CN102628127A - High-strength corrosion-resisting nickel base alloy and manufacturing method thereof - Google Patents
High-strength corrosion-resisting nickel base alloy and manufacturing method thereof Download PDFInfo
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Abstract
The invention relates to a high-strength corrosion-resisting nickel base alloy and a manufacturing method thereof. The high-strength corrosion-resisting nickel base alloy comprises the following chemical components by weight percent: not more than 0.04% of carbon (C), about 20.0%-26.0% of chromium (Cr), about 6.0%-10.0% of cobalt (Co), about 4.0%-8.0% of tungsten (W), not more than 1.0% of molybdenum (Mo), not more than 1.0% of Ferrum (Fe), not more than 0.5% of silicon (Si), not more than 0.5% of manganese (Mn), about 0.8%-1.3% of niobium (Nb), about 0.3%-0.7% of titanium (Ti), about 0.6%-1.0% of aluminum (Al), about 0.1%-0.4% of zirconium (Zr), not more than 0.003% of boron (B), tiny lanthanum (La) or rare-earth element (Re), and the balance of nickel (Ni) and inevitable impurity element. Vacuum melting and electroslag remelting are adopted, and then solution treatment and ageing treatment are performed.
Description
Technical field
The present invention relates to a kind of high strength anti-corrosion nickel-bass alloy material; Combination with good high-temperature intensity, plasticity, high temperature microstructure stability, toughness and antioxidant/curability; Go for large-scale diesel engine valve body material and the pressure-containing member in pyritous oxidation/vulcanization environment; Be the nickel-base alloy that to cast He can weld, belong to field of material engineering technology.
Background technology
Nickel-base alloy (Ni-Cr alloy, Ni-Cr-Mo alloy, Ni-Cu alloy etc.) has absolute advantage with respect to the stainless steel of iron-based under the corrosive environment of many complicacies and hot conditions, be widely used in aerospace, electric power, the field of petrochemical industry.
All the time, the non-corrosive metal that uses under the development higher temperature condition and under harsh moderate temperature conditions the high strength anti-corrosion alloy of life-time service be researchist's target.For example, constantly need provide more advanced alloy to keep two industrial circles of industry development: oil motor valve and coal firing boiler 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 construction equipment of working is in the open air used large diesel engine, usually because factors such as power is big, energy consumption height are difficult to use high-quality low-sulfur fuel, often causes important part fails such as valve because of sulphur corrosion.And the maintenance of these mechanical parts needs professional machinery again, and is very inconvenient and consuming time, and these diesel motors are faced with again and improve working temperature to improve power and efficient now, have aggravated the update of alloy.In addition, the naval vessel then faces more complicated salt corrosion with oil motor.
In the coal-burning power plant, face the efficient two large problems of environmental protection, all be faced with in the world wide through improving vapor temperature and pressure to improve this realistic problem of efficient of coal firing boiler.The efficient in 600 ℃ of current ultra supercritical power stations generally is no more than 45%, and when vapor temperature reaches 700 ℃ of pressure and reaches 35Mpa, efficiency of plant will reach about 50%.The vapor temperature of coal-burning power plant is to 700 ℃ of development in recent years.The boi1er tube long term operation had both required higher high temperature strength and anti-oxidant/sulphur corrosion performance in HTHP and sulfuration/oxidation corrosion environment, consider ME performance, welding property and some processing characteristicies of boi1er tube again.
For satisfying the new intensity and the corrosion resistance nature demand of high-power advanced oil motor valve and following ultra supercritical coal-fired plant boiler pipe alloy; The ferritic of former use, solid solution austenite 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/curability 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, Ti, Al; Nickel-base alloy with superior anti-sulphur 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 at heavy construction machinery with oil motor and naval vessel with oil motor and the broad prospect of application in the high-parameters power plant boiler, 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 corrosion-resistant high strength anti-corrosion nickel-base alloy of high-temperature heat-resistance 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 strength anti-corrosion nickel-base alloy chemical ingredients provided by the present invention and mass percent thereof do; In the chemical constitution of alloy (massfraction) contain cobalt (Co), the 4.0%-8.0% of the chromium (Cr) that is no more than 0.04% carbon (C), 20.0%-26.0%, 6.0%-10.0% tungsten (W), be no more than 1.0% molybdenum (Mo), be no more than 1.0% iron (Fe), be no more than 0.5% silicon (Si), be no more than 0.5% manganese (Mn), the zirconium (Zr) of the aluminium (Al) of the titanium (Ti) of the niobium (Nb) of 0.8-1.3%, 0.3%-0.7%, 0.6%-1.0%, 0.1%-0.4%, be no more than 0.003% boron (B), can contain the lanthanum (La) or the REE (Re) of trace, surplus is nickel (Ni) and unavoidable impurities element.
