CN102634739A - Corrosion-resisting stainless steel and manufacturing process thereof - Google Patents
Corrosion-resisting stainless steel and manufacturing process thereof Download PDFInfo
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Abstract
The invention provides corrosion-resisting stainless steel and a manufacturing process of the corrosion-resisting stainless steel. The corrosion-resisting stainless steel comprises the following chemical components in percentage by weight: less than 0.10% of C, 15-22% of Cr, 0.6-3.0% of Mo, 9.0-10.5% of Ni, 0.40-2.0% of B, less than 0.5% of Cu, less than 1% of Si, less than 0.9% of Mn, 0.2-0.6% of Ti, less than 0.3% of Al, less than 0.05% of N, less than 0.04% of P, less than 0.01% of S and inevitable impurity elements. Therefore, the corrosion-resisting stainless steel has higher hot and cold fatigue resistance, anti-fracture toughness, thermal shock resistance, good hot-working property, and welding performance; the smelting process is simple; and the processing cost is low.
Description
Technical field
The invention belongs to technical field of stainless steel materials, relate to a kind of noncorroding metal material and ME thereof, particularly a kind of anticorrosive stainless steel and ME thereof.
Background technology
Boron is a kind of special element, and ordination number is 5, between metal and nonmetal between, can metallizing again can with nonmetal chemical combination.Boron is the main alloy element in the cast steel with high chromium, in high boron, high chrome cast steel, adds an amount of B, promptly can replace the part carbon atom in the carbide, forms the alloy carbide of boracic, and the carbide volume(tric)fraction is increased along with the increase of boron content.And the carbide containing boron average hardness than (Cr, Fe)
7C
3The type carbide improves, and the high stainless steel of boracic is easier to the friction Induced martensitic transformation, produces work hardening, and it is high that its resistance to abrasion does not have the boron stainless steel yet.Simultaneously, because the difference of atomic size causes the lattice distortion, the microhardness of matrix is improved.Moreover, because the boron atomic radius is less, very easily produces and gather partially at crystal boundary.The boron that gathers partially on crystal boundary can suppress ferritic cenotype forming core, helps improving the hardening capacity and the hardenability of cast steel with high chromium.These effects of boron are favourable to improving the cast steel with high chromium abrasion resistance.But the boron add-on is too much, will cause fragility boride quantity to increase, and causes that the stainless steel flexible descends; Damage stainless intensity and toughness; When the boron add-on less, boride comparatively small amt in the stainless steel, not obvious to the wear resistance effect that improves cast steel.
The solubleness of boron in iron is little, and the boron major part that therefore adds in the iron will form boride.Control the percent by volume of boride hard phase through controlling boron content, control matrix carbon content through the control carbon content, and then the performance of control matrix, promptly through controlling the content of boron and carbon respectively, to realize the wear resistance and the toughness of material.Add nickel in the steel and can improve hardening capacity, add the carbide that molybdenum can form molybdenum, improve the wear resistance of steel.Can form boride and add boron in the steel, because boride hardness is high, wear resistance is high; Red hardness is good; Can replace molybdenum,, and comprise brittle eutectic boride owing to contain the no precipitate ferrite area tough, that plasticity is excellent in the boron-containing steel tissue because boron can improve the hardening capacity of steel; Thereby absorbed the various stress that in quenching process, produce, and suppressed crackle from brittle eutectic boride generation and expansion.Therefore, add boron in the steel and can replace nickel and molybdenum.And the chromium that in steel, adds certain content can improve the content of boron in austenite, adds the elements such as chromium, molybdenum and vanadium bigger than iron atom radius in the iron alloy, helps to improve the solid solubility of boron in ferrous alloy, improves the ferrous alloy performance.
