CN104711482A - Nitrogen-controlled martensitic stainless steel and manufacturing method thereof - Google Patents
Nitrogen-controlled martensitic stainless steel and manufacturing method thereof Download PDFInfo
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Abstract
The invention relates to a nitrogen-controlled martensitic stainless steel and a manufacturing method thereof. The nitrogen-controlled martensitic stainless steel is composed of the following components in percentage by weight: 0.05-0.35% of C, 0.01-1.0% of Si, 0.01-2.5% of Mn, at most 0.04% of P, at most 0.01% of S, 11.0-15.0% of Cr, 0.05-0.15% of N, 0.05-0.25% of V, 0.01-1.5% of Mo, 0-0.1% of Nb, 0-0.1% of Ti, and the balance of Fe and inevitable impurities. All the elements simultaneously satisfy the following relationships: 0.1%<=C+N<=0.4%, and 0.05%<=V+Ti+Nb<=0.25%. The hardness of the steel is 30-50 HRC, the 20-DEG C Charpy V-notch longitudinal impact work is greater than 30J, and the steel has favorable compatibility between high hardness and high toughness.
Description
Technical field
The invention belongs to Martensite Stainless Steel field, be specifically related to a kind of control nitrogen 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. are to obdurability and the corrosion-resistant field that has certain requirements.Wherein, middle Low Carbon Martensite Stainless Steel requires to have higher hardness (30 ~ 40HRC) and good toughness (summer is than v-notch ballistic work > 30J) simultaneously.Martensitic steel improves the intensity after thermal treatment, hardness mainly through adding carbon, but carbon content raising can reduce toughness.So high strength and high tenacity are a pair performance tradeoff of martensitic steel all the time.
Chinese patent CN103255340 discloses a kind of thermoforming steel plate and preparation method of high-strong toughness, the method of quenching+Composition Design is utilized to realize heterogeneous structure, overcome the problem that after high-strength vehicle steel is shaped, intensity is high, toughness is not enough, but it remains with carbon is main reinforced alloys element, then coordinate the intensity and the toughness that reach the best with the optimization of technique; The shortcoming of this patent is that higher carbon easily causes the carbon segregation of finished product, has larger impact to the performance uniformity of steel plate and corrosion resistance nature.Chinese patent CN103243275 discloses a kind of low-alloy high-strength steel, obtains bainite+martensite+austenite heterogeneous structure by Composition Design and temper, reaches good strong plasticity and toughness cooperation.CN103045950 also discloses a kind of low alloying low cost steel, is increased hardness of steel by rapid quenching and carbon redistribution, be ensure that good toughness.But in Chinese patent CN103243275, CN103045950,20 DEG C of Charpy-V impact powers are only≤25J, and toughness is not enough.
Summary of the invention
The object of the present invention is to provide a kind of control nitrogen Martensite Stainless Steel and manufacture method thereof, this steel still can keep excellent mechanical property after quench treatment---high rigidity and high tenacity, Rockwell hardness is 30 ~ 50HRC, ballistic work > 30J.
For achieving the above object, technical scheme of the present invention is:
A kind of control nitrogen Martensite Stainless Steel, its chemical component weight per-cent is: C:0.05 ~ 0.35%, Si:0.01 ~ 1.0%, Mn:0.01 ~ 2.5%, P≤0.04%, S≤0.01%, Cr:11.0 ~ 15.0%, N:0.05 ~ 0.15%, V:0.05 ~ 0.25%, Mo:0.01 ~ 1.5%, Nb:0 ~ 0.1%, Ti:0 ~ 0.1%, all the other are Fe and inevitable impurity, and above-mentioned element needs satisfied following relation simultaneously: 0.1%≤C+N≤0.4%, 0.05%≤V+Ti+Nb≤0.25%.
Further, the hardness of described control nitrogen Martensite Stainless Steel is 30 ~ 50HRC, and 20 DEG C of summers are than V-type impact of collision merit > 30J.
The microstructure of control nitrogen Martensite Stainless Steel of the present invention is martensite+residual austenite heterogeneous structure.