High strength anti-corrosion nickel-base alloy provided by the present invention and method of manufacture thereof, its manufacturing technology steps is:
(1) steel scrap, ferrochrome are melted in electric furnace; The molten clear back of molten steel adds nickel plate, ferrotungsten, molybdenum-iron, ferro-cobalt, 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; To wrap with sheet iron less than the composite inoculating nucleating agent that the particulate state ferro-niobium below the 12mm, zirconium, lanthanum (La) or REE (Re) magnesium-rare earth 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;
(3) molten steel that bag endomorphism inoculation crosses be will pass through and foundry goods or consumable electrode in sand mold or metal mold, poured into, 1400～1450 ℃ of melt cast temperature;
(4) 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;
(5) alloying element homogenizing annealing; Carry out solution treatment and ageing treatment behind the thermo forming again.
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 a spot of Zr (0.1-0.4%) in the alloy, Si (maximum 0.5%) 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 vulcanized gas, the minimum value of Cr content should be greater than 20.0%, 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%.
Co is a kind of important matrix element, and Co is of value to the maintenance of hot hardness and intensity in high temperature range, and useful to thermophilic corrosion-resistance.But, because the price of Co is high, generally should not add too much, make it keep a suitable content to get final product.The desirable scope of Co content is between 6.0-10.0%.
Mo element and W element also are important solution strengthening elements, content be controlled at respectively less than 1.0% and 4.0-8.0% between, obviously harmful to the anti-oxidant of alloy and sulfuration when excessive adding, and possibly be unfavorable for processing characteristics.
The Nb element is strengthening element and a grain-size control element important in the alloy of the present invention between 0.8-1.3%.As the precipitation strength element, (Ti, Nb) C as grain stabilizer, control grain-size to Nb and Ti and C reaction formation primary carbide when hot-work on the other hand with the Ti element for one side and Al.Simultaneously, excessive N b reduces the protective value of sull.
Al is the key element of alloy of the present invention, and not only because Al is of value to anti-oxidant, and it forms γ ' strengthening phase with Ti and Nb with Ni.Al content is limited between the 0.6-1.0%.Too high Al content will significantly reduce plasticity, stability and the toughness of alloy, reduce the processing temperature scope of alloy.Simultaneously, in high temperature vulcanized environment, also because high Al content causes interior oxidation and sulphur corrosion to increase.
The Ti element is a kind of important strengthening element between 0.3-0.7%.The Ti element also is important grain size stabilized agent simultaneously, forms primary carbide (Ti, Nb) C with Nb.Oxidation in will taking place easily during the Ti too high levels and cause reducing the plasticity of alloy substrate.
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 0.5%, is higher than this content, will in sull, form MnCr
2O
4The spinel phase, thus Cr reduced
2O
3The protective value of film.
The Si element is the important element among the present invention, because Si is finally at Cr
2O
3The following formation SiO of protective membrane
2Layer improves antioxidant and curability, and Si content is being effectively below 0.5%, and excessive Si will cause alloy to form other phases at crystal boundary, and influence plasticity, toughness and the working ability of alloy.
The Fe element reduces the high-temperature corrosion resistance performance of alloy, forms FeCr with the Cr sull on surface after its oxidation
2O
4Spinel reduces Cr mutually
2O
3Integrity, therefore, Fe content should remain on below 1.0%.
The Zr element between 0.1-0.4% and B element (less than 0.003%) help to keep the hot strength and the rupture ductility of alloy together.The excessive of these elements will cause crystal boundary liquefaction and significantly reduce the hot-work ability.The Zr element also obviously is increased in the adhesive capacity of alloy surface protective oxide film under cyclic oxidation/etching condition in above-mentioned scope.
C should remain on below 0.04%, 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 most important matrix component of Ni element, in order to guarantee phase stability, enough hot strength, plasticity, toughness and good working ability, its content must remain on more than 50%.
Alloy of the present invention can be through conventional smelting process preparation, and preferably smelting program is being carried out var or esr for carrying out vacuum induction melting earlier, reduces impurity element and melting defective as far as possible, and reduces the segregation of alloying element.Afterwards, carry out the alloying element homogenizing annealing.Carry out solution treatment and ageing treatment behind the thermo forming again.Fig. 1-5 is the detected result of the nickel-base alloy 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, microstructure analysis result and the differing temps respectively.
