CN103710638A - Martensitic stainless steel and manufacturing method thereof - Google Patents

Martensitic stainless steel and manufacturing method thereof Download PDF

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CN103710638A
CN103710638A CN201310740156.9A CN201310740156A CN103710638A CN 103710638 A CN103710638 A CN 103710638A CN 201310740156 A CN201310740156 A CN 201310740156A CN 103710638 A CN103710638 A CN 103710638A
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stainless steel
martensite stainless
manufacture method
toughness
room temperature
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CN103710638B (en
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余式昌
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Baowu Special Metallurgy Co Ltd
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Baosteel Special Steel Co Ltd
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Abstract

The invention relates to martensitic stainless steel and a manufacturing method thereof. The martensitic stainless steel comprises the following chemical components in percentage by weight: 0.05-0.10% of C, no more than 1.0% of Si, 0.5-1.2% of Mn, no more than 0.035% of P, 0.02-0.05% of S, 0.3-0.8% of Ni, 12.5-14.0% of Cr, 0.2-0.7% of Mo, 0.02-0.05% of N, 0.001-0.003% of Ca, 0.08-0.12% of C+N and the balance of Fe and inevitable impurities. According to the invention, by reasonably controlling the chemical components, the martensitic stainless steel has high room-temperature strength and moderate-temperature strength, favorable toughness and excellent machining property.

Description

A kind of Martensite Stainless Steel and manufacture method thereof
Technical field
The invention belongs to stainless material field, relate in particular to a kind of Martensite Stainless Steel and manufacture method thereof, Martensite Stainless Steel has high room temperature strength (during room temperature, yield strength is greater than 450MPa), medium temperature intensity ((300 ℃ time yield strength be greater than 400MPa), good toughness (0 ℃ time V-type ballistic work be greater than 50J) and excellent machinability, is particularly useful for the manufacture of the device support plates such as nuclear power, water power.
Background technology
Be accompanied by the green energy resource industrial expansions such as nuclear power, water power, also more and more higher to the requirement of material.The device support such as nuclear power, water power plate with Martensite Stainless Steel except the room temperature strength of having relatively high expectations, good toughness, because use temperature reaches 300 ℃, therefore need good medium temperature intensity, because supporting miscellaneous part, need machining hole or groove etc. onboard in addition, therefore need good machinability.
General low chromium martensitic stainless steel is for to intensity and toughness reguirements higher field all.The low chromium martensitic stainless steel of middle and high carbon for conventional ingredient, as 2Cr13,3Cr13,4Cr13, its carbon content is high, although there is good middle cryogenic mechanics performance, but its plasticity, toughness are poor, and because hardness is higher, cause machining difficulty, be not therefore suitable for the device support plates such as nuclear power that manufacture need to have high room temperature strength, medium temperature intensity, good toughness and excellent machinability simultaneously, water power.
And for the low chromium martensitic stainless steel of low-carbon (LC) of conventional ingredient, as 410S, its carbon content is low, plasticity is better, but warm mechanical property is difficult to meet back up pad steel requirement in material, machinability is not very good yet in addition, is not therefore suitable for device support plates such as manufacturing nuclear power, water power yet.
Based on this, Chinese patent CN200910201443.6 discloses a kind of high-strength plasticity, high/low-temperature impact toughness and erosion resistance Martensite Stainless Steel, its chemical composition is: carbon: 0.10-0.15%, silicon: 0.20-0.50%, manganese: 0.50-1.50%, nickel: 2.00-4.00%, chromium: 15.00-17.00%, molybdenum: 0.03-0.30%, nitrogen: 0.020-0.200%, rare earth: 0.01-0.10%, copper≤0.25%, sulphur≤0.025%, phosphorus≤0.040%, remaining is Fe and inevitable impurity.This patent is to utilize high carbon nitrogen content to reach high strength, put forward high nickel content simultaneously and guarantee good plasticity, toughness, but its cost is higher, and its machinability is difficult to guarantee simultaneously.
Chinese patent CN200710164219.5 discloses a kind of easy cutting Martensite Stainless Steel chemical composition: C:0.10% to 1.20%, Si:0.10% to 2.00%, Mn:0.80% to 2.00%, S:0.10% to 0.30%, Cr:10.5% to 18.0%, Pb:0.03% to 0.30%, Te:0.01% to 0.10%, B:0.0005% to 0.010% and O:0.005% to 0.030%, surplus is Fe and inevitable impurity substantially.This steel grade is higher containing Pb and S, have good machinability, but its toughness is poor, easily causes other steel grades to pollute and have environmental issue while smelting containing Pb in addition.