In present component design:
C: be important austenizer, obtain fully austenitic structure when C can ensure high temperature; C is the important element of hardness after guarantee thermal treatment, is also important solution strengthening element and precipitation strength element; C can be present in steel with the form of interstitial atom, and reheating in process after quenching can complete reallocation by alternate diffusion, stable residual austenite structure; Too high C content increases fragility on the one hand, also damages solidity to corrosion on the other hand.Therefore, it is 0.05 ~ 0.35% that C content of the present invention controls, and with nitrogen element with the use of.
N: the same with C be austenizer, can exist with interstitial atom form, there is solution strengthening effect, the solubleness of N in austenite is higher than C, in heat treatment process, the precipitate of N is less, the N in the base of solid solution simultaneously can improve stainless corrosion resistance nature, therefore N is that one can improve Martensite Stainless Steel intensity, can improve again the element of corrosion resistance nature.Therefore, N content of the present invention controls is 0.05 ~ 0.15%.
Si: join in steel mainly as reductor, play solution strengthening effect.In raising high temperature oxidation resistance, Si also has obvious effect.But Si content high ductibility is deteriorated in steel, therefore, consider from the workability improving ferritic stainless steel, control Si content is 0.01 ~ 1.0%.
Mn:Mn is deoxidant element and solution strengthening element, can significantly improve the intensity of steel, but Mn too high levels is unfavorable for annealing softening.Therefore, Mn content of the present invention controls is 0.01 ~ 2.5%.
P:P is harmful element, therefore reduces as best one can according to production control level.
S:S is also a kind of harmful element, and the sulfide of formation not only can produce hot-short but also can reduce solidity to corrosion, and usual S content controls as≤0.01%, to avoid the deleterious effect of S.
Cr: be improve the corrosion proof element of stainless steel, but Cr is strong ferrite former, content Gao Shihui makes low-carbon martensitic steels austenitizing difficulty, and cost also can be made to improve.Therefore, Cr content of the present invention controls 11 ~ 15%.
Nb:Nb is stainless steel micro alloying element, at high temperature can be combined with C, forms tiny NbC, plays the effect of precipitation strength matrix, in addition all right refinement high temperature austenite crystal grain of the interpolation of Nb, thus optimizes final martensitic stucture.But because Nb is strong ferrite former, Nb too much adds membership and reduces austenite phase field, thus be difficult to after making cooling form martensitic stucture.Therefore in the present invention, Nb selects added elements, and content controls 0 ~ 0.1%.
Ti:Ti is also a kind of strong ferrite former, and excessive the adding of Ti makes martensite be difficult to be formed.But the Ti of trace can form TiN in molten steel, in solidification of molten steel process, play the effect of non-homogeneous heterogeneous forming core, the proportion of equiaxed grain of slab can be improved, thus improve the toughness of Martensite Stainless Steel final finished.Therefore, in the present invention, Ti selects added elements, and content controls 0 ~ 0.1%.
C, N: in order to reach austenite completely, the object of high rigidity (30 ~ 50HRC), high tenacity, C and N must be with the use of, specific requirement 0.1%≤C+N≤0.4%.Too high C+N can make the austenitizing phase region of material become large, and cooling forms excessive needle type martensite, and needle type martensite will inevitably worsen the mechanical property of material, makes the much higher hard of material, and extension property and impelling strength are deteriorated; In addition, carbon nitrogen content more than 0.4%, more free state carbon nitrogen elements are separated out from matrix, form the precipitate such as chromium carbide, chromium nitride, these precipitates are separated out at grain boundaries, taken away the chromium element of grain boundaries solid solution, crystal boundary corrosion resisting property is declined, and easily there is grain boundary corrosion in material simultaneously.And lower than 0.1% carbon and nitrogen, the intensity of material, hardness can be made again cannot to reach requirement, because carbon, nitrogen are the most effective strengthening elements in Martensite Stainless Steel.Therefore, carbon nitrogen content should reach above-mentioned requirements.
V, Ti, Nb: be all strong carbonitride element, wherein, in the present invention, V and N element form tiny VN precipitated phase, this precipitated phase is separated out when hot rolling, effectively can play the effect of Second Phase Precipitation strengthening, Nb and Ti is then mainly combined with carbon, plays the effect of fixing free state carbon, avoid carbon and chromium to react, reduce corrosion resistance nature of the present invention.Because in the present invention, N content is higher, and C content is relatively low, and therefore Ti and Nb is for selecting addition element, and the present invention controls 0.05%≤V+Ti+Nb≤0.25%.
