CN104294160A - High-hardness high-toughness low-carbon martensite stainless steel and manufacturing method thereof - Google Patents
High-hardness high-toughness low-carbon martensite stainless steel and manufacturing method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
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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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
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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
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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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
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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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium 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
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
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Abstract
Provided are high-hardness high-toughness low-carbon martensite stainless steel and a manufacturing method thereof. The stainless steel comprises the chemical composition by the weight percentage: 0.05-0.15% of C, not more than 1.0% of Si, not more than 1.2% of Mn, not more than 0.04% of P, not more than 0.01% of S, 11.0-13.0% of Cr, 0.01-0.10% of N, 0.10%<=C+N<=0.20%, V+Ti+Nb<=0.05%, and the balance Fe and inevitable impurities. The manufacturing method comprises the steps: smelting, casting, annealing, heating to 880-1000 DEG C, carrying out heat preservation for 5-30 min, then rapidly cooling at a speed of not less than 30 DEG C/s to a martensite and austenite two-phase region, making the volume percentage of austenite reach 10%-20%, then heating to 350-500 DEG C, carrying out heat preservation for 10-30 min, and cooling to the room temperature to obtain the high-hardness high-toughness low-carbon martensite stainless steel. The Rockwell hardness is 30-40 HRC, the Charpy V-notch impact energy is greater than 30 J, mechanical properties are stable, and the stainless steel can completely meet requirements of bicycle and motorcycle brake disc steel.
Description
Technical field
The present invention relates to metallic substance and working method thereof, be specifically related to a kind of high hardness high toughness Low Carbon Martensite Stainless Steel and manufacture method thereof.
Background technology
Martensite Stainless Steel is chrome stainless steel, is widely used in that cutter is cut, measurer, turbine blade etc. be to obdurability and the corrosion-resistant field that has certain requirements.Wherein, Low Carbon Martensite Stainless Steel may be used for bike, motorbike brake disc manufacture, requires to have high rigidity and high tenacity simultaneously.But, high strength and high tenacity are a pair performance tradeoff of martensitic steel all the time, martensitic steel improves the hardness after thermal treatment mainly through adding carbon, but carbon content raising can reduce toughness, therefore, low carbon martensite is difficult to obtain high rigidity (Rockwell hardness 30 ~ 40HRC) and high tenacity (summer is greater than 30J than v-notch ballistic work) simultaneously under normal circumstances.For this reason, people have done a lot of research work, and have made some progress.
Conventional martensitic stainless steel, as 20Cr13 uses after quenching+tempering thermal treatment, the object of tempering is to eliminate quenching stress and obtaining stable tissue, but Martensite Stainless Steel often unavoidably occurs temper brittleness when tempering.Problem due to fragility aspect limits the stainless use of conventional martensitic.
Propose a kind of Martensite Stainless Steel of high Mn content in Chinese patent CN101684540B, improved intensity and the hardness of steel by the strengthening effect of Mn, N, this steel only needs quenching heat treatment just can obtain good obdurability and corrosion resistance nature.But quenched martensite is easy to soften in heat-processed, can affect result of use as during disc brake.
Chinese patent CN1697889A improves quenching hardness by C, N, add Mo, Ti, Nb, V, Zr to improve resistance to temperability, in order to prevent the appearance of delta ferrite, Ni is added at steel grade, also require in this Chinese patent to add the elements such as Nb, V, Zr, Ta and Hf, its objective is that crystal grain thinning improves quenching toughness.But the manufacturing cost of this invention steel is very high undoubtedly.
Equally, Chinese patent CN1354272A also adds the elements such as molybdenum, niobium, vanadium in steel, increases anti-temper softening performance on the one hand, improves corrosion resistance nature on the other hand.This Chinese patent also requires the hot workability adding B, Ca, Mg, La etc. to improve steel in addition.But adding of a large amount of precious metal greatly improves production cost, and adds manufacture difficulty.
Summary of the invention
The object of the present invention is to provide a kind of high hardness high toughness Low Carbon Martensite Stainless Steel and manufacture method thereof, produce the low cost Martensite Stainless Steel with high rigidity (Rockwell hardness 30 ~ 40HRC) and high tenacity (summer is greater than 30J than v-notch ballistic work).
