CN105132701A - Slag system used for preparing nickel base alloy through electroslag remelting and use method of slag system - Google Patents
Slag system used for preparing nickel base alloy through electroslag remelting and use method of slag system Download PDFInfo
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Abstract
The invention provides a slag system used for preparing a nickel base alloy through electroslag remelting and a use method of the slag system. The slag system comprises, by mass, 65%-70% of CaF2, 10%-16% of Al2O3, 10%-16% of CaO, 2%-5% of MgO, 2%-5% of TiO2 and not more than 0.8% of impurities. When the slag system is used, prepared slag is baked and then added to an argon-shielded electric slag furnace crystallizer to be melted, then 700 DEG C advanced ultra-supercritical coal fired boiler nickel base alloy is remelted, and slow cooling and mold stripping are conducted after remelting. According to the slag system used for preparing the nickel base alloy through electroslag remelting and the use method of the slag system, burning losses of easily-oxidized elements in the alloy can be effectively reduced, the head and tail distribution of the alloy can be uniform, the segregation degree of elements is reduced, and the surface quality problem of electroslag remelting can be effectively solved.
Description
Technical field
The present invention relates to a kind of electroslag remelting slag, particularly the slag system of the advanced ultra supercritical coal firing boiler nickel-base alloy of a kind of esr 700 DEG C and using method thereof.
Background technology
700 DEG C of advanced ultra supercritical coal firing boilers require that vapor pressure reaches 35Mpa, superheater and reheater temperature and reaches more than 700 DEG C and 720 DEG C respectively.Therefore, under this exacting terms, the austenitic heat-resistance steels such as 600 DEG C of ultra supercritical coal firing boilers Super304H, HR3C cannot meet actual requirement, thus superheater and reheater high temperature section must use nickel-bass alloy material.
The candidate material that the nickel-base alloys such as Inconel740, GH4700 use as 700 DEG C of advanced ultra supercritical coal firing boilers, its purity must improve further, could meet the enduring quality of New-type boiler to material and the actual requirement of corrosion resisting property.Due to electroslag remelting technique, to have technology and equipment relatively simple, technique suitability is strong, the advantages such as the metal produced is pure, inclusion is few, dense structure, therefore esr is the important smelting process of 700 DEG C of advanced ultra supercritical coal firing boiler nickel-base alloys.
But, in the esr process of 700 DEG C of advanced ultra supercritical coal firing boiler nickel-base alloys, often there is the oxidizable melting loss of elements such as Al, Ti and problem pockety end to end, its burn out rate is generally up to more than 15%, both easily caused ingot casting off analysis and alloy structure performance uneven, be also unfavorable for economizing on resources and reducing costs.Meanwhile, for the nickel-base alloy containing the easy segregation element such as Nb, Ti, in process of setting, dendritic segregation is comparatively serious, and the segregation coefficient maximum value of individual element even more than 4, can often cause the generation of harmful phase.In addition, because this type of nickel-base alloy interalloy kind is more, thus fusing point is low, if slag system is selected improper, then steel ingot is cast and easily occurred surface quality problems afterwards.
Slag system has vital effect in esr process, 70%CaF conventional at present
2+ 30%A1
2o
3and 60%CaF
2+ 20%A1
2o
3the slag systems such as+20%CaO are in esr 700 DEG C advanced ultra supercritical coal firing boiler nickel-base alloy process, and the problems referred to above are not effectively solved, and thus metallurgical quality is unsatisfactory.
Summary of the invention
In order to solve 700 DEG C of existing slag system Problems existing of advanced ultra supercritical coal firing boiler nickel-base alloy esr, exemplary embodiment of the present invention provides a kind of esr 700 DEG C advanced ultra supercritical coal firing boiler nickel-base alloy slag system.Described slag system can reduce the burn out rate of the oxidizable element such as Al, Ti, and makes it be evenly distributed end to end.In addition, described nickel-base alloy slag system can also alleviate the segregation degree of the easy segregation element such as Nb, Ti, eliminates harmful phase.
According to an aspect of the present invention, provide a kind of esr 700 DEG C advanced ultra supercritical coal firing boiler nickel-base alloy slag system, its chemical composition comprises by mass percentage: CaF
2: 65% ~ 70%, A1
2o
3: 10% ~ 16%, CaO:10% ~ 16%, MgO:2% ~ 5%, TiO
2: 2% ~ 5%, all the other are impurity, and wherein, the content of impurity is not more than 0.8%, and SiO in impurity
2≤ 0.4%, that is, in impurity, SiO
2content be less than or equal to 0.4% of slag system total mass.