US Patent No. 6146475 discloses a kind of easy cutting Martensite Stainless Steel chemical composition: C:0.06-0.10%, Si≤0.4%, Mn≤0.5%, P≤0.06%, S:0.15-0.55%, Ni≤0.25%, Cr:12.00-12.60%, Mo≤0.10%, Cu≤0.5%, N≤0.04%, surplus is Fe and inevitable impurity.This steel grade obtains good machinability by controlling high sulphur content, but this steel grade toughness and solidity to corrosion are poor.
US Patent No. 2003138342 discloses a kind of solidity to corrosion and the good Martensite Stainless Steel chemical composition of toughness: C≤0.02%, Si≤1.0%, Mn≤1.5%, P≤0.04%, S≤0.01%, Al≤0.1%, Ni:1.5-4.0%, Cr:11-15%, Mo:0.5-2.0%, N≤0.02%, surplus is Fe and inevitable impurity.This patent is by high nickel content and control extremely low sulphur content, obtains good toughness, the solidity to corrosion of passing well by adding molybdenum, but its cost is higher and machinability is difficult to guarantee.
Summary of the invention
The object of the present invention is to provide a kind of Martensite Stainless Steel and manufacture method thereof, by rational chemical Composition Control, make Martensite Stainless Steel there is high room temperature strength (during room temperature, yield strength is greater than 450MPa), medium temperature intensity (300 ℃ time yield strength be greater than 400MPa), good toughness (0 ℃ time V-type ballistic work be greater than 50J) and excellent machinability.
For achieving the above object, the present invention mainly adopts following technical scheme:
A Martensite Stainless Steel, its chemical composition is by weight percentage: C:0.05~0.10%, Si≤1.0%, Mn:0.5~1.2%, P≤0.035%, S:0.02~0.05%, Ni:0.3~0.8%, Cr:12.5~14.0%, Mo:0.2~0.7%, N:0.02~0.05%, Ca:0.001~0.003%, C+N=0.08~0.12%, all the other are Fe and inevitable impurity.
Definite principle of the chemical composition of Martensite Stainless Steel of the present invention is as follows:
Carbon: be strong austenite former, can improve the intensity of steel.Carbon content can not be too low, otherwise room temperature and medium temperature intensity are on the low side, too much unsuitable, can reduce solidity to corrosion and reduce toughness, so carbon content is preferentially 0.05~0.10% while surpassing 0.08%.
Silicon: as reductor, add, when content is lower, the mechanical property of steel do not had to large impact, but add too much, can make processing and toughness deteriorated, so the access control of silicon below 1.0% for well.
Manganese: be weak austenite element, play the effect of stable austenite, can suppress the deleterious effect of sulphur in stainless steel, improve thermoplasticity, but too high meeting increases the tendency that intermetallic compound forms, and also can reduce solidity to corrosion, should be controlled between 0.5~1.2%.
Phosphorus: be the impurity element in steel, for thermoplasticity and corrosion proof consideration, this constituent content is more few better, should be controlled at P≤0.035%.
Sulphur: be the impurity element in steel, for thermoplasticity and corrosion proof consideration, this constituent content is more few better, but sulphur forms sulfide in steel, favourable to the machinability of material, therefore preferred sulphur content is 0.02~0.05%.
Chromium: improve corrosion proof important element, can improve stainless steel solidity to corrosion in oxidizing acid, improve its local corrosion ability such as anticorrosion stress-resistant, spot corrosion and crevice corrosion in chloride soln.When too low, solidity to corrosion is poor, but chromium too high levels, can increase ferrite and intermetallic compound is separated out tendency, is therefore preferably 12.5~14.0%.
Nickel: the element as strong formation and expansion austenitic area, can improve the stability of austenite structure and improve hot workability, but the price of nickel is higher, therefore preferably nickel content should be controlled between 0.3~0.8%.
Molybdenum: be ferrite former, can improve alloy corrosion resistance, in Martensite Stainless Steel, add the temper resistance that molybdenum can improve Martensite Stainless Steel, improve its medium temperature intensity, but consideration price factor should not be added, and is therefore preferably controlled between 0.2~0.7%.