First the manufacture method of control nitrogen Martensite Stainless Steel of the present invention, comprise the steps:, smelts by composition according to claim 1, be cast as steel billet or continuously cast bloom; Then, hot-rolled steel sheet or steel band are made in hot rolling, and hot-rolled temperature is 1150 ~ 1250 DEG C; Then, anneal; Again the steel plate after annealing or steel band are heated to 850 ~ 1000 DEG C, insulation 5 ~ 30min, is then quickly cooled to martensite and austenite two-phase region with the speed of >=30 DEG C/s; Then, steel plate or steel band are reheated to 350 ~ 500 DEG C, insulation 10 ~ 30min, air cooling is to room temperature.
Hot rolling Heating temperature of the present invention is 1150 ~ 1250 DEG C: in component system of the present invention, N element starts to separate out at about 1250 DEG C, and along with the rising of temperature, amount of precipitation is increasing.Therefore, hot rolling Heating temperature of the present invention is set between 1150 ~ 1250 degree, in order to prevent the precipitation of N, allowing N better dissolve in the base, improving intensity of the present invention, the mechanical properties such as hardness.
Adopt ordinary method to anneal after hot rolling of the present invention, after annealing, be organized as ferrite+carbide, there is lower hardness and higher extension property, be applicable to stamping-out, shearing, rolling processing.
Steel plate after annealing or steel band are heated to 850 ~ 1000 DEG C by the present invention, insulation 5 ~ 30min, mainly for ensureing that steel can complete austenitizing, the abundant solid solution of carbon, nitride.Because Martensite Stainless Steel at high temperature can form austenite structure, and form austenitic temperature and its composition and have certain relation.In component system of the present invention, it forms austenitic temperature is 800 ~ 950 DEG C, consider that phase in version needs certain superheating temperature, and the superheating temperature of 50 DEG C can ensure comparing completely of tissue.Therefore, annealing temperature of the present invention is decided to be 850 ~ 1000 DEG C.And the thickness of soaking time and steel plate has close relationship, actual from the production of steel, the time is decided to be 5 ~ 30min.
The present invention is quickly cooled to martensite and austenite two-phase region with the speed of >=30 DEG C/s, is cooled between Ms (martensite start) point (Ms) and finishing temperature (Mf) by temperature, obtains 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 percentage × 100 in Martensite Stainless Steel; The method of calculation of Mf temperature are: Mf (DEG C)=Ms-250.
The present invention cools fast in order to the speed of >=30 DEG C/s can avoid carbon, nitride is separated out in process of cooling.In component system of the present invention, when speed of cooling is lower than 30 DEG C/s, the solid solution atoms be solid-solubilized in austenitic matrix such as carbon nitrogen have time enough to separate out from matrix, form carbonitride, carbon and nitrogen atoms just cannot reach the effect of solution strengthening, and the intensity of Martensite Stainless Steel and hardness just cannot arrive requirement of the present invention.
The present invention reheats to 350 ~ 500 DEG C, and insulation 10 ~ 30min, makes carbon, nitrogen interstitial atom from martensitic stucture by diffusing in austenite structure, and the austenite structure stability not completing martensitic transformation is increased.Due under the speed of cooling of >=30 DEG C/s, carbon and nitrogen atoms forms oversaturated body-centered cubic comprehensively, now martensite intensity hardness is very high, but toughness is not enough, after reheating 350 ~ 500 DEG C, carbon and nitrogen atoms can move freely, but can not structural transformation be there is again in matrix, such one side eliminates unrelieved stress, forms again stable tissue on the one hand, effectively improves toughness of the present invention.
Beneficial effect of the present invention:
The present invention is by conservative control C, N content, make the Martensite Stainless Steel of middle low-carbon (LC) in intensity and hardness, reach the stainless index of high carbon martensite, and toughness and solidity to corrosion retain in the characteristic of Low Carbon Martensite Stainless Steel, effectively solve Martensite Stainless Steel intensity, toughness, solidity to corrosion etc. conflicting, be difficult to a difficult problem of mating.
