CN100415926C - Microalloyed nickel chromium high-temperature alloy material and method for preparing the same - Google Patents
Microalloyed nickel chromium high-temperature alloy material and method for preparing the same Download PDFInfo
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Abstract
The present invention discloses a micro-alloyed nickel chromium high-temperature alloy material and a preparation method thereof. The present invention is characterized in that the present invention contains the following chemical components: 0.45 to 0.5% of carbon, 1.6 to 2.0% of silicon, 0.8 to 1.2% of manganese, less than 0.03% of phosphorus, less than 0.025% of sulfur, 24 to 27% of chromium, 33 to 36% of nickel, less than 0.5% of molybdenum, less than 0.35% of tungsten, 0.8 to 1.0% of niobium, 0.05 to 0.1% of titanium, 0.02 to 0.03% of boron, 0.03 to 0.05% of zirconium, 0.01 to 0.1% of cerium and the rest of ferrum. The present invention is made in the processing steps of compounding, a melting period, a reduction period, tapping, micro-alloying treatment, etc.; the present invention has the advantage of good high temperature property and can satisfy the requirements of various working conditions. Manufactured products of the present invention has the advantages of stable quality and favorable performance and the qualified rate of the products can reach more than 98.5 percent.
Description
Technical field:
The present invention relates to alloy technology, is nickel chromium high-temperature alloy material of a kind of microalloying processing and preparation method thereof specifically, and it has higher anticorrosive, impervious carbon and creep rupture strength.
Background technology:
Nickel chromium high-temperature alloy is mainly used in petrochemical complex, metallurgy and heat treatment industry, and the subject matter that exists is that corrosion resistance nature, antioxidant property, anti-carburizing energy and high temperature creep strength can not satisfy the service requirements that improves day by day at present.
Summary of the invention:
The objective of the invention is to overcome the deficiency of above-mentioned prior art, and the nickel chromium high-temperature alloy material that provides a kind of microalloying to handle.
Another object of the present invention provides a kind of preparation method of nickel chromium high-temperature alloy material of microalloying processing.
Corrosion resistance nature, antioxidant property, anti-carburizing energy and the high temperature creep strength that the present invention has mainly solved existing nickel chromium high-temperature alloy can not satisfy the problem of service requirements.
In order to reach above-mentioned purpose, the present invention is achieved in that the nickel chromium high-temperature alloy material that microalloying is handled, its special character is that it contains following chemical ingredients, carbon 0.45-0.5%, silicon 1.6-2.0%, manganese 0.8-1.2%, phosphorus less than 0.03%, sulphur less than 0.025%, chromium 24-27%, nickel 33-36%, molybdenum less than 0.5%, tungsten less than 0.35%, niobium 0.8-1.0%, titanium 0.05-0.1%, boron 0.02-0.03%, zirconium 0.03-0.05%, cerium 0.01-0.1%, surplus be iron.