Utilize the good thermal neutron sorption of boron (B), the stainless steel that is added with boron can be used as nuclear fuel and carries with container, controls material and blocking material with thermal neutrons such as finishing the nuclear fuel storage rack.Generally, the used usefulness of nuclear plant finishes nuclear fuel, before processing plant is untreated again, is taken care of in the pond in the power station.Because the demand that in limited space, can how to take care of to the greatest extent with finishing nuclear fuel is arranged, the trend that in boronated stainless steel, increases boron content, makes the attenuation of steel plate thickness is just arranged.
Austenitic stainless steel is formed with the passive state epithelium because of its surface, so erosion resistance is outstanding, can improves resistance characteristic, have the energising of requirement to use electrical accessory so it can be used as to erosion resistance owing to make it contain boron.As not only requiring outstanding erosion resistance, but also requiring the purposes example of the energising of low contact resistance, for example have and utilize hydrogen and oxygen to carry out the separator for fuel battery that direct current generates electricity with electrical accessory.
The hot-work of boronated stainless steel is to carry out repeatedly with process furnace steel billet heating and processing such as forging or calendering being prevented that processed material temperature from descending, so that when guaranteeing hot workability, carry out hot-work.Because hot workability can descend when boron content increased, process so just need frontier defense to end processed material temperature trailing edge, consequently, the essential number of occurrence that increases heating and processing.Therefore, the processing of the thin thickness of the increase of boron content or steel will cause manufacturing cost to rise.
In addition, to the boronated stainless steel built-up welding time, guarantee enough throat thickness for preventing crackle, cause number of weld passes to increase, the welding number increases.In addition, when producing welding crack, this will become starting point and cause the generation that the limit is split then, so, be difficult to prevent fully the generation that the limit is split.
Summary of the invention
The objective of the invention is to solve deficiency of the prior art; Overcome and avoided problem noted earlier; Combination through elements such as Cr, B, Ni, Nb, Re; Heat-and corrosion-resistant austenitic stainless steel with superior corrosion resistance is provided; Thereby satisfy nuclear power industry and zinc-plated industry to the stainless requirement of this project corrosion resistance heat-and corrosion-resistant, have already and zinc-plated industry, large-scale power, petrochemical industry, environmental protection equipment and the broad prospect of application in process furnace, used the electrician.
For realizing above-mentioned purpose, the present invention can realize through following basic design of chemical composition and technical scheme: a kind of anticorrosive stainless steel chemical component provided by the present invention and mass percent thereof do;
C＜0.10%, Cr 15～22%, and Mo 0.6～3.0%, and Ni 9.0～10.5%, and B 0.40～2.0%; Cu＜0.5%, Si＜1%, Mn＜0.9%, Ti 0.2～0.6%, Al＜0.3%; N＜0.05%, P＜0.04%, S＜0.01 and unavoidable impurities element.
Anticorrosive stainless steel provided by the present invention and ME thereof, its manufacturing technology steps is:
(1) steel scrap, ferrochrome are melted in electric furnace; The molten clear back of molten steel adds copper coin, ferrosilicon, ferromanganese, and the control carbon content reaches requirement, the stokehold be adjusted to branch qualified after; Melt temperature is increased to 1560～1620 ℃; Add silicocalcium and carry out preliminary dexidation, add the aluminium final deoxygenation, add the fusing of ferrotianium and ferro-boron then in regular turn;
(2) when ferrotianium and ferro-boron all after the fusing, will be less than the particulate state magnesium-rare earth below the 12mm and metallic cerium, Si
3N
4, composite inoculating nucleating agent that Nb and K formed wraps with sheet iron, after 160～200 ℃ temperature baking, is placed on the bottom of ladle, with the method that pours in the bag to smelting the good molten steel inoculation that goes bad;
(3) will pass through the molten steel that bag endomorphism inoculation crosses and in sand mold or metal mold, pour into foundry goods, 1400～1450 ℃ of melt cast temperature;
(4) after the casting finish, subcritical annealing was carried out in insulation in 4-6 hour under 700～750 ℃ of temperature, and matrix is resolved into the mixtinite of ferritic and carbide, made its hardness be reduced to 30～35HRC, so that carry out mechanical workout;
(5) after the casting finish; Or after mechanical workout; Foundry goods or workpiece were heat-treated 920～1150 ℃ of insulations in 2-4 hour, make its sclerosis, carry out air cooling then to room temperature to form austenite; So that in alloy substrate, form martensitic microstructure, the hardness of the material after this thermal treatment process of process is handled can reach HRC50～65.If desired, can the material after the thermal treatment be carried out temper at 150～200 ℃, tempering insulation time 2-4 hour, with the stove air cooling to room temperature, with further adjustment hardness.