According to exemplary embodiment of the present invention, the temperature of fusion of described esr 700 DEG C advanced ultra supercritical coal firing boiler nickel-base alloy slag system can be 1225 DEG C ~ 1240 DEG C.
According to exemplary embodiment of the present invention, the resistivity of described esr 700 DEG C advanced ultra supercritical coal firing boiler nickel-base alloy slag system when 1600 DEG C of temperature can be 0.24 Ω cm ~ 0.28 Ω cm, and viscosity is 0.03Pas ~ 0.05Pas.
According to a further aspect in the invention, provide a kind of method using esr 700 DEG C advanced ultra supercritical coal firing boiler nickel-base alloy slag system, said method comprising the steps of:
(1) adopt starting material fine fodder to prepare burden, to make slag charge, wherein, the chemical composition of the slag charge made comprises by mass percentage: CaF
2: 65% ~ 70%, A1
2o
3: 10% ~ 16%, CaO:10% ~ 16%, MgO:2% ~ 5%, TiO
2: 2% ~ 5%, all the other are impurity, and wherein, the content of impurity is not more than 0.8%, and SiO in impurity
2≤ 0.4%;
(2) the abundant mix and blend of slag charge will prepared, then put into roaster and be heated to 750 DEG C, afterheat baking is 5h at least, ready access upon use;
(3) slag charge good for afterheat baking is joined in argon shield crystallizer for electroslag furnace equably by feeder carry out heating slagging operation, wherein, argon flow amount is 5NL/min ~ 8NL/min, and changing slag voltage is 33V ~ 38V, and changing slag electric current is 5800A ~ 6500A;
(4) after slag charge fusing, at the advanced ultra supercritical coal firing boiler nickel-base alloy of argon shield electroslag refusion in the stove 700 DEG C, wherein, argon flow amount is 5NL/min ~ 8NL/min, and remelting voltage is 40V ~ 45V, and melting current is 7500A ~ 8000A; Molten speed is determined by crystallizer for electroslag furnace size: v=(0.7 ~ 0.8) D, wherein: v: molten speed, kg/h; D: crystallizer for electroslag furnace diameter, mm;
(5), after esr terminates, the depanning of nickel-base alloy Slow cooling is made, mould cool time at least 1 hour.
The mentality of designing of the esr that exemplary embodiment according to the present invention provides 700 DEG C advanced ultra supercritical coal firing boiler nickel-base alloy slag system is as described below:
Slag system is with CaF
2for base, contribute to the fusing point of reduction slag, viscosity and surface tension.Meanwhile, because its specific conductivity is higher, high CaF is therefore kept
2content can obtain the slag system of low-resistivity, is conducive to suitably reducing slag temperature and electrode melting speed and increases solidified front thermograde, thus reducing dendrite interval, alleviate element segregation degree and eliminate harmful phase.Therefore, by CaF
2content control 65% ~ 70%.
A1
2o
3obviously can reduce the specific conductivity of slag, namely improve the resistivity of slag, thus significantly can reduce power consumption, cost-saving.But A1
2o
3the fusing point of slag and viscosity can be made to raise, and meanwhile, in order to alleviate element segregation degree, its content can not be too high.Therefore, by A1
2o
3content control 10% ~ 16%.
CaO can increase the basicity of slag, is conducive to esr desulfurization; But its water-absorbent is comparatively strong, easily brings hydrogen and oxygen in alloy.Therefore, the content of CaO is controlled 10% ~ 16%.
MgO can prevent from appraising at the current rate oxide compound in slag bath oxygen uptake and slag to metal pool oxygen supply, but easily makes the viscosity of slag improve.Therefore, the content of MgO is controlled 2% ~ 5%.
TiO
2can suppress the scaling loss of Ti in titaniferous nickel-base alloy, but it is the oxide compound that appraises at the current rate, oxygen supply can be transmitted to metal pool.Therefore, by TiO
2content controls 2% ~ 5%.
In addition, this slag system is with CaF
2-Al
2o
3-CaO slag system is base, due at w (CaF
2)=65% ~ 70% and w (CaO): w (Al
2o
3) ≈ 1:1 place is the cold zone of this ternary phase diagrams, the temperature of fusion of this slag system thus designed as base is minimum reaches 1225 DEG C, can meet the requirement lower than nickel-base alloy fusing point 100 DEG C ~ 150 DEG C, is conducive to obtaining good esr surface quality.