The preparation method of the nickel chromium high-temperature alloy material that microalloying of the present invention is handled, it comprises following processing step:
A, batching; Furnace charge mainly by this steel grade returns smaller or equal to 30%, all the other are pure nickel, carbon steel and ferrochrome, the average carbon content of furnace charge is allocated into by specification composition lower limit, the average phosphorus content of furnace charge and sulphur content all should be lower by 0.005%～0.010% than limiting the quantity of of specification composition, and the chromium of furnace charge and nickel content are allocated into by the lower limit of specification composition;
B; Melting period; Energising is earlier melted, and along with the fusing of bottom furnace charge, smashes material, and add furnace charge successively, after most of furnace charge fusing, add the slag making materials slag making and cover molten steel, under 1600 ℃ of-1650 ℃ of temperature, when 95% furnace charge is molten clear, get the steel sample and carry out total analysis, and remaining furnace charge is added in the stove, behind the furnace charge fine melt, reduce power, turndown is skimmed and is made new slag in addition;
C; Reduction period; Elder generation's deoxidation and adjustment composition, be transferred to peak power, add ferromanganese 80%Mn and ferrosilicon 75%Si deoxidation, and adjust silicon, manganese content, add low carbon ferrochromium and coke powder then and adjust chromium, carbon content, final deoxygenation and add ferro-niobium, molybdenum-iron, ferrotungsten etc. adds SiCa (60-40) alloy again, about add-on 0.3%, add ferro-niobium fusings such as (60%Nb) during 1650 ℃-1680 ℃ of molten steel temperatures;
D; Tapping and microalloying are handled; sampling and argon shield are fed in raw material out, and ladle is interior to be handled; after getting the steel sample in the stove and carrying out total analysis and adjust composition; reduce power; skim and with argon shield liquid level 2-3 minute; (35%Zr 50%Si), taps when being warming up to 1710 ℃ ± 10 ℃ to add the FeSiZr alloy; the sampling casting; when in waiting to wrap molten steel 1/4 being arranged, with pure titanium bits, metallic cerium, ferro-boron (24%B, granularity 2～3mm) adds with steel stream; finish during molten steel to 2/3 reinforced in the bag; evenly stir molten steel in the bag, sampling is analyzed eventually, and the casting of molten steel amount is determined in qualified back.
The preparation method of the nickel chromium high-temperature alloy material that microalloying of the present invention is handled, the slag making materials of the melting period of step b is a lime powder: Fluorspar Powder=1: 2, its add-on are 1.0-1.5%.
The present invention is based on domestic existing ZG40Ni35Cr25NbW standard of materials; take argon shield, circulating deoxidation melting technology; the interpolation of control Ti, Zr, microalloy elements such as Ce, B is handled; thereby material is handled through microalloying; form the nickel chromium high-temperature alloy material that microalloying is handled; realize crystal grain thinning, purification and reinforcement crystal boundary, increase the sticking power between protective membrane and matrix, thereby improve anticorrosive, the impervious carbon and the creep rupture strength of material.
The adding of Ti among the present invention, because the avidity of Ti and C is much larger than the avidity of Cr and C, therefore the affiliation that adds of Ti alleviates because of the carbide of Cr and separates out the intergranular corrosion that causes and near the poor chromium district the crystal boundary, and the carbide of the Ti that forms is more stable than the carbide of Cr, do not fusing below 1038 ℃, thereby playing good strengthening effect.
The adding of B can delay crystal boundary cracking and strong to the hot strength of austenitic stainless steel among the present invention, B can also suppress separating out of the M23C6 of crystal boundary place, though B solubleness in the Fe-Ni-Cr-Mo alloy is lower, but when lower concentration, B can replace partial C as interstitial element, forms M23 (C, B) 6, this increases the lattice parameter of carbide, thereby is mated preferably between the opposite face of carbide and austenitic matrix.It is 1150-1250 ℃ eutectic that but the B too high levels can form fusing point, produces red brittleness.
The Zr of trace can improve the creep rupture strength and the plasticity of alloy by purifying and strengthening crystal boundary.
Proper C e helps to stablize the Cr2O3 oxide compound, improves the tackiness of oxide film and matrix, reduces the rate of oxidation of alloy, and the resistance to high temperature oxidation that improves alloy is had unusual effect.
Its performance of nickel chromium high-temperature alloy material that the microalloying of embodiments of the invention 1 is handled is as follows: the contrast of normal temperature mechanical property:
The contrast of high temperature, short time mechanical property:
The contrast of high-temperature and durable mechanical property:
Compared with the prior art the nickel chromium high-temperature alloy material that a kind of microalloying of the present invention is handled has outstanding substance point and marked improvement, 1, constant product quality, product qualified rate reaches more than 98.5%, and the national levels such as delivering to metallurgic product quality supervision and test center, Hubei Province of taking a sample respectively detects the detection that normal temperature mechanical property, high temperature, short time mechanical property and high-temperature and durable mechanical property have been done by unit, the result proves, the high-temperature alloy furnace tube of the nickel chromium high-temperature alloy material that microalloying is handled is functional, and performance index reach the index of expection; 2, nickel chromium high-temperature alloy material and the boiler tube and the pipe fitting of microalloying processing have the good high-temperature performance under the high temperature, can satisfy the requirement of various operating modes.
