticity and energy absorption capability, the nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate of the present embodiment, is requiring that higher field has obvious advantage.
Claims (10)
1. a nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate, it is characterized in that, composition is by weight percentage: C:0.56 ± 0.03%, Cu:0.5 ± 0.1%, Mn:1.5 ± 0.2%, Al:1.5 ± 0.1%, Si:0.5 ± 0.1%, Mo:0.2 ± 0.02%, Ti:0.1 ± 0.02%, surplus is Fe and inevitable impurity, and steel plate thickness is 1.5~3.0mm.
2. nanoscale according to claim 1 bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate, it is characterised in that its tensile strength is 1700~1850MPa, yield strength is 650~730MPa, and extensibility is 32~38%.
3. nanoscale according to claim 1 bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate, it is characterized in that, its microstructure is made up of the ferrite crystal grain of isometry, the particle diameter of crystal grain is at 1~12 μm, bar shaped austenite in ferrite grain boundaries region accounts for the 20~30% of the crystal grain gross area, the austenitic width of bar shaped is 100~300nm, and length is 2~10 μm;The length of the bar-shaped Cu precipitate of nanoscale is 30~100nm, and width is 10~50nm, and Dispersed precipitate is in bar shaped austenite.
4. the preparation method of the nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate described in claim 1, it is characterised in that comprise the following steps:
Step 1, ingot casting:
By the composition proportion of steel plate, under noble gas or nitrogen atmosphere are protected, smelt and pour into ingot casting;
Step 2, hot rolling:
(1) by ingot casting, heat to 1150~1230 DEG C of insulation 2~3h;
(2) by the ingot casting after insulation, carrying out hot rolling, start rolling temperature is 1150~1250 DEG C, and finishing temperature is 950~1050 DEG C, and hot rolling overall reduction is 60~90%;
(3) by the steel plate after hot rolling, it is cooled to 750~850 DEG C with the speed of 40~60 DEG C/s, is incubated 0.5~1h, then water-cooled is to room temperature, it is thus achieved that hot rolled steel plate;
Step 3, warm-rolling:
By hot rolled steel plate, carrying out 6~10 passage warm-rollings, before every time warm-rolling, be annealed processing, until warm-rolling overall reduction is 60~75%, air cooling is to room temperature, it is thus achieved that warm-rolling steel plate;Wherein, annealing temperature is 720~780 DEG C, and annealing time is 30min;
Step 4, heat treatment:
(1) by warm-rolling steel plate, heat to 800~850 DEG C with the speed of 100~200 DEG C/s, be incubated 120~180s;
(2) then, it is quickly cooled to 380~420 DEG C with the speed of 80~100 DEG C/s, is incubated 4~6min, obtains nanoscale bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate.
5. the preparation method of nanoscale according to claim 4 bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate, it is characterised in that in described step 1, smelting temperature is 1620~1680 DEG C;In described step 1, noble gas or nitrogen atmosphere protection refer to: by smelting equipment, be evacuated to vacuum≤100Pa, pass into noble gas or nitrogen to normal pressure, then smelt;Described noble gas is argon.
6. the preparation method of nanoscale according to claim 4 bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate, it is characterised in that in described step 2 (3), carry out 4~10 passage hot rollings.
7. the preparation method of nanoscale according to claim 4 bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate, it is characterised in that in described step 3, adopts holding furnace to be annealed processing.
8. the preparation method of nanoscale according to claim 4 bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate, it is characterised in that described step 4, the equipment of employing is electric pole type salt bath furnace.
9. the preparation method of nanoscale according to claim 4 bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate, it is characterised in that in described step 4 (1), adding thermal medium is NaCl.
10. the preparation method of nanoscale according to claim 4 bar-shaped copper precipitated phase Strengthening and Toughening marine steel plate, it is characterised in that in described step 4 (2), adding thermal medium is KNO3And NaNO2, KNO3And NaNO2Mass ratio be 55: 45.
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