CN102634741A - High-temperature heat-resistant and corrosion-resistant stainless steel and manufacturing method thereof - Google Patents
High-temperature heat-resistant and corrosion-resistant stainless steel and manufacturing method thereof Download PDFInfo
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- CN102634741A CN102634741A CN201210132920XA CN201210132920A CN102634741A CN 102634741 A CN102634741 A CN 102634741A CN 201210132920X A CN201210132920X A CN 201210132920XA CN 201210132920 A CN201210132920 A CN 201210132920A CN 102634741 A CN102634741 A CN 102634741A
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Abstract
The invention discloses a high-temperature heat-resistant and corrosion-resistant stainless steel and a manufacturing method of the stainless steel. The stainless steel comprises the following chemical compositions by weight: less than 0.08% of C, less than 1.50% of Si, less than 2.00% of Mn, less than 0.045% of P, less than 0.03% of S, 24.0%-26.0% of Cr, 19.0%-22.0% of Ni, 0.5%-1.0% of Nb, less than 0.003% of B, less than 0.01% of La or Re, and the balance of Fe and inevitable impurity elements. The preferential smelting procedures are as follows: conducting vacuum induction melting firstly, then conducting vacuum arc remelting or electroslag remelting, conducting hot processing formation and then conducting solid-solution treatment and ageing treatment.
Description
Technical field
The present invention relates to a kind of high-temperature heat-resistance corrosion-resistant stainless steel; Combination with good high-temperature intensity, plasticity, high temperature microstructure stability, toughness and antioxidant/sulfuration/hydrogenation/carbonation properties; Go for the material and the flat pieces in pyritous oxidation/sulfuration/hydrogenation/carbonization environment that use in large-scale power, petrochemical industry, the environmental protection equipment; Be the nickel-base alloy that to cast He can weld, belong to field of material engineering technology.
Background technology
The high-temperature heat-resistance corrosion-resistant stainless steel has absolute advantage with respect to common stainless steel (18-8 series, Martensite Stainless Steel, ferritic stainless steel etc.) under the corrosive environment of many complicacies and hot conditions, be widely used in the fields such as environmental protection equipment under electric power, petrochemical complex, the severe environment.
All the time, the heat-and corrosion-resistant stainless steel that uses under the development higher temperature condition and under harsh moderate temperature conditions the heat-and corrosion-resistant stainless steel of life-time service be researchist's target.For example, constantly need provide more advanced alloy to keep four industrial circles of industry development: environmental protection equipment and process furnace under electric power, petrochemical complex, the severe environment are used alloy.The application in these fields has common ground, need improve constantly the intensity when under higher temperature, using, and improves anti-sulphur corrosion simultaneously, can use safely in useful life period to guarantee parts.
Long-term environmental protection equipment such as desulfurizer of working in the open air, usually because factor such as temperature is high, the oxidation of sulfureted environment is abominable, often to cause the environmental protection equipment life-span very short because of sulphur corrosion.And the maintenance of these environmental protection equipments needs professional machinery again, and is very inconvenient and consuming time, and these environmental protection equipments are faced with again and improve working temperature to raise the efficiency now, have aggravated the update of alloy.
In petrochemical complex and power equipment, face environmental protection and efficient two large problems, all be faced with in the world wide through improving working temperature and pressure to raise the efficiency this realistic problem.Long term operation had both required higher high temperature strength and anti-oxidant/sulfuration/hydrogenation/graphitic corrosion performance in HTHP and sulfuration/oxidation/hydrogenation/graphitic corrosion environment, consider ME performance, welding property and some processing characteristicies of equipment again.
For satisfying corrosion resistance nature demand under new intensity, temperature and the complicated atmosphere; The stainless steel of former use and some aged hardened alloys that just using at other field so far can not satisfy the demand of hot strength, maximum operation (service) temperature and phase stability, antioxidant/sulfuration/hydrogenation/carbonation properties usually simultaneously.For example; Typical age hardening type nickel-base alloy; The Cr content that must improve alloy to be strengthening anti-curability, but increases the reinforcement of Cr content not only bad for alloy, and if add excessive; Cause in alloy, separating out fragility σ phase, μ phase or α-Cr and form mutually, increase the danger of alloy embrittlement.