Martensite Stainless Steel prepared by the present invention is martensite+residual austenite heterogeneous structure, has high rigidity and high tenacity simultaneously; Particularly after quench treatment, still can keep excellent mechanical property, specifically the hardness of steel is 30 ~ 50HRC, 20 DEG C of summers, than v-notch ballistic work > 30J, have the matched well of high rigidity and high tenacity, meet the requirement of cutter steel completely.
Accompanying drawing explanation
Fig. 1 is the precipitation content variation with temperature schematic diagram of N in the embodiment of the present invention 1 component system.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention will be further described.
The wear-resisting steel plate of following examples 1-5 and the steel plate of comparative example 1,2, the weight percent of its chemical composition is as shown in table 1.The manufacture method of the wear-resisting steel plate of embodiment 1-5 and the steel plate of comparative example 1,2 is: smelt by table 1 composition, cast, hot-rolled steel sheet or steel band are made in hot rolling, and hot-rolled temperature is 1150 ~ 1250 DEG C, annealing; Steel plate after annealing or steel band are heated to 850 ~ 1000 DEG C, and insulation 5 ~ 30min, then cools (air-cooled) to martensite and austenite two-phase region fast with the speed of >=30 DEG C/s; Reheat to 350 ~ 500 DEG C, insulation 10 ~ 30min, air cooling is to room temperature.The concrete technology parameter of embodiment 1-5 and comparative example 1,2 is as shown in table 2.
Carry out Mechanics Performance Testing to the steel plate of embodiment of the present invention 1-5 and comparative example 1,2, its result is as shown in table 3.As shown in Table 3, the hardness of steel of the present invention is 30 ~ 50HRC, and 20 DEG C of summers, than v-notch ballistic work > 30J, have the matched well of high rigidity and high tenacity, meet the requirement of cutter steel completely.
Fig. 1 is the precipitation content variation with temperature of N in the Thermo-Calc phasor computed in software embodiment of the present invention 1 component system, as shown in Figure 1, in component system of the present invention, N element starts to separate out at about 1250 DEG C, along with the rising of temperature, Phase Proportion increases to more than 25% by 0, and amount of precipitation is increasing.Therefore, hot rolling Heating temperature of the present invention is set in the precipitation exactly in order to prevent N between 1150 ~ 1250 DEG C, allows N better dissolve in the base, improves mechanical property of the present invention.
Table 1 unit: wt%
| Numbering | C | Si | Mn | P | S | Cr | N | V | Nb | Ti | Mo | C+N | V+Ti+Nb |
| Embodiment 1 | 0.05 | 0.33 | 2.45 | 0.02 | 0.004 | 12.3 | 0.05 | 0.05 | 0 | 0 | 0.01 | 0.10 | 0.05 |
| Embodiment 2 | 0.08 | 0.53 | 1.34 | 0.02 | 0.006 | 11.2 | 0.07 | 0.07 | 0 | 0 | 0.01 | 0.15 | 0.07 |
| Embodiment 3 | 0.10 | 0.27 | 1.78 | 0.03 | 0.002 | 11.8 | 0.09 | 0.08 | 0.1 | 0 | 0.5 | 0.19 | 0.18 |
| Embodiment 4 | 0.23 | 0.42 | 0.35 | 0.02 | 0.001 | 15.0 | 0.14 | 0.15 | 0 | 0.05 | 1.1 | 0.37 | 0.2 |
| Embodiment 5 | 0.35 | 0.32 | 0.56 | 0.02 | 0.001 | 12.6 | 0.05 | 0.2 | 0 | 0.05 | 1.5 | 0.40 | 0.25 |
| Comparative example 1 | 0.13 | 0.42 | 0.35 | 0.02 | 0.001 | 11.5 | 0.03 | 0.01 | 0 | 0 | 0 | 0.16 | 0.02 |
| Comparative example 2 | 0.15 | 0.32 | 0.56 | 0.02 | 0.001 | 12.6 | 0.04 | 0 | 0 | 0 | 0 | 0.19 | ≤0.01 |
Table 2
Table 3
Claims (6)
1. a control nitrogen Martensite Stainless Steel, its composition by weight percent is: C:0.05 ~ 0.35%, Si:0.01 ~ 1.0%, Mn:0.01 ~ 2.5%, P≤0.04%, S≤0.01%, Cr:11.0 ~ 15.0%, N:0.05 ~ 0.15%, V:0.05 ~ 0.25%, Mo:0.01 ~ 1.5%, Nb:0 ~ 0.1%, Ti:0 ~ 0.1%, all the other are Fe and inevitable impurity, and above-mentioned element needs satisfied following relation simultaneously: 0.1%≤C+N≤0.4%, 0.05%≤V+Ti+Nb≤0.25%.