The performance of alloy material is by the metallographic structure of metallic substance decision, and certain material structure depends on the chemical ingredients and the thermal treatment process thereof of material, and definite foundation of chemical ingredients of the present invention is:
C, C have the element of guaranteeing the intensity effect.But when its content nearly surpasses 0.08%, will become the reason of erosion resistance variation, hot workability variation etc.Therefore, its content is preferably below 0.08%.And be preferably more than 0.01%.
Cr is for having the element that improves the erosion resistance effect, because its content is 5% can produce a desired effect when above.Cr is the principal element in the alloy of the present invention.In boronated stainless steel, add Cr and can improve the hardening capacity of steel, the tissue of refinement steel helps reducing the fragility of boride.When the content of Cr in the steel greater than 12% the time, carbide be mainly high firmness (Cr, Fe)
7C
3The type carbide, thus make alloy have good resistance to abrasion, and Cr also has good oxidation-resistance and corrosion resistance nature simultaneously.In boronated stainless steel chromatize on the one hand can solid solution in matrix; Improve matrix hardening capacity; Chromium also has solid solution in boride and reduce the brittle effect of boride on the other hand; Chromium also promotes the increase of boron solid solution capacity in matrix, has indirect raising cast steel hardening capacity, improves the effect of temper resistance.But when the Cr too high levels, the smelting of material difficulty, castability worsens, and cost increases.Comprehensive above factor, the present invention is controlled at 15～22% with Cr content.
B:B is a kind of special element, and ordination number is 5, between metal and nonmetal between, can metallizing again can with nonmetal chemical combination.Boron is the main alloy element in the cast steel with high chromium, in high boron, high chrome cast steel, adds an amount of B, promptly can replace the part carbon atom in the carbide, forms the alloy carbide of boracic, and the carbide volume(tric)fraction is increased along with the increase of boron content.And the carbide containing boron average hardness than (Cr, Fe)
7C
3The type carbide improves, and the boron-containing high-chromium steel is easier to the friction Induced martensitic transformation, produces work hardening, and it is high that its resistance to abrasion does not have the boron high chromium steel yet.Simultaneously, because the difference of atomic size causes the lattice distortion, the microhardness of matrix is improved.Moreover, because the boron atomic radius is less, very easily produces and gather partially at crystal boundary.The boron that gathers partially on crystal boundary can suppress ferritic cenotype forming core, helps improving the hardening capacity and the hardenability of cast steel with high chromium.These effects of boron are favourable to improving the cast steel with high chromium abrasion resistance.But the boron add-on is too much, will cause fragility boride quantity to increase, and causes that the cast steel with high chromium flexible descends; The intensity and the toughness of infringement cast steel; When the boron add-on less, boride comparatively small amt in the cast steel, not obvious to the wear resistance effect that improves cast steel.Comprehensive above reason, the present invention is controlled at 0.4～2.0% with B content
Cu:Cu is non-carbide and boride forming element, mainly is dissolved in matrix, can obviously improve the hardening capacity of matrix, is dissolved in the effect that copper in the matrix improves the high-boron cast steel erosion resistance in addition.The copper add-on is very few, and not obvious to the hardening capacity effect that improves high-boron cast steel, add-on is too much, and part copper also can be separated out at grain boundary precipitate, reduces the wear resistance of high-boron cast steel on the contrary, takes all factors into consideration, and copper content is controlled at 0.3～2.6%.