Nitrogen: be strong austenite former, improve hardenability and the intensity of steel, but add-on too much can make toughness variation, be therefore preferably controlled between 0.02~0.05%.
Calcium: calcium is processed can control oxide morphology, and compound by oxide compound-sulfide, can improve toughness, cutting and machinability, but calcium contents is when too much, can cause inclusion too much to affect on the contrary the toughness of material, therefore preferably be controlled at 0.001~0.003%.
Martensite Stainless Steel of the present invention will have high medium temperature intensity, good toughness and excellent machinability, and first this will carry out specific aim design from chemical composition.
Obtain the Martensite Stainless Steel that room temperature strength and medium temperature intensity are good, the control of nitrogen and carbon content is effective and the most most economical method, nitrogen and carbon are strong austenite formers, increasing carbon and nitrogen content can increase the stability of austenitic stainless steel, martensite intensity and the hardness of quenching and tempering are increased, the precipitate of carbon and nitrogen also can increase intensity and the hardness of material in addition, but excessive carbon and nitrogen element, can make in whole steel is all martensitic stucture, there is no ferritic structure, the plasticity that causes Martensite Stainless Steel, toughness is poor, and device support plate belongs to industrial use, plasticity to material, toughness reguirements is higher, therefore need to be on the basis of Low Carbon Martensite Stainless Steel, by improving carbon nitrogen content in rational scope, therefore the present invention by carbon content control 0.05~0.10%, nitrogen control of element is 0.02~0.05%, and C+N total content is controlled at 0.08~0.12%.
In order further to guarantee to obtain good medium temperature intensity; the present invention has added appropriate molybdenum; the interpolation of molybdenum not only can improve the solidity to corrosion of steel; the room temperature strength that at room temperature can solution strengthening further guarantees steel; in drawing process, can improve martenaging martempering stability, thereby improve the middle temperature mechanical property of material.
In order to obtain good toughness when guaranteeing Martensite Stainless Steel intensity, by adding appropriate nickel, it is one of method, rationally determine in addition the content of nickel equivalent forming element Ni, Mn, N, C and chromium equivalent forming element Cr, Si, Mo, control in Martensite Stainless Steel and contain a small amount of ferrite content, can make it have good toughness, when ferrite content is too low, the toughness of Martensite Stainless Steel is poor, and ferrite content is when higher, the room temperature strength of material and medium temperature intensity are difficult to guarantee.
By controlling appropriate sulphur content in chemical composition and guaranteeing that sulfide disperse distributes to improve easy cutting and the machinability of material, can because of excessive sulfide existence, not cause the plasticity and toughness of material and solidity to corrosion too poor simultaneously yet.And by calcium, process and further control oxide morphology, make oxide compound-sulfide compound, can further improve cutting and machinability, reach Sulphur Steel effect, can improve toughness simultaneously.
The manufacture method of Martensite Stainless Steel of the present invention, comprises the steps: 1) proportioning of above-mentioned chemical composition smelts, and casting obtains continuously cast bloom or static ingot; 2) heating, hot rolling, described Heating temperature is 1100~1150 ℃, presses continuously cast bloom or static ingot thickness described heat-up time and determines: 1~1.2min/mm; Finishing temperature is 960~1020 ℃; 3) cooling; 4) high tempering carries out high tempering at 700~750 ℃, and the high tempering time presses steel plate thickness and determines: 6~7min/mm; 5) pickling, obtains Martensite Stainless Steel.
Further, described smelting mode adopts electric furnace+AOD stove+LF stove mode to smelt.
Again, described cooling step is: with 0.5 ℃/more than s speed, be quickly cooled to below 200 ℃, then air cooling is to room temperature.
Have, after described hot rolling, obtain hot-rolled sheet, the thickness of described hot-rolled sheet is 20~40mm.
In the manufacture method of Martensite Stainless Steel of the present invention, the principle of design of processing condition is as follows:
In smelting process, in the refining later stage (being in LF stove smelting process), carry out calcium processing, guarantee that calcium contents is between 0.001~0.003%, increase the forming core particle in molten steel, can make sulphide inclusion modifacation, form complex sulfide, make continuously cast bloom or static ingot medium sulphide content be uniformly distributed plasticity and toughness and the machinability that is conducive to improve material.
The selection of the Heating temperature of hot rolling is mainly: Heating temperature can not be too high, if too high, will cause as-cast structure thick, thick as-cast structure will cause thick As rolled tissue, thereby be unfavorable for refinement material grains, but too low meeting causes material deformation drag to improve, increased the manufacture difficulty of material, therefore Heating temperature being formulated is 1100~1150 ℃.