Embodiment:
In order to understand better and to implement, describe nickel chromium high-temperature alloy material of a kind of microalloying processing of the present invention and preparation method thereof in detail below in conjunction with embodiment.
Embodiment 1, accurately takes by weighing following material: specification is the low carbon ferrochromium 125Kg of FeCr69C0.25, specification is the electrolytic nickel 115Kg of Ni99.90,30# carbon steel 90Kg, this steel grade returns 80Kg, specification is the ferro-niobium 4.8Kg of FeNb60, specification is the ferromanganese 5Kg of FeMn82C1.5, specification is the ferrosilicon 5.5Kg of FeSi75, specification is the silicocalcium 1Kg of Ca31Si60, specification is the ferrotungsten 0.6Kg of FeW80, specification is the zirconium silicon alloy 0.38Kg of FeSi50Zr35, specification is the ferro-aluminum 1Kg of FeMo70, coke powder 1.2Kg, titanium 0.28Kg, cerium 0.1Kg, specification is the ferro-boron 0.35Kg of FeB23; Add furnace charge then in neutral Medium Frequency Induction Heating Furnace, furnace charge is mainly this steel grade returns, electrolytic nickel, carbon steel and most of low carbon ferrochromium; Energising is earlier melted, when beginning to switch on, supply with about 60% power, treat that rush of current stops after, gradually power is increased to maximum value, along with the fusing of crucible bottom furnace charge, often smash material, prevent " bridging ", and add furnace charge successively, after most of furnace charge fusing, add the slag making materials slag making and cover molten steel, slag making materials is a lime powder: Fluorspar Powder=1: 2, its add-on is 1.5%, under 1600 ℃ of-1650 ℃ of temperature, when 95% furnace charge is molten clear, gets the steel sample and carry out total analysis, and with in remaining furnace charge adding stove, behind the furnace charge fine melt, reduce power, turndown is skimmed and is made new slag in addition; Elder generation's deoxidation and adjustment composition, be transferred to peak power, add ferromanganese and ferrosilicon deoxidation, and adjust silicon, manganese content, add remaining low carbon ferrochromium and coke powder then and adjust chromium, carbon content, final deoxygenation and add ferro-niobium, molybdenum-iron, ferrotungsten etc. adds silicocalcium more again, adds fusings such as ferro-niobium during 1650 ℃-1680 ℃ of molten steel temperatures; Sampling and argon shield are fed in raw material out and are handled in the ladle, after getting the steel sample in the stove and carrying out total analysis and adjust composition, reduce power; skim and with argon shield liquid level 2-3 minute, add the zirconium silicon alloy, tapping when being warming up to 1715 ℃; the sampling casting; when in waiting to wrap molten steel 1/4 being arranged, titanium, cerium, ferro-boron are added with steel stream, finish during molten steel to 2/3 reinforced in the bag; evenly stir molten steel in the bag; sampling is analyzed eventually, and molten steel amount 400Kg casts.
The nickel chromium high-temperature alloy material that aforesaid method makes, its chemical ingredients is as follows after testing, and carbon 0.452%, silicon 1.86%, manganese 1.08%, phosphorus 0.0295%, sulphur 0.024%, chromium 25.08%, nickel 34.71%, molybdenum 0.21%, tungsten 0.14%, niobium 0.82%, titanium 0.081%, boron 0.022%, zirconium 0.038%, cerium 0.031%, iron are less than 35.42%.