The advanced ultra supercritical coal firing boiler nickel-base alloy slag system of the esr that exemplary embodiment according to the present invention provides 700 DEG C and using method thereof, effectively can not only reduce the scaling loss of oxidizable element and make it be evenly distributed end to end, the segregation degree of easy segregation element can also be alleviated, eliminate the harmful phase in nickel-base alloy.Meanwhile, slag system temperature of fusion is mated well with 700 DEG C of advanced ultra supercritical coal firing boiler nickel-base alloy fusing points, can effectively solve esr surface quality problems.
Embodiment
embodiment 1
The chemical composition of the esr 700 DEG C advanced ultra supercritical coal firing boiler nickel-base alloy slag system of the present embodiment comprises by mass percentage: CaF
2: 68.3%, A1
2o
3: 13%, CaO:12%, MgO:3%, TiO
2: 3%, all the other are impurity, wherein, SiO
2content account for 0.32% of the total content of nickel-base alloy slag system.The temperature of fusion of described nickel-base alloy slag system is 1228 DEG C; At 1600 DEG C of temperature, the resistivity of described nickel-base alloy slag system is 0.25 Ω cm, and viscosity is 0.036Pas.
The advanced ultra supercritical coal firing boiler nickel-base alloy of esr 700 DEG C is Inconel740, and this alloy melting point is 1288 DEG C ~ 1362 DEG C.Crystallizer diameter is 280mm, and slag charge quality is 24kg.
The concrete using method of described nickel-base alloy slag system is as follows:
(1) starting material fine fodder is adopted to prepare burden according to the slag charge composition of above-mentioned setting; The chemical composition of the slag charge made is comprised by weight percentage: CaF
2: 68.3%, A1
2o
3: 13%, CaO:12%, MgO:3%, TiO
2: 3%, all the other are impurity, wherein, SiO
2content account for 0.32% of the total content of nickel-base alloy slag system;
(2) by the abundant mix and blend of the described slag charge prepared, then put into roaster and be heated to 750 DEG C, afterheat baking 6h, ready access upon use;
(3) evenly join in argon shield crystallizer for electroslag furnace by slag charge good for afterheat baking by feeder, wherein, argon flow amount is 6NL/min, and changing slag voltage is 35V, and changing slag electric current is 6200A.
(4) after slag charge fusing, at argon shield electroslag refusion in the stove Inconel740 alloy, wherein, argon flow amount is 6NL/min, and remelting voltage is 43V, and melting current is 7800A, and molten speed is 210kg/h;
(5), after esr terminates, by the depanning of Inconel740 alloy Slow cooling, mould cool time is 2 hours.
Carry out chemical composition analysis to oxidizable element ti, Al content in the Inconel740 alloy ESR ingot produced, its result is as shown in table 1.As can be seen from Table 1, in ESR ingot, the deviation end to end of Ti, Al content only has 0.08% and 0.04% respectively, and namely deviation is less end to end, and visible Ti, Al distribute relatively even end to end.In addition, the average burn out rate of Ti, Al is respectively 7.65% and 6.12%, and thus the rate of recovery is higher.
Ti, Al content in table 1:Inconel740 alloy ESR ingot
| Element | ESR ingot head | ESR ingot afterbody | Deviation end to end | Mean value | Consumable electrode | Average burn out rate |
| Ti(wt％) | 1.85 | 1.77 | 0.08 | 1.81 | 1.96 | 7.65％ |
| Al(wt％) | 0.94 | 0.90 | 0.04 | 0.92 | 0.98 | 6.12％ |
Carry out detection computations to the segregation coefficient of segregation element Nb easy in Inconel740 alloy ESR ingot, Ti, result is as shown in table 2.As can be seen from Table 2, in ESR ingot, the segregation coefficient of Nb, Ti is all less than 2, and finds no harmful phase in microtexture, and thus element segregation controls better.