Hot rolling is controlled according to the thickness of continuously cast bloom or static ingot definite heat-up time: 1~1.2min/mm, its object: will guarantee that on the one hand material heat penetration and temperature are even, prevent that on the other hand original grain from growing up in heat-processed, because if Heating temperature causes continuously cast bloom grain growth long time.
Finishing temperature is controlled at 960~1020 ℃, at this temperature, be conducive to dynamic recrystallization, obtain tiny high temperature austenite tissue, this temperature is a little more than more than austenitizing temperature simultaneously, can avoid precipitated phase to separate out, be conducive to follow-up process of cooling and obtain good tissue.Speed with 0.5 ℃/s after hot rolling is quickly cooled to below 200 ℃, in order to utilize the high temperature rolling cooling normalizing effect that plays steel fast, can save follow-up quenching heat treatment operation (conventional Martensite Stainless Steel needs quenching process just can guarantee material property), save the process cost of this Martensite Stainless Steel, also can avoid the risk of hardening break or distortion, ultra-long and ultra-thick specification also can avoid needing special quenching apparatus simultaneously.
High tempering thermal treatment temp is controlled at 700~750 ℃ carries out, and tempering time is determined according to steel plate thickness: 6~7min/mm, and can be so that tempered martensite makes the intensity of material and toughness obtain good coupling.
Compared with prior art, beneficial effect of the present invention is:
1, by improving carbon nitrogen content in rational scope, appropriate molybdenum and nickel have been added, rationally determine in addition the content of nickel equivalent forming element Ni, Mn, N, C and chromium equivalent forming element Cr, Si, Mo, control the ferrite content in Martensite Stainless Steel, make Martensite Stainless Steel there is the matched well of high room temperature strength, medium temperature intensity and good toughness;
2, by calcium, process and appropriate sulphur content and guarantee that sulfide disperse distributes to improve easy cutting and the machinability of material;
3, by rationally determining that the measures such as hot rolling Heating temperature, finishing temperature and speed of cooling have reduced quenching process, have reduced production cost.
The present invention is by above-mentioned chemical composition design and process control, and the Martensite Stainless Steel of acquisition has high room temperature strength (during room temperature, yield strength is greater than 450MPa), medium temperature intensity (300 ℃ time yield strength be greater than 400MPa), good toughness (0 ℃ time V-type ballistic work be greater than 50J) and excellent machinability.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is further elaborated, should be clear and definite, these embodiment are only for specific description of embodiments of the present invention, and are not used in protection scope of the present invention is formed to any restriction.
Table 1 is depicted as the composition of embodiment of the present invention steel and comparative example steel, and all the other are iron for composition.Table 2 is depicted as the performance of embodiment of the present invention steel and comparative example steel.
Embodiment 1
Adopt electric furnace+AOD+LF melting, be cast into 200mm continuously cast bloom, 1120 ℃ of Heating temperatures, time inside furnace 220min, finishing temperature is controlled at 990 ℃, hot-rolled sheet thickness 30mm, speed with 0.8 ℃/s is chilled to below 200 ℃ soon, and then air cooling, to room temperature, carries out high tempering thermal treatment at 720 ℃, tempering time 180min, obtains martensitic stainless steel material after pickling.This sheet material has excellent room temperature, medium temperature intensity and good toughness, by controlling calcium contents and sulphur content, has guaranteed the machinability that it is good.All properties is listed in table 2.
Embodiment 2
Adopt electric furnace+AOD+LF melting, be cast into 150mm continuously cast bloom, 1150 ℃ of Heating temperatures, time inside furnace 160min, finishing temperature is controlled at 1010 ℃, hot-rolled sheet thickness 20mm, speed with 1.0 ℃/s is chilled to below 200 ℃ soon, and then air cooling, to room temperature, carries out high tempering thermal treatment at 740 ℃, tempering time 140min, obtains martensitic stainless steel material after pickling.This sheet material has excellent room temperature, medium temperature intensity and good toughness, by controlling calcium contents and sulphur content, has guaranteed the machinability that it is good.All properties is listed in table 2.