2. control nitrogen Martensite Stainless Steel according to claim 1, is characterized in that, the hardness of described control nitrogen Martensite Stainless Steel is 30 ~ 50HRC, and 20 DEG C of summers are than V-type impact of collision merit > 30J.
3. control nitrogen Martensite Stainless Steel according to claim 1 and 2, is characterized in that, the microstructure of described control nitrogen Martensite Stainless Steel is martensite+residual austenite heterogeneous structure.
4. the manufacture method of control nitrogen Martensite Stainless Steel as claimed in claim 1, is characterized in that, comprising: first, smelt by composition according to claim 1, be cast as steel billet or continuously cast bloom; Then, hot-rolled steel sheet or steel band are made in hot rolling, and hot-rolled temperature is 1150 ~ 1250 DEG C; Then, anneal; Again the steel plate after annealing or steel band are heated to 850 ~ 1000 DEG C, insulation 5 ~ 30min, is then quickly cooled to martensite and austenite two-phase region with the speed of >=30 DEG C/s; Then, steel plate or steel band are reheated to 350 ~ 500 DEG C, insulation 10 ~ 30min, air cooling is to room temperature.
5. the manufacture method of control nitrogen Martensite Stainless Steel according to claim 4, is characterized in that, the hardness of described control nitrogen Martensite Stainless Steel is 30 ~ 50HRC, and 20 DEG C of summers are than V-type impact of collision merit > 30J.
6. the manufacture method of the control nitrogen Martensite Stainless Steel according to claim 4 or 5, is characterized in that, the microstructure of described control nitrogen Martensite Stainless Steel is martensite+residual austenite heterogeneous structure.
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| CN106086631A (en) * | 2016-08-23 | 2016-11-09 | 钢铁研究总院 | High-hardness, wearable height nitrogen martensite stainless bearing steel and preparation method thereof |
| 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 |
| CN107779778A (en) * | 2017-09-22 | 2018-03-09 | 钢铁研究总院 | A kind of rail fastener stainless steel spring material |
| CN107849669A (en) * | 2015-07-16 | 2018-03-27 | 山特维克知识产权股份有限公司 | Drill tool assembly |
| CN108692116A (en) * | 2017-03-31 | 2018-10-23 | Lg电子株式会社 | Soft stainless steel tube |
| CN109930084A (en) * | 2019-03-29 | 2019-06-25 | 宜兴市佳信数控科技有限公司 | A kind of steel pin compression molding elevator counterweight block and preparation method thereof |
| CN113981317A (en) * | 2021-10-27 | 2022-01-28 | 山西帝思曼特殊金属科技有限公司 | Nitrogen-containing martensitic stainless steel for cutter and manufacturing method thereof |
| WO2022111908A1 (en) * | 2020-11-24 | 2022-06-02 | Otto-Von-Guericke-Universität Magdeburg | Martensitic stainless steel alloy having optimized hardness and corrosion resistance |
| EP4098757A4 (en) * | 2020-01-27 | 2023-12-27 | Proterial, Ltd. | Method for producing martensitic stainless steel strip, and martensitic stainless steel strip |
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| EP4098757A4 (en) * | 2020-01-27 | 2023-12-27 | Proterial, Ltd. | Method for producing martensitic stainless steel strip, and martensitic stainless steel strip |
| WO2022111908A1 (en) * | 2020-11-24 | 2022-06-02 | Otto-Von-Guericke-Universität Magdeburg | Martensitic stainless steel alloy having optimized hardness and corrosion resistance |
| CN113981317A (en) * | 2021-10-27 | 2022-01-28 | 山西帝思曼特殊金属科技有限公司 | Nitrogen-containing martensitic stainless steel for cutter and manufacturing method thereof |
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Application publication date: 20150617 |