Embodiment 2, accurately take by weighing following material: specification is the low carbon ferrochromium 165Kg of FeCr69C0.25, specification is the electrolytic nickel 175Kg of Ni99.90,30# carbon steel 80Kg, this steel grade returns 80Kg, specification is the ferro-niobium 7.5Kg of FeNb60, specification is the ferromanganese 5.2Kg of FeMn82C1.5, specification is the ferrosilicon 5.7Kg of FeSi75, specification is the silicocalcium 1.3Kg of Ca31Si60, specification is the zirconium silicon alloy 0.5Kg of FeSi50Zr35, specification is the molybdenum-iron 1.7Kg of FeMo70, specification is the ferrotungsten 1.2Kg of FeW80, coke powder 2Kg, titanium 0.2Kg, cerium 0.2Kg, specification is the ferro-boron 0.5Kg of FeB23; Add furnace charge then in neutral Medium Frequency Induction Heating Furnace, furnace charge is mainly this steel grade returns, electrolytic nickel, carbon steel and most of low carbon ferrochromium; Energising is earlier melted, when beginning to switch on, supply with about 60% power, treat that rush of current stops after, gradually power is increased to maximum value, along with the fusing of crucible bottom furnace charge, often smash material, prevent " bridging ", and add furnace charge successively, after most of furnace charge fusing, add the slag making materials slag making and cover molten steel, slag making materials is a lime powder: Fluorspar Powder=1: 2, its add-on is 1.5%, under 1600 ℃ of-1650 ℃ of temperature, when 95% furnace charge is molten clear, gets the steel sample and carry out total analysis, and with in remaining furnace charge adding stove, behind the furnace charge fine melt, reduce power, turndown is skimmed and is made new slag in addition; Elder generation's deoxidation and adjustment composition, be transferred to peak power, add ferromanganese and ferrosilicon deoxidation, and adjust silicon, manganese content, add remaining low carbon ferrochromium and coke powder then and adjust chromium, carbon content, final deoxygenation and add ferro-niobium, molybdenum-iron, ferrotungsten etc. adds silicocalcium again, adds fusings such as ferro-niobium during 1650 ℃-1680 ℃ of molten steel temperatures; Sampling and argon shield are fed in raw material out and are handled in the ladle, after getting the steel sample in the stove and carrying out total analysis and adjust composition, reduce power; skim and with argon shield liquid level 2-3 minute, add the zirconium silicon alloy, tapping when being warming up to 1718 ℃; the sampling casting; when in waiting to wrap molten steel 1/4 being arranged, titanium, cerium, ferro-boron are added with steel stream, finish during molten steel to 2/3 reinforced in the bag; evenly stir molten steel in the bag; sampling is analyzed eventually, and molten steel amount 500Kg casts.
The nickel chromium high-temperature alloy material that aforesaid method makes, its chemical ingredients is as follows after testing, and carbon 0.462%, silicon 1.73%, manganese 1.18%, phosphorus 0.029%, sulphur 0.022%, chromium 25.87%, nickel 36.27%, molybdenum 0.23%, tungsten 0.18%, niobium 0.848%, titanium 0.081%, boron 0.024%, zirconium 0.035%, cerium 0.039%, iron are less than 33%.
Claims (4)
1. the nickel chromium high-temperature alloy material handled of microalloying, it is characterized in that it contains following chemical ingredients, carbon 0.45-0.5%, silicon 1.6-2.0%, manganese 0.8-1.2%, phosphorus less than 0.03%, sulphur less than 0.025%, chromium 24-27%, nickel 33-36%, molybdenum less than 0.5%, tungsten less than 0.35%, niobium 0.8-1.0%, titanium 0.05-0.1%, boron 0.02-0.03%, zirconium 0.03-0.05%, cerium 0.01-0.1%, surplus be iron.