The segregation coefficient of Nb, Ti in table 2Inconel740 alloy ESR ingot
| Element | Nb | Ti |
| The massfraction (%) of interdendritic element | 2.77 | 2.32 |
| The massfraction (%) of the dry element of dendrite | 1.41 | 1.28 |
| Segregation coefficient | 1.96 | 1.81 |
After carrying out quality test to Inconel740 alloy ESR ingot, ingot body surface finds no the surface quality problems such as slag runner, corrugated and waistband shape defect, the mixing of slag gold.
embodiment 2
The chemical composition of the esr 700 DEG C advanced ultra supercritical coal firing boiler nickel-base alloy slag system of the present embodiment comprises by mass percentage:
CaF
2: 66.2%, A1
2o
3: 14%, CaO:14%, MgO:3%, TiO
2: 2%, all the other are impurity, wherein, SiO
2content account for 0.36% of nickel-base alloy slag system total content.The temperature of fusion of described nickel-base alloy slag system is 1233 DEG C; At 1600 DEG C of temperature, the resistivity of described nickel-base alloy slag system is 0.26 Ω cm, and viscosity is 0.041Pas.
The advanced ultra supercritical coal firing boiler nickel-base alloy of esr 700 DEG C is GH4700, and this alloy melting point is 1298 DEG C ~ 1370 DEG C.Crystallizer diameter is 350mm, and slag charge quality is 38kg.
The concrete using method of described nickel-base alloy slag system is as follows:
(1) adopt starting material fine fodder to prepare burden according to the slag charge composition of above-mentioned setting, wherein, the chemical composition of described nickel-base alloy slag system comprises by mass percentage: CaF
2: 66.2%, A1
2o
3: 14%, CaO:14%, MgO:3%, TiO
2: 2%, all the other are impurity, wherein, SiO
2content account for 0.36% of nickel-base alloy slag system total content.；
(2) the abundant mix and blend of slag charge will prepared, then puts into roaster and is heated to 750 DEG C, afterheat baking 5h, ready access upon use;
(3) evenly join in argon shield crystallizer for electroslag furnace by slag charge good for afterheat baking by feeder, argon flow amount is 6NL/min, and changing slag voltage is 36V, and changing slag electric current is 6300A.
(4) after slag charge fusing, at argon shield electroslag refusion in the stove GH4700 alloy, wherein, argon flow amount is 6NL/min, and remelting voltage is 45V, and melting current is 7900A, and molten speed is 245kg/h.
(5), after esr terminates, by the depanning of GH4700 alloy Slow cooling, mould cool time is 1.5 hours.
Carry out chemical composition analysis to the content of the oxidizable element ti in GH4700 alloy ESR ingot, Al, its result is as shown in table 3.As can be seen from Table 3, the deviation end to end of Ti, Al content in ESR ingot only has 0.04%, and namely deviation is less end to end, and visible Ti, Al are evenly distributed end to end.In addition, the average burn out rate of Ti, Al is respectively 5.08% and 5.41%, and thus the rate of recovery is higher.
Ti, Al content in table 3GH4700 alloy ESR ingot
| Element | ESR ingot head | ESR ingot afterbody | Deviation end to end | Mean value | Consumable electrode | Average burn out rate |
| Ti(wt％) | 1.70 | 1.66 | 0.04 | 1.68 | 1.77 | 5.08％ |
| Al(wt％) | 1.42 | 1.38 | 0.04 | 1.40 | 1.48 | 5.41％ |
Carry out detection computations to the segregation coefficient of the easy segregation element Nb in GH4700 alloy ESR ingot, Ti, result is as shown in table 4.As can be seen from Table 4, in ESR ingot, the segregation coefficient of Nb, Ti is all less than 2, and finds no harmful phase in microtexture, and thus element segregation controls better.
The segregation coefficient of Nb, Ti in table 4GH4700 alloy ESR ingot
| Element | Nb | Ti |
| The massfraction (%) of interdendritic element | 2.16 | 2.12 |
| The massfraction (%) of the dry element of dendrite | 1.16 | 1.25 |
| Segregation coefficient | 1.86 | 1.70 |
After carrying out quality test to GH4700 alloy ESR ingot, ingot body surface finds no the surface imperfection such as slag runner, corrugated and waistband shape defect, the mixing of slag gold.
Claims (5)
1. esr prepares a slag system for nickel-base alloy, it is characterized in that, the chemical composition of described slag system comprises by mass percentage: CaF
2: 65% ~ 70%, Al
2o
3: 10% ~ 16%, CaO:10% ~ 16%, MgO:2 ~ 5%, TiO
2: 2 ~ 5%, all the other are impurity, and wherein, the content of impurity is not more than 0.8%, and SiO in impurity
2≤ 0.4%.
2. slag system according to claim 1, is characterized in that, the temperature of fusion of described slag system is 1225 DEG C ~ 1240 DEG C.