Embodiment 3
Adopt electric furnace+AOD+LF melting, die casting 365mm slab ingot, 1100 ℃ of Heating temperatures, time inside furnace 420min, finishing temperature is controlled at 970 ℃, hot-rolled sheet thickness 40mm, speed with 0.6 ℃/s is chilled to below 200 ℃ soon, and then air cooling, to room temperature, carries out high tempering thermal treatment at 710 ℃, tempering time 240min, obtains martensitic stainless steel material after pickling.This sheet material has excellent room temperature, medium temperature intensity and good toughness, by controlling calcium contents and sulphur content, has guaranteed the machinability that it is good.All properties is listed in table 2.
Embodiment 4
Adopt electric furnace+AOD+LF melting, be cast into 365 slab ingots, first carry out rolling-cogging, cogging, to 150mm, is then carried out hot rolling, 1150 ℃ of hot rolling Heating temperatures, time inside furnace 160min, finishing temperature is controlled at 1010 ℃, and hot-rolled sheet thickness 20mm is chilled to below 200 ℃ soon with the speed of 1.0 ℃/s, then air cooling is to room temperature, at 740 ℃, carry out high tempering thermal treatment, tempering time 140min, obtains martensitic stainless steel material after pickling.This sheet material has excellent room temperature, medium temperature intensity and good toughness, by controlling calcium contents and sulphur content, has guaranteed the machinability that it is good.All properties is listed in table 2.
Comparative example
Comparative example 1 is conventional 410S Low Carbon Martensite Stainless Steel, and comparative example 2 is similar Martensite Stainless Steel composition of the present invention, but C+N value is not in span of control of the present invention.From performance list, can find out, comparative example 1 is because the constituent contents such as carbon, nitrogen and molybdenum are low, make martensitic poor stability, when high tempering, there is amount of ferrite, cause room temperature, middle temperature mechanical property and impact property all very poor, and being difficult for chip breaking while not having sulfur-bearing to cause machining, surface accuracy is poor.
Comparative example 2 due to carbon and nitrogen content too high, make in microstructure ferrite content low, cause Martensite Stainless Steel room temperature, medium temperature intensity higher, and plasticity and toughness are poor.Therefore the performance of comparative example difference guarantees the matched well of room temperature strength, medium temperature intensity, toughness and machinability.
Table 1 unit: weight percent
Figure BDA0000448573710000081
Table 2
Figure BDA0000448573710000082
From above-mentioned table 2 performance comparison, can find, Martensite Stainless Steel of the present invention is compared with existing steel grade, has excellent room temperature strength, medium temperature intensity, good toughness and machinability.
Be noted that above embodiment is only unrestricted in order to technical scheme of the present invention to be described.Although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement the technical scheme of invention, and not depart from the scope of technical solution of the present invention, it all should be encompassed in claim scope of the present invention.

Claims (5)

1. a Martensite Stainless Steel, its chemical component weight per-cent is: C:0.05~0.10%, Si≤1.0%, Mn:0.5~1.2%, P≤0.035%, S:0.02~0.05%, Ni:0.3~0.8%, Cr:12.5~14.0%, Mo:0.2~0.7%, N:0.02~0.05%, Ca:0.001~0.003%, C+N=0.08~0.12%, all the other are Fe and inevitable impurity.
2. the manufacture method of Martensite Stainless Steel as claimed in claim 1, it comprises the steps:
1) smelt, cast
Proportioning by chemical composition described in claim 1 is smelted, and casting obtains continuously cast bloom or static ingot;
2) heating, hot rolling
Continuously cast bloom or Heating Steel Ingots, 1100~1150 ℃ of Heating temperatures, press heat-up time continuously cast bloom or
Static ingot thickness is determined: 1~1.2min/mm; 960~1020 ℃ of finishing temperatures;
3) cooling;
4) high tempering
At 700~750 ℃, carry out high tempering, the high tempering time presses steel plate thickness and determines: 6~7min/mm;
5) pickling, obtains Martensite Stainless Steel.
3. the manufacture method of Martensite Stainless Steel according to claim 2, is characterized in that, described smelting mode adopts electric furnace+AOD stove+LF stove mode to smelt.
4. the manufacture method of Martensite Stainless Steel according to claim 2, is characterized in that, described step 3) is cooled to: with 0.5 ℃/more than s speed, be quickly cooled to below 200 ℃, then air cooling is to room temperature.
5. the manufacture method of Martensite Stainless Steel according to claim 2, is characterized in that, after described hot rolling, obtains hot-rolled sheet, and the thickness of described hot-rolled sheet is 20~40mm.
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