For achieving the above object, the present invention mainly adopts following technical scheme:
A kind of high hardness high toughness Low Carbon Martensite Stainless Steel, its chemical component weight per-cent is: C:0.05 ~ 0.15%, Si≤1.0%, Mn≤1.2%, P≤0.04%, S≤0.01%, Cr:11.0 ~ 13.0%, N:0.01 ~ 0.10%, 0.10%≤C+N≤0.20%, V+Ti+Nb≤0.05%, all the other are Fe and inevitable impurity.
Further, in described Martensite Stainless Steel, austenitic percent by volume reaches 10% ~ 20%.
Again, the Rockwell hardness of described Martensite Stainless Steel is 30 ~ 40HRC, and the summer is greater than 30J than v-notch ballistic work.
In the Composition Design of high hardness high toughness Low Carbon Martensite Stainless Steel of the present invention:
Carbon: carbon is present in martensitic stucture with the form crossing solid solution, the content direct relation of carbon, to the rear martensitic strength degree of quenching, must ensure that the carbon content in steel is not less than 0.05%.Carbon is present in steel with the form of interstitial atom, reheating in process after quenching can complete reallocation by alternate diffusion, stable residual austenite structure, also have good toughness, but too high carbon content can increase fragility while making material have high rigidity like this.In order to get a desired effect, require that carbon content is 0.05 ~ 0.15%, and with nitrogen element with the use of.
Silicon: join in steel mainly as reductor, play solution strengthening effect.In raising high temperature oxidation resistance, silicon also has obvious effect.But silicone content is high in steel, its ductility deteriorates.Therefore, consider from the workability improving ferritic stainless steel, silicone content should be not more than 1.0%.
Manganese: manganese is deoxidant element and solution strengthening element, can significantly improve the intensity of steel.But Fe content is too high is unfavorable for annealing softening, and its content is not more than 1.2%.
Phosphorus: phosphorus is harmful element, therefore, reduces according to production control level, phosphorus≤0.04% in the present invention as best one can.
Sulphur: sulphur is also a kind of harmful element, the sulfide of formation not only can produce hot-short but also can reduce solidity to corrosion, and the content of usual sulphur controls lower than 0.01%, to avoid the deleterious effect of sulphur.
Chromium: be improve the corrosion proof element of stainless steel, but chromium is strong ferrite former, content Gao Shihui makes low-carbon martensitic steels austenitizing difficulty, and cost also can be made to improve, and chromium content controls 11 ~ 13%.
Nitrogen: the same with carbon be austenizer, can exist with interstitial atom form, there is solution strengthening effect.Can significantly improve solidity to corrosion when nitrogen is present in steel with solution, its effect is about 20 times of chromium.Martensite Stainless Steel can experience the tissue change process of high temperature iron ferritic-austenite-ferrite+carbide in process of production, the solid solution capacity of nitrogen in high temperature iron ferritic lower than 0.10%, if gas hole defect can be caused when content is more than 0.10% to produce.Therefore, Control of Nitrogen Content is 0.01 ~ 0.10%.
Carbon and nitrogen with the use of, jointly can improve quenching hardness.Compared with the effect of single element, carbon and nitrogen with the use of time have obvious advantage, nitrogen has the effect suppressing Carbide Precipitation on the one hand, carbon content can be reduced after adding nitrogen on the other hand and can obtain same rigidity, therefore lower carbon content can make that the Precipitation Temperature of carbon reduces, amount of precipitation reduces, and finally makes material while obtaining high rigidity, have better toughness, solidity to corrosion.In order to obtain stable high rigidity (30 ~ 40HRC), require 0.10%≤C+N≤0.20%, too high C+N can make much higher hard, the degraded toughness of material.
Vanadium, titanium, niobium: be all strong carbon, nitride element, all very easily form carbon, nitride with interstitial element in hot-work or heat treatment process, and make its atom lose the ability of reallocating in alternate diffusion, this is disadvantageous for steel of the present invention.The present invention utilizes carbon, nitrogen to carry out stable austenite phase in the reallocation of two-phase region, finally obtains high tenacity, therefore must the strict content controlling strong carbon, nitride forming element, control V+Ti+Nb≤0.05%.