Ti: in high boron, add an amount of titanium, can thinning solidification structure, can also the refinement boride, promote the suspension of boride network to distribute with isolated.Ti+2B=TiB takes place in the titanium adding high-boron cast steel
2Reaction forms blocky TiB
2, the improvement that promotes iron boron cpd form and distribution is had a significant effect, help improving the mechanical property that contains boron cast steel.The high-boron cast steel melt added the titanium elements fixed nitrogen earlier before adding boron, can stabilize and increase the boron yield.In addition; Titanium is strong carbon, nitrogen compound forming element, and the carbide of titanium, nitride and carboritride can be separated out as first precipitated phase in process of setting, promotes the refinement of solidified structure; And the segregation that alleviates boron, help improving the intensity and the toughness of cast steel with high chromium.The titanium add-on is too much, causes the compound quantity of titanium to increase, with thick block TiB occurring
2, reduce the intensity and the toughness of cast steel on the contrary, take all factors into consideration, titanium content is controlled at 0.2～0.6%.
Si, the Si that is added are to have the element that improves the oxidation-resistance effect as Oxygen Scavenger.But when its content surpasses 1%, can increase the welding crack susceptibility.Therefore, its content is preferably below 1%.
Mn:Mn can increase the hardening capacity of steel strongly, and martensitic stucture is easy to get after the quenching.Manganese can also play the effect of reductor and sweetening agent, can cleaning molten steel.Adding an amount of manganese in the High Boron Steel, mainly is in order to improve the hardening capacity of steel, and add-on is too much, and tissue that will the alligatoring steel increases the hot cracking tendency of High Boron Steel.To take all factors into consideration, manganese is controlled at＜and 0.9%.
N, N and B combine to cause the toughness variation.For guaranteeing enough toughness, its content is preferably below 0.05%.
Mo is below 5%, and Cu is below 0.5%, and Al is below 0.3%:
These elements just can further be brought into play the effect that improves erosion resistance as long as optionally its content is controlled in the above-mentioned content range.Therefore, when these effects of needs, can contain the above-mentioned element in above-mentioned content range alone or in combination.
P is the impurity element in the steel, and because of its content surpasses at 0.04% o'clock, the welding crack susceptibility can increase, so its content is preferably below 0.04%.
S is the impurity element in the steel, can increase because of its content surpasses 0.01% o'clock welding crack susceptibility, so its content is preferably below 0.01%.
Beneficial effect
Compared with prior art, the present invention has following advantage:
Anticorrosive stainless steel of the present invention have since in the matrix carbon content extremely low, thereby have higher cold-resistant thermal fatigue, anti-fracture toughness property and thermal shock resistance, have good hot workability and welding property, and smelting technology is simple, tooling cost is low.Owing to contain a large amount of chromium, have good antioxidant property, corrosion resistance nature.Owing in the stainless steel composition, add alloying elements such as an amount of molybdenum, nickel, thereby further improved the hardenability and the hardness of material, improve softening resistance, wear resisting property under the high temperature.
Anticorrosive stainless steel of the present invention is applied widely, can be widely used in nuclear fuel and carry with container, uses fields such as isolating material with the neutron masking material and the fuel cell of nuclear energy relevant devices such as complete nuclear fuel storage shelf.
Embodiment
Below in conjunction with embodiment the present invention is made further detailed description.