The present invention overcomes and has avoided problem noted earlier; Combination through elements such as Cr, Nb, Ni, Re; High-temperature heat-resistance corrosion-resistant stainless steel with superior anti-sulfuration/hydrogenation/graphitic corrosion atmosphere is provided, makes alloy in the high temperature range below 800 ℃, have the good combination of intensity, plasticity, phase stability and toughness and processing characteristics, have in large-scale power, petrochemical industry, environmental protection equipment and the broad prospect of application in process furnace, used.
Summary of the invention
The objective of the invention is to solve deficiency of the prior art; A kind of good combination with hot strength, plasticity, phase stability, toughness and antioxidant/sulfuration/hydrogenation/carbonation properties is provided, is suitable for medium-term and long-term high-temperature heat-resistance corrosion-resistant stainless steel and the method for manufacture of using thereof of sulfur-bearing atmosphere under high-temperature.
For realizing above-mentioned purpose, the present invention can realize through following basic design of chemical composition and technical scheme:
A kind of high-temperature heat-resistance corrosion-resistant stainless steel chemical ingredients provided by the present invention and mass percent thereof do; In the chemical constitution of alloy (massfraction) contain＜phosphorus (P) of the manganese (Mn) of the silicon (Si) of 0.08% carbon (C), contain＜1.50%, contain＜2.00%, contain＜0.045%, contain＜0.03% sulphur (S), the niobium (Nb) of the nickel (Ni) of the chromium (Cr) of 24.0%-26.0%, 19.0%-22.0%, 0.5%-1.0%,＜lanthanum (La) or the REE (Re) of 0.003% boron (B), can contain＜0.01, surplus is iron (Fe) and unavoidable impurities element.
High-temperature heat-resistance corrosion-resistant stainless steel provided by the present invention and method of manufacture thereof, its manufacturing technology steps is:
(1) smelt: alloy of the present invention can be through conventional smelting process preparation, carries out vacuum induction melting earlier headed by the preferably smelting program, and steel scrap, ferrochrome are melted in electric furnace; The molten clear back of molten steel adds 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 ferro-boron fusing then in regular turn; After ferro-boron all melts; To wrap with sheet iron less than the composite inoculating nucleating agent that the particulate state niobium (Nb) below the 12mm and lanthanum (La) or REE (Re) are formed; 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; To pass through the molten steel that bag endomorphism inoculation crosses and in metal mold, pour into consumable electrode, 1400～1450 ℃ of melt cast temperature.
(2) the good consumable electrode of pour into a mould is carried out var or esr, reduce impurity element and melting defective as far as possible, and reduce the segregation of alloying element.
(3) alloying element homogenizing annealing.Carry out solution treatment and ageing treatment behind the thermo forming again.Fig. 1-3 is the detected result of the high-temperature heat-resistance corrosion-resistant stainless steel instance smelted within the scope of the present invention, has provided the cyclic oxidation dynamic behavior under alloy at room temperature and pyritous tensile strength and stretching plastic result and the differing temps respectively.
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:
The Cr element is the key element of alloy of the present invention, because Cr has guaranteed the formation of necessary high temperature oxidation resisting and sulfuration protective membrane.With minor N b (0.5-1.0%) in the alloy, Si (maximum 1.5%) together, make under the high temperature protection essence of protective membrane strengthen more with effectively.These trace elements have increased the adhesivity of protective membrane, the compactness and the anti-resolving power of film.The minimum value of Cr content has guaranteed and can show the sull that forms complete Cr at alloy.In sulfuration/hydrogenation/carburizing atmosphere, the minimum value of Cr content should be greater than 22.0%, the formation of promote the oxidation film when Cr content is higher, but do not change the essence that alloy shows sull.The peak of Cr content is by the stability and the processibility decision of alloy, and its value is no more than 26.0%.
The Mn element uses as effective sweetening agent when the smelting of alloy, but in alloy, it reduces the provide protection of protective membrane; Thereby Mn content is limited in below 2.0%, is higher than this content; To in sull, form MnCr2O4 spinel phase, thereby reduce the protective value of Cr2O3 film.
The Si element is the important element among the present invention; Because Si finally forms the SiO2 layer below the Cr2O3 protective membrane; Improve antioxidant and curability; Si content is being effectively below 0.5%, and excessive Si will cause alloy to form other phases at crystal boundary, and influences plasticity, toughness and the working ability of alloy.