The manufacture method of high hardness high toughness Low Carbon Martensite Stainless Steel of the present invention, comprises the steps:
(1) smelt, cast
Smelt by following compositions, be cast as strand, the chemical component weight per-cent of Low Carbon Martensite Stainless Steel is: C:0.05 ~ 0.15%, Si≤1.0%, Mn≤1.2%, P≤0.04%, S≤0.01%, Cr:11.0 ~ 13.0%, N:0.01 ~ 0.10%, 0.10%≤C+N≤0.20%, V+Ti+Nb≤0.05%, all the other are Fe and inevitable impurity;
(2) above-mentioned strand is rolled into hot-rolled steel sheet or steel band, and anneals;
(3) after annealing, be heated to 880 ~ 1000 DEG C of insulation 5 ~ 30min, then martensite and austenite two-phase region is quickly cooled to the speed being not less than 30 DEG C/s, austenitic percent by volume is made to reach 10 ~ 20%, reheat to 350 ~ 500 DEG C of insulation 10 ~ 30min, be cooled to room temperature and obtain high hardness high toughness Low Carbon Martensite Stainless Steel, the Rockwell hardness of the high-intensity high-tenacity Low Carbon Martensite Stainless Steel obtained is 30 ~ 40HRC, and the summer is greater than 30J than v-notch ballistic work.
The impact of processing condition in the above-mentioned manufacture method of the present invention:
(1) steel billet of mentioned component or Hot Charging of Continuous Casting Slab are rolled into hot-rolled steel sheet or steel band, and adopt conventional method to anneal, be organized as ferrite+carbide after annealing, there is lower hardness and higher extension property, be applicable to the processing such as stamping-out, shearing, calendering.
(2) steel band after annealing is heated to 880 ~ 1000 DEG C of insulation 5 ~ 30min, mainly for ensureing that steel can complete austenitizing, the abundant solid solution of carbon, nitride.
(3) then martensite and austenite two-phase region is quickly cooled to the speed being not less than 30 DEG C/s, be cooled between Ms (martensite start) point (Ms) and finishing temperature (Mf) by temperature, obtain martensite and austenitic duplex tissue, the method of calculation of Ms temperature are: Ms (DEG C)=539-430 × [C+N]-30 × [Mn]-12 × [Cr]-5.0 × [Si], and wherein [C], [Si], [Mn], [Cr], [N] are respectively C, Si, Mn, Cr, N weight percent in Martensite Stainless Steel; The method of calculation of Mf temperature are: Mf (DEG C)=Ms-250.
In process of cooling after heating and thermal insulation, carbonitride can have the tendency of precipitation because of supersaturation, therefore must ensure higher speed of cooling, test shows that speed of cooling is not less than 30 DEG C/s and carbonitride can be avoided to separate out in process of cooling and ensure higher heat treatment hardness value.In order to ensure that higher speed of cooling can adopt air-cooled, air cooling, oil cooling and other mode.
(4) reheat to 350 ~ 500 DEG C of insulation 10 ~ 30min, make carbon, nitrogen interstitial atom from martensitic stucture by diffusing in austenite structure, the austenite structure stability not completing martensitic transformation is increased, to such an extent as to can stablize to room temperature in follow-up process of cooling, this contributes to the toughness improving steel of the present invention.
(5) air cooling is to room temperature, obtains martensite+austenite heterogeneous structure, and austenitic percent by volume is 10 ~ 20%.If the contribution of austenite structure ratio very little for toughness is not obvious; If austenite structure ratio is too high, the carbon content spread from martensite is not enough to stable austenite, and in follow-up process of cooling, austenite is likely generated martensite by quenching again, is disadvantageous to raising toughness of material.This stable tissue has high rigidity and high tenacity on the one hand, and on the other hand owing to being incubated at 350 ~ 500 DEG C, internal stress is little, mechanical property quite stable.
Beneficial effect of the present invention:
1. the present invention by carbon and nitrogen with the use of, make steel of the present invention when low-carbon (LC), there is higher hardness and toughness simultaneously.
2. the present invention's control V+Ti+Nb≤0.05%, greatly reduces the growing amount of carbon, nitride, makes carbon, nitrogen carry out stable austenite phase in the diffusion reallocation of martensite and austenite two-phase region, finally while acquisition high rigidity, obtains high tenacity.