(1) steel scrap, ferrochrome are melted in electric furnace; The molten clear back of molten steel adds copper coin, ferrosilicon, ferromanganese, and the control carbon content reaches requirement, the stokehold be adjusted to branch qualified after; Melt temperature is increased to 1560～1620 ℃; Add silicocalcium and carry out preliminary dexidation, add the aluminium final deoxygenation, add the fusing of ferrotianium and ferro-boron then in regular turn;
(2) when ferrotianium and ferro-boron all after the fusing, will be less than the particulate state magnesium-rare earth below the 12mm and metallic cerium, Si
3N
4, composite inoculating nucleating agent that Nb and K formed wraps with sheet iron, after 160～200 ℃ temperature baking, is placed on the bottom of ladle, with the method that pours in the bag to smelting the good molten steel inoculation that goes bad;
(3) will pass through the molten steel that bag endomorphism inoculation crosses and in sand mold or metal mold, pour into foundry goods, 1400～1450 ℃ of melt cast temperature;
(4) after the casting finish, subcritical annealing was carried out in insulation in 4-6 hour under 700～750 ℃ of temperature, and matrix is resolved into the mixtinite of ferritic and carbide, made its hardness be reduced to 30～35HRC, so that carry out mechanical workout;
(5) after the casting finish; Or after mechanical workout; Foundry goods or workpiece were heat-treated 920～1150 ℃ of insulations in 2-4 hour, make its sclerosis, carry out air cooling then to room temperature to form austenite; So that in alloy substrate, form martensitic microstructure, the hardness of the material after this thermal treatment process of process is handled can reach HRC50～65.If desired, can the material after the thermal treatment be carried out temper at 150～200 ℃, tempering insulation time 2-4 hour, with the stove air cooling to room temperature, with further adjustment hardness.
The anticorrosive stainless steel chemical component of table 1 (weight percent)
Claims (1)
1. anticorrosive stainless steel and ME thereof, it is characterized in that: in massfraction, contain C＜0.10%, Cr 15～22%; Mo 0.6～3.0%, and Ni 9.0～10.5%, and B 0.40～2.0%, Cu＜0.5%; Si＜1%, Mn＜0.9%, Ti 0.2～0.6%, Al＜0.3%; N＜0.05%, P＜0.04%, S＜0.01 and unavoidable impurities element; Its manufacturing technology steps is:
(1) steel scrap, ferrochrome are melted in electric furnace; The molten clear back of molten steel adds copper coin, ferrosilicon, ferromanganese, and the control carbon content reaches requirement, the stokehold be adjusted to branch qualified after; Melt temperature is increased to 1560～1620 ℃; Add silicocalcium and carry out preliminary dexidation, add the aluminium final deoxygenation, add the fusing of ferrotianium and ferro-boron then in regular turn;
(2) after ferrotianium and the whole fusings of ferro-boron; The composite inoculating nucleating agent that to be formed less than particulate state magnesium-rare earth and metallic cerium, Si3N4, Nb and the K below the 12mm is wrapped with sheet iron; After the baking of 160～200 ℃ temperature, be placed on the bottom of ladle, with the method that pours in the bag to smelting the good molten steel inoculation that goes bad;
(3) will pass through the molten steel that bag endomorphism inoculation crosses and in sand mold or metal mold, pour into foundry goods, 1400～1450 ℃ of melt cast temperature;
(4) after the casting finish, subcritical annealing was carried out in insulation in 4-6 hour under 700～750 ℃ of temperature, and matrix is resolved into the mixtinite of ferritic and carbide, made its hardness be reduced to 30～35HRC, so that carry out mechanical workout;
(5) after the casting finish; Or after mechanical workout; Foundry goods or workpiece were heat-treated 920～1150 ℃ of insulations in 2-4 hour, make its sclerosis, carry out air cooling then to room temperature to form austenite; So that in alloy substrate, form martensitic microstructure, the hardness of the material after this thermal treatment process of process is handled can reach HRC50～65.If desired, can the material after the thermal treatment be carried out temper at 150～200 ℃, tempering insulation time 2-4 hour, with the stove air cooling to room temperature, with further adjustment hardness.