The Fe element reduces the high-temperature corrosion resistance performance of alloy, forms the integrity that the FeCr2O4 spinel reduces Cr2O3 mutually with the Cr sull on surface after its oxidation, and therefore, Fe content is well below 18 8 series stainless steels.
C should remain on below 0.08%, forms primary carbide with Ti and Nb and helps to control grain-size, and the primary carbide of these elements is stable in the hot-work scope (1050-1160 ℃) of alloy of the present invention.Simultaneously, these carbide also help to strengthen crystal boundary raising enduring quality.
The Ni element is important austenite former, and in order to guarantee phase stability, enough hot strength, plasticity, toughness and good working ability, its content must remain on more than 19%.
Usually, alloy of the present invention is particularly useful for electric power, petrochemical industry, environmental protection equipment, process furnace etc. and is operated in the high temperature flat pieces in the vulcanized gas for a long time.
Beneficial effect
Compared with prior art, the present invention has following advantage:
The element combinations that alloy of the present invention sets is suitable in sulfur-bearing atmosphere, using for a long time.Can reach the stability of not destroying some reinforcement precipitated phases in the alloy, the purpose that does not produce the fragility phase, simultaneously through control Cr content range (24.0-26.0%); Through limiting the scope of some alloy elements, less than 1.5%, Mn content is less than 2.0% like Si content; Ni content is between 19.0-22.0%, and C is less than 0.08%, in the alloying element scope of above-mentioned qualification; Can obtain enough anti-oxidant/sulfuration/hydrogenation/carbonation properties, be unlikely to influence the integrated application performance of alloy again.Generally speaking, when obtaining maximum high-temperature corrosion resistance performance as possible, cause alloy to lose essential hot strength.The balance of the logical adjustment of alloy of the present invention precipitation-hardening element nb, Cr, Ni, the excessive adding of strengthening element not only reduces phase stability and reduces plasticity and toughness, and the difficulty when causing stainless steel to be made reduces.The scope that each alloy element in the alloy is chosen has reasonableness according to its function separately.
Description of drawings
Fig. 1 be in the scope of the invention high-temperature heat-resistance corrosion-resistant stainless steel from room temperature to pyritous tensile strength with the ys curve.
Fig. 2 be in the scope of the invention high-temperature heat-resistance corrosion-resistant stainless steel from room temperature to pyritous stretching plastic curve.
Fig. 3 is the high-temperature oxidation resistant kinetic curve of high-temperature heat-resistance corrosion-resistant stainless steel in the scope of the invention.
Embodiment
Below in conjunction with embodiment the present invention is made further detailed description.
(1) smelt: alloy of the present invention can be through conventional smelting process preparation, carries out vacuum induction melting earlier headed by the preferably smelting program, and steel scrap, ferrochrome are melted in electric furnace; The molten clear back of molten steel adds 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 ferro-boron fusing then in regular turn; After ferro-boron all melts; To wrap with sheet iron less than the composite inoculating nucleating agent that the particulate state lanthanum (La) below the 12mm or REE (Re) are formed; 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; To pass through the molten steel that bag endomorphism inoculation crosses and in metal mold, pour into consumable electrode, 1400～1450 ℃ of melt cast temperature.
(2) the good consumable electrode of pour into a mould is carried out var or esr, reduce impurity element and melting defective as far as possible, and reduce the segregation of alloying element.
(4) alloying element homogenizing annealing.Carry out solution treatment and ageing treatment behind the thermo forming again.Fig. 1-3 is the detected result of the high-temperature heat-resistance corrosion-resistant stainless steel instance smelted within the scope of the present invention, has provided the cyclic oxidation dynamic behavior under alloy at room temperature and pyritous tensile strength and stretching plastic result and the differing temps respectively.