3. in manufacture method of the present invention, after annealing, after heating austenitizing, controlled cooling model stops temperature between Ms and Mf temperature, obtain martensite and add the tissue that residual austenite two-phase is master, carbon in intensification again subsequently and insulating process in martensite, nitrogen spread enrichment in austenite, carbon in austenite, nitrogen content increase impel its stability to strengthen, after this thermal treatment, obtain the microstructure that martensite adds retained austenite, make the present invention obtain high tenacity while obtaining high rigidity.The temperature and time reheated in the process should match, and final purpose makes carbon complete alternate redistributing, and austenitic stability increased, remains in process of cooling subsequently, thus improves the toughness after thermal treatment.
4. the steel plate Rockwell hardness that Composition Design of the present invention combines obtained with manufacturing process is 30 ~ 40HRC, and the summer is greater than 30J than v-notch ballistic work, stable mechanical property, can meet the requirement of bike, motorbike brake disc steel completely.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is described in further detail.
The chemical composition of the embodiment of the present invention 1 ~ 5 and comparative example 1 ~ 2 is see table 1, and concrete fabrication process parameters is as shown in table 2, and after testing, the performance of the high-intensity high-tenacity Low Carbon Martensite Stainless Steel that embodiment 1 ~ 5 obtains is as shown in table 3.
Table 1 unit: weight percent
| Numbering | C | Si | Mn | P | S | Cr | N | C+N | V+Ti+Nb |
| Embodiment 1 | 0.05 | 0.33 | 0.59 | 0.02 | 0.004 | 12.3 | 0.05 | 0.10 | 0.02 |
| Embodiment 2 | 0.08 | 0.53 | 1.20 | 0.02 | 0.006 | 11.2 | 0.04 | 0.12 | 0.01 |
| Embodiment 3 | 0.10 | 0.27 | 0.78 | 0.03 | 0.002 | 11.8 | 0.09 | 0.19 | 0.01 |
| Embodiment 4 | 0.13 | 0.39 | 0.31 | 0.01 | 0.003 | 12.8 | 0.04 | 0.17 | ≤0.01 |
| Embodiment 5 | 0.15 | 0.41 | 0.52 | 0.02 | 0.003 | 11.7 | 0.01 | 0.16 | 0.02 |
| Comparative example 1 | 0.13 | 0.42 | 0.35 | 0.02 | 0.001 | 11.5 | 0.03 | 0.16 | 0.02 |
| Comparative example 2 | 0.15 | 0.32 | 0.56 | 0.02 | 0.001 | 12.6 | 0.07 | 0.22 | ≤0.01 |
From table 1 ~ 3, carbon and nitrogen are the principal elements of hardness after guarantee steel heat treatment of the present invention, and C+N=0.10% in embodiment 1, after thermal treatment, hardness is 30HRC, ensures that C+N >=0.10% just can guarantee that hardness reaches more than 30HRC as seen.
The Heating temperature that table 2 is listed meets the requirement of 880 ~ 1000 DEG C, and Heating temperature should match with the time, and final purpose is complete austenitizing.If should by soaking time proper extension when Heating temperature is lower, material thickness is larger, vice versa.
The chemical composition of comparative example 1 is close with embodiment 4, but do not adopt quenching of the present invention+reheat components matching technique during thermal treatment, and adopt traditional 920 DEG C of quenchings+250 DEG C of tempering heat treatment, after result thermal treatment, hardness reaches 40HRC, but the summer is only 13J than v-notch ballistic work, far below 30J, visible, the steel meeting present component is also needed to adopt the heat treating method of regulation just can obtain satisfactory performance.
In comparative example 2, C+N is 0.22%, exceed the requirement of C+N≤0.20%, result hardness after 880 DEG C of quenchings+500 DEG C reheat composition partition reaches 43HRC, summer is 26J than v-notch ballistic work, the former has exceeded the requirement of Rockwell hardness between 30 ~ 40HRC, and the latter's ballistic work is lower than 30J.So the content of chemical composition of the present invention, particularly C+N requirement according to the invention just must can obtain satisfactory performance.
In sum, in high hardness high toughness Low Carbon Martensite Stainless Steel prepared by the present invention, austenitic percent by volume reaches 10% ~ 20%, Rockwell hardness is between 30 ~ 40HRC, ballistic work is greater than 30J, there is high rigidity and high tenacity simultaneously, the requirement of bike, motorbike brake disc steel can be met, also may be used for other have requirement field to hardness and toughness.