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| CN104198135A (en) * | 2014-08-26 | 2014-12-10 | 宁波工程学院 | Detection device and detection method for sealing performances of expansion tanks |
| CN104451406A (en) * | 2014-11-18 | 2015-03-25 | 山东省源通机械股份有限公司 | Highly saline-alkaline corrosion resistant stainless steel casting and preparation method thereof |
| CN104480408A (en) * | 2014-12-10 | 2015-04-01 | 无锡鑫常钢管有限责任公司 | OCr18Ni9 small-diameter seamless stainless steel capillary tube and production process thereof |
| CN105039869A (en) * | 2015-08-11 | 2015-11-11 | 中国人民解放军装甲兵工程学院 | Alloy powder used for laser remanufacturing of martensitic stainless steel parts and preparation method |
| CN105063496A (en) * | 2015-09-02 | 2015-11-18 | 祁同刚 | Ferritic stainless steel and manufacturing process thereof |
| CN105908065A (en) * | 2016-05-11 | 2016-08-31 | 曾松盛 | VC<p>-enhanced medium-manganese abrasion-resistant alloy material, preparation method and abrasion-resistant part |
| CN106609336A (en) * | 2015-10-26 | 2017-05-03 | 威尔机械江苏有限公司 | Acid-resistant stainless steel and production method thereof |
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| CN110306100A (en) * | 2018-03-25 | 2019-10-08 | 江苏万恒铸业有限公司 | The method of-kind of optimization CN7M stainless cast steel part performance |
| CN111826583A (en) * | 2019-04-15 | 2020-10-27 | 沈阳铸造研究所有限公司 | High-corrosion-resistance boron stainless steel material and preparation method and application thereof |
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| CN104198135A (en) * | 2014-08-26 | 2014-12-10 | 宁波工程学院 | Detection device and detection method for sealing performances of expansion tanks |
| CN104451406A (en) * | 2014-11-18 | 2015-03-25 | 山东省源通机械股份有限公司 | Highly saline-alkaline corrosion resistant stainless steel casting and preparation method thereof |
| CN104480408B (en) * | 2014-12-10 | 2016-08-31 | 无锡鑫常钢管有限责任公司 | A kind of 0Cr18Ni9 minor diameter seamless capillary stainless steel tube and production technology |
| CN104480408A (en) * | 2014-12-10 | 2015-04-01 | 无锡鑫常钢管有限责任公司 | OCr18Ni9 small-diameter seamless stainless steel capillary tube and production process thereof |
| CN105039869A (en) * | 2015-08-11 | 2015-11-11 | 中国人民解放军装甲兵工程学院 | Alloy powder used for laser remanufacturing of martensitic stainless steel parts and preparation method |
| CN105063496A (en) * | 2015-09-02 | 2015-11-18 | 祁同刚 | Ferritic stainless steel and manufacturing process thereof |
| CN106609336A (en) * | 2015-10-26 | 2017-05-03 | 威尔机械江苏有限公司 | Acid-resistant stainless steel and production method thereof |
| CN105908065A (en) * | 2016-05-11 | 2016-08-31 | 曾松盛 | VC<p>-enhanced medium-manganese abrasion-resistant alloy material, preparation method and abrasion-resistant part |
| CN105908065B (en) * | 2016-05-11 | 2017-12-22 | 曾松盛 | A kind of VCpManganese wear resistant alloy material, preparation method and wear-resisting spare part in enhancing |
| CN110306100A (en) * | 2018-03-25 | 2019-10-08 | 江苏万恒铸业有限公司 | The method of-kind of optimization CN7M stainless cast steel part performance |
| CN110273098A (en) * | 2019-04-12 | 2019-09-24 | 上海大学 | Nuclear screening austenitic stainless steel alloy material and preparation method thereof |
| CN111826583A (en) * | 2019-04-15 | 2020-10-27 | 沈阳铸造研究所有限公司 | High-corrosion-resistance boron stainless steel material and preparation method and application thereof |
| CN111826583B (en) * | 2019-04-15 | 2022-02-15 | 沈阳铸造研究所有限公司 | High-corrosion-resistance boron stainless steel material and preparation method and application thereof |
| CN112899575A (en) * | 2021-01-20 | 2021-06-04 | 钢铁研究总院 | Austenitic stainless steel wire material manufactured based on cold metal transition arc additive manufacturing and process |
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Application publication date: 20120815 |