Table 1 high-temperature heat-resistance corrosion-resistant stainless steel chemical ingredients (weight percent)
Claims (8)
1. high-temperature heat-resistance corrosion-resistant stainless steel and method of manufacture thereof; It is characterized in that: in massfraction; Contain＜0.08% carbon (C), contain＜1.50% silicon (Si), contain＜2.00% manganese (Mn), contain＜0.045% phosphorus (P), contain＜0.03% sulphur (S), the niobium (Nb) of the nickel (Ni) of the chromium (Cr) of 24.0%-26.0%, 19.0%-22.0%, 0.5%-1.0%,＜0.003% boron (B), contain＜0.01% lanthanum (La) or REE (Re), surplus is iron (Fe) and unavoidable impurities element; Its manufacturing technology steps is:
(1) smelt: can be through conventional smelting process preparation, carry out vacuum induction melting earlier headed by the preferably smelting program, steel scrap, ferrochrome are melted in electric furnace; The molten clear back of molten steel adds 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 ferro-boron fusing then in regular turn; After ferro-boron all melts; To wrap with sheet iron less than the composite inoculating nucleating agent that the particulate state lanthanum (La) below the 12mm or REE (Re) are formed; 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; To pass through the molten steel that bag endomorphism inoculation crosses and in metal mold, pour into consumable electrode, 1400～1450 ℃ of melt cast temperature.
(2) the good consumable electrode of pour into a mould is carried out var or esr, reduce impurity element and melting defective as far as possible, and reduce the segregation of alloying element;
(4) alloying element homogenizing annealing; Carry out solution treatment and ageing treatment behind the thermo forming again;
2. high-temperature heat-resistance corrosion-resistant stainless steel according to claim 1 and method of manufacture thereof, it contains the chromium (Cr) of (in quality %) 24-26%.
3. according to the high-temperature heat-resistance corrosion-resistant stainless steel and the method for manufacture thereof of claim 1, it contains the silicon (Si) of (in quality %)＜1.50%.
4. high-temperature heat-resistance corrosion-resistant stainless steel according to claim 1 and method of manufacture thereof, it contains the manganese (Mn) of (in quality %)＜2.00%.
5. high-temperature heat-resistance corrosion-resistant stainless steel according to claim 1 and method of manufacture thereof, it contains the phosphorus (P) of (in quality %)＜0.045%.
6. high-temperature heat-resistance corrosion-resistant stainless steel according to claim 1 and method of manufacture thereof, it contains the sulphur (S) of (in quality %)＜0.03%.
7. high-temperature heat-resistance corrosion-resistant stainless steel according to claim 1 and method of manufacture thereof, it contains the nickel (Ni) of (in quality %) 19.0%-22.0%.
8. high-temperature heat-resistance corrosion-resistant stainless steel according to claim 1 and method of manufacture thereof, it contains the niobium (Nb) of (in quality %) 0.5%-1.0%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108130469A (en) * | 2017-12-20 | 2018-06-08 | 吴方立 | Antiscour, anti-corrosive alloy material and its smelting technology |
| CN109856005A (en) * | 2018-12-25 | 2019-06-07 | 力信（江苏）能源科技有限责任公司 | A kind of cell size solid content test device and test method |
| CN110079723A (en) * | 2019-05-20 | 2019-08-02 | 燕山大学 | High-strength high-plastic 304 stainless steel of one kind and preparation method thereof |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58202993A (en) * | 1982-05-19 | 1983-11-26 | Daido Steel Co Ltd | Welding wire rod of stainless steel |
| JPH07216451A (en) * | 1994-01-31 | 1995-08-15 | Nisshin Steel Co Ltd | Production of stainless steel material having high welding softening resistance, high strength, and high ductility |
-
2012
- 2012-05-03 CN CN201210132920XA patent/CN102634741A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58202993A (en) * | 1982-05-19 | 1983-11-26 | Daido Steel Co Ltd | Welding wire rod of stainless steel |
| JPH07216451A (en) * | 1994-01-31 | 1995-08-15 | Nisshin Steel Co Ltd | Production of stainless steel material having high welding softening resistance, high strength, and high ductility |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108130469A (en) * | 2017-12-20 | 2018-06-08 | 吴方立 | Antiscour, anti-corrosive alloy material and its smelting technology |
| 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 |
| CN109856005A (en) * | 2018-12-25 | 2019-06-07 | 力信（江苏）能源科技有限责任公司 | A kind of cell size solid content test device and test method |
| CN110079723A (en) * | 2019-05-20 | 2019-08-02 | 燕山大学 | High-strength high-plastic 304 stainless steel of one kind and preparation method thereof |
| CN110079723B (en) * | 2019-05-20 | 2020-04-21 | 燕山大学 | High-strength high-plasticity 304 stainless steel and preparation method thereof |
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Application publication date: 20120815 |