2. the preparation method of the nickel chromium high-temperature alloy material handled of the described microalloying of claim 1, it comprises following processing step:
A batching: furnace charge mainly by this steel grade returns smaller or equal to 30%, all the other are pure nickel, carbon steel and ferrochrome, the average carbon content of furnace charge is allocated into by specification composition lower limit, the average phosphorus content of furnace charge and sulphur content all should be lower by 0.005%～0.010% than limiting the quantity of of specification composition, and the chromium of furnace charge and nickel content are allocated into by the lower limit of specification composition;
B melting period: energising is earlier melted, and along with the fusing of bottom furnace charge, smashes material, and add furnace charge successively, after most of furnace charge fusing, add the slag making materials slag making and cover molten steel, under 1600 ℃ of-1650 ℃ of temperature, when 95% furnace charge is molten clear, get the steel sample and carry out total analysis, and remaining furnace charge is added in the stove, behind the furnace charge fine melt, reduce power, turndown is skimmed and is made new slag in addition;
C reduction period: first deoxidation and adjustment composition, be transferred to peak power, add ferromanganese 80%Mn and ferrosilicon 75%Si deoxidation, and adjust silicon, manganese content, add low carbon ferrochromium and coke powder then and adjust chromium, carbon content, final deoxygenation and add ferro-niobium, molybdenum-iron, ferrotungsten adds the CaSi alloy that contains 40%Ca, 60%Si again, about add-on 0.3%, add the ferro-niobium fusing that contains 60%Nb during 1650 ℃-1680 ℃ of molten steel temperatures;
D tapping and microalloying are handled: sampling and argon shield are fed in raw material out, and ladle is interior to be handled; after getting the steel sample in the stove and carrying out total analysis and adjust composition; reduce power; skim and with argon shield liquid level 2-3 minute; add the FeSiZr alloy that contains 35%Zr, 50%Si; tapping when being warming up to 1710 ℃ ± 10 ℃; the sampling casting; when in waiting to wrap molten steel 1/4 being arranged; with pure titanium bits, metallic cerium with contain 24%B and the ferro-boron of granularity 2～3mm adds with steel stream, finish during molten steel to 2/3 reinforcedly in the bag, evenly stir molten steel in the bag; sampling is analyzed eventually, and the casting of molten steel amount is determined in qualified back.
3. the preparation method of the nickel chromium high-temperature alloy material that microalloying according to claim 2 is handled, the slag making materials that it is characterized in that the melting period of step b is a lime powder: Fluorspar Powder=1: 2, its add-on are 1.0-1.5%.
4. the preparation method of the nickel chromium high-temperature alloy material that microalloying according to claim 2 is handled is characterized in that described stove is neutral Frequency Induction Heating electric furnace.
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| CN103173692B (en) * | 2013-04-10 | 2016-05-25 | 刘少光 | High temperature alloy, the Alloy funnel cap that adopts this alloy manufacture and the manufacturing process of this blast cap |
| CN103409679B (en) * | 2013-07-30 | 2016-02-10 | 青岛新力通工业有限责任公司 | Zirconium, titanium micro-alloyed Adding Way in smelting process |
| CN106929739A (en) * | 2017-04-20 | 2017-07-07 | 天津达祥精密工业有限公司 | A kind of microalloying chromium nickel series austenite heat resisting steel and its preparation method and application |
| CN108531730A (en) * | 2018-04-10 | 2018-09-14 | 抚顺特殊钢股份有限公司 | The vacuum induction furnace smelting technique of lanthanum element recovery rate in a kind of raising high temperature alloy |
| CN110846550B (en) * | 2019-12-02 | 2021-08-24 | 抚顺特殊钢股份有限公司 | Intermediate frequency furnace smelting process for nitrogen-containing and niobium-containing high-temperature alloy |
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| US5021215A (en) * | 1989-01-30 | 1991-06-04 | Sumitomo Metal Industries, Ltd. | High-strength, heat-resistant steel with improved formability and method thereof |
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