Usually, alloy of the present invention is particularly useful for making the valve of large-scale diesel engine mover, and vapor temperature reaches 700 ℃ ultra supercritical coal-fired plant boiler pipe etc. and is operated in the high-temperature bearing parts 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 (20.0-26.0%); Through limiting the scope of some alloy elements, less than 1.0%, W content is between 4.0-8.0% like Mo content; Fe content is less than 1.0%, and C is less than 0.04%, in the alloying element scope of above-mentioned qualification; Can obtain enough anti-oxidant/curabilities, 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 logical balance of adjusting precipitation-hardening element nb, Ti, Al of alloy of the present invention obtains nearly 10% strengthening phase on the matrix of nickel.The excessive adding of strengthening element has improved plasticity and toughness, keeps intensity and corrosion resistance nature again.
Description of drawings
Fig. 1 be in the scope of the invention nickel-base alloy from room temperature to pyritous tensile strength with the ys curve.
Fig. 2 be in the scope of the invention nickel-base alloy from room temperature to pyritous stretching plastic curve.
Fig. 3 is the pattern of the age hardening phase γ ' in the nickel-base alloy in the scope of the invention.
Fig. 4 is the microstructure image of nickel-base alloy in the scope of the invention.
Fig. 5 is the high-temperature oxidation resistant kinetic curve of nickel-base alloy in the scope of the invention.
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 nickel plate, ferrotungsten, molybdenum-iron, ferro-cobalt, 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; To wrap with sheet iron less than the composite inoculating nucleating agent that the particulate state ferro-niobium below the 12mm, zirconium, lanthanum (La) or REE (Re) magnesium-rare earth 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;
(3) molten steel that bag endomorphism inoculation crosses be will pass through and foundry goods or consumable electrode in sand mold or metal mold, poured into, 1400～1450 ℃ of melt cast temperature;
(4) 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.
(5) alloying element homogenizing annealing.Carry out solution treatment and ageing treatment behind the thermo forming again.
High strength anti-corrosion nickel-base alloy chemical ingredients is seen table 1.
Table 1 high strength anti-corrosion nickel-base alloy chemical ingredients (weight percent)
Claims (8)
1. high strength anti-corrosion nickel-bass alloy material and method of manufacture thereof is characterized in that, in mass percent, contain: carbon (C),＜0.04%; Chromium (Cr), 20.0%-26.0%; Cobalt (Co), 6.0%-10.0%; Tungsten (W), 4.0%-8.0%; Molybdenum (Mo),＜1.0%; Iron (Fe),＜1.0%; Silicon (Si),＜0.5%; Manganese (Mn),＜0.5%; Niobium (Nb), 0.8-1.3%; Titanium (Ti), 0.3%-0.7%; Aluminium (Al), 0.6%-1.0%; Zirconium (Zr), 0.1%-0.4%; Boron (B),＜0.001%; And the lanthanum (La) or the REE (Re) that can contain trace, surplus is the unavoidable impurities element in nickel (Ni) and the smelting process; Its manufacturing technology steps is:
(1) steel scrap, ferrochrome are melted in electric furnace; The molten clear back of molten steel adds nickel plate, ferrotungsten, molybdenum-iron, ferro-cobalt, 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; To wrap with sheet iron less than the composite inoculating nucleating agent that the particulate state ferro-niobium below the 12mm, zirconium, lanthanum (La) or REE (Re) magnesium-rare earth 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;
(3) molten steel that bag endomorphism inoculation crosses be will pass through and foundry goods or consumable electrode in sand mold or metal mold, poured into, 1400～1450 ℃ of melt cast temperature;
(4) 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;
(5) alloying element homogenizing annealing; Carry out solution treatment and ageing treatment behind the thermo forming again.
2. a kind of high strength anti-corrosion nickel-bass alloy material according to claim 1, it contains the chromium (Cr) of (in quality %) 22-24%.
3. a kind of high strength anti-corrosion nickel-bass alloy material according to claim 1 and method of manufacture thereof, it contains the tungsten (W) of (in quality %) 4.0-7.0%.
4. a kind of high strength anti-corrosion nickel-bass alloy material according to claim 1 and method of manufacture thereof, it contains the molybdenum (Mo) of (in quality %)＜0.8%.
5. a kind of high strength anti-corrosion nickel-bass alloy material according to claim 1 and method of manufacture thereof, it contains the silicon (Si) of (in quality %)＜0.3%.
6. a kind of high strength anti-corrosion nickel-bass alloy material according to claim 1 and method of manufacture thereof, it contains the niobium (Nb) of (in quality %) 0.9-1.1%, the titanium (Ti) of 0.4-0.6% and the aluminium (Al) of 0.7-0.9%.
7. a kind of high strength anti-corrosion nickel-bass alloy material according to claim 1 and method of manufacture thereof, it contains the boron (B) of (in quality %)＜0.002%.
8. a kind of high strength anti-corrosion nickel-bass alloy material according to claim 1 and method of manufacture thereof, it contains the zirconium (Zr) of (in quality %) 0.2-0.4%.
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