It should be noted that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted.Although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to the technical scheme of invention or equivalent replacement, and not depart from the scope of technical solution of the present invention, it all should be encompassed in right of the present invention.
Claims (4)
1. a high hardness high toughness Low Carbon Martensite Stainless Steel, its chemical component weight per-cent is: C:0.05 ~ 0.15%, Si≤1.0%, Mn≤1.2%, P≤0.04%, S≤0.01%, Cr:11.0 ~ 13.0%, N:0.01 ~ 0.10%, 0.10%≤C+N≤0.20%, V+Ti+Nb≤0.05%, all the other are Fe and inevitable impurity.
2. high hardness high toughness Low Carbon Martensite Stainless Steel as claimed in claim 1, it is characterized in that, in described Martensite Stainless Steel, austenitic percent by volume reaches 10% ~ 20%.
3. high hardness high toughness Low Carbon Martensite Stainless Steel as claimed in claim 1 or 2, it is characterized in that, the Rockwell hardness of described Martensite Stainless Steel is 30 ~ 40HRC, and the summer is greater than 30J than v-notch ballistic work.
4. a manufacture method for high hardness high toughness Low Carbon Martensite Stainless Steel, comprises the steps:
1) smelt, cast
Smelt by following compositions, be cast as strand, the chemical component weight per-cent of Low Carbon Martensite Stainless Steel is: C:0.05 ~ 0.15%, Si≤1.0%, Mn≤1.2%, P≤0.04%, S≤0.01%, Cr:11.0 ~ 13.0%, N:0.01 ~ 0.10,0.10%≤C+N≤0.20%, V+Ti+Nb≤0.05%, all the other are Fe and inevitable impurity;
2) above-mentioned strand is rolled into hot-rolled steel sheet or steel band, and anneals;
3) after annealing, be heated to 880 ~ 1000 DEG C, insulation 5 ~ 30min, then martensite and austenite two-phase region is quickly cooled to the speed being not less than 30 DEG C/s, make austenitic percent by volume reach 10% ~ 20%, reheat to 350 ~ 500 DEG C of insulation 10 ~ 30min, be cooled to room temperature and obtain Martensite Stainless Steel, the Rockwell hardness of described Martensite Stainless Steel is 30 ~ 40HRC, and the summer is greater than 30J than v-notch ballistic work.
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Cited By (13)
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| CN104711482A (en) * | 2015-03-26 | 2015-06-17 | 宝钢不锈钢有限公司 | Nitrogen-controlled martensitic stainless steel and manufacturing method thereof |
| CN105821330A (en) * | 2016-05-09 | 2016-08-03 | 山东泰山钢铁集团有限公司 | Martensite stainless steel and smelting process |
| CN106480377A (en) * | 2016-10-09 | 2017-03-08 | 宝钢不锈钢有限公司 | Martensitic stain less steel and its manufacture method with excellent mechanical property and antioxygenic property |
| CN108642391A (en) * | 2018-06-07 | 2018-10-12 | 成都先进金属材料产业技术研究院有限公司 | Martensitic stain less steel and preparation method thereof |
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| CN110656293A (en) * | 2019-11-01 | 2020-01-07 | 育材堂（苏州）材料科技有限公司 | Mo-containing high-hardness stainless steel, heat treatment process and formed member |
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| CN112575261A (en) * | 2020-12-09 | 2021-03-30 | 广东省科学院材料与加工研究所 | Composite modified martensitic alloy cast steel and preparation method thereof |
| CN113510340A (en) * | 2021-08-10 | 2021-10-19 | 哈尔滨电气动力装备有限公司 | Welding and postweld heat treatment process method for martensite precipitation hardening stainless steel material |
| CN113966405A (en) * | 2019-06-05 | 2022-01-21 | 山特维克材料技术公司 | Martensitic stainless steel alloy |
| CN114395740A (en) * | 2022-01-07 | 2022-04-26 | 山西太钢不锈钢股份有限公司 | Niobium monostable sizing low-chromium martensitic stainless steel and preparation method thereof |
| CN115491609A (en) * | 2022-10-12 | 2022-12-20 | 福建青拓特钢技术研究有限公司 | Low-carbon martensitic stainless steel for brake disc and manufacturing method thereof |
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