3. nickel-base alloy slag system according to claim 1, is characterized in that, the resistivity of described slag system 1600 DEG C time is 0.24 Ω cm ~ 0.28 Ω cm.
4. nickel-base alloy slag system according to claim 1, is characterized in that, the viscosity of described slag system 1600 DEG C time is 0.03Pas ~ 0.05Pas.
5. use esr to prepare a method for the slag system of nickel-base alloy, it is characterized in that, said method comprising the steps of:
(1) adopt starting material fine fodder to prepare burden, to make slag charge, wherein, slag charge chemical composition comprises by mass percentage: CaF
2: 65% ~ 70%, Al
2o
3: 10% ~ 16%, CaO:10% ~ 16%, MgO:2% ~ 5%, TiO
2: 2% ~ 5%, all the other are impurity, and wherein, the content of impurity is not more than 0.8%, and SiO in impurity
2≤ 0.4%;
(2) the abundant mix and blend of slag charge will prepared, then put into roaster and be heated to 750 DEG C, afterheat baking is 5h at least, ready access upon use;
(3) slag charge good for afterheat baking is joined in argon shield crystallizer for electroslag furnace equably by feeder carry out heating slagging operation, wherein, argon flow amount is 5NL/min ~ 8NL/min, and changing slag voltage is 33V ~ 38V, and changing slag electric current is 5800A ~ 6500A;
(4) after slag charge fusing, at the advanced ultra supercritical coal firing boiler nickel-base alloy of argon shield electroslag refusion in the stove 700 DEG C, wherein, argon flow amount is 5NL/min ~ 8NL/min, and remelting voltage is 40V ~ 45V, and melting current is 7500A ~ 8000A; Molten speed is determined by crystallizer for electroslag furnace size: v=(0.7 ~ 0.8) D, wherein: v: molten speed, kg/h; D: crystallizer for electroslag furnace diameter, mm;
(5), after esr terminates, the depanning of nickel-base alloy Slow cooling is made, mould cool time at least 1 hour.
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| CN105734302A (en) * | 2016-04-29 | 2016-07-06 | 重庆钢铁(集团)有限责任公司 | GH4169 alloy steel electroslag remelting refining slag and method for performing electroslag re-melting on GH4169 alloy steel |
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| CN108342586A (en) * | 2018-03-28 | 2018-07-31 | 东北大学 | A kind of slag system and its application method for smelting GH984G nickel-base alloys |
| CN108728662A (en) * | 2018-06-14 | 2018-11-02 | 湖州久立永兴特种合金材料有限公司 | A kind of N06625 nickel-base alloys electro-slag re-melting method and the slag system used |
| CN108728662B (en) * | 2018-06-14 | 2020-02-18 | 湖州久立永兴特种合金材料有限公司 | Electroslag remelting method for N06625 nickel-based alloy and slag system used by electroslag remelting method |
| CN108715939A (en) * | 2018-07-06 | 2018-10-30 | 抚顺特殊钢股份有限公司 | A kind of electric slag refusion and smelting technique of the N06625 alloys of high-purity segregation-free |
| CN109554558A (en) * | 2018-11-26 | 2019-04-02 | 抚顺特殊钢股份有限公司 | A kind of GH738 alloy electroslag smelting technique |
| CN110004301A (en) * | 2019-04-26 | 2019-07-12 | 辽宁辽重新材有限公司 | A kind of Large Ultra-Supercritical rotor steel FB2 electroslag production technology |
| CN110004301B (en) * | 2019-04-26 | 2021-04-16 | 辽宁辽重新材有限公司 | FB2 electroslag production process for large ultra-supercritical rotor steel |
| CN110331301B (en) * | 2019-06-25 | 2021-03-09 | 河钢股份有限公司 | Method for remelting hastelloy by electroslag |
| CN110331301A (en) * | 2019-06-25 | 2019-10-15 | 河钢股份有限公司 | A kind of method of electroslag remelting Hastelloy |
| CN110938745A (en) * | 2019-11-19 | 2020-03-31 | 河南中原特钢装备制造有限公司 | 825 nickel-based alloy electroslag remelting slag system and preparation method thereof |
| CN110846515A (en) * | 2019-11-21 | 2020-02-28 | 重庆材料研究院有限公司 | Preparation method of nickel-based alloy 690 with ultralow gas content |
| CN111394591A (en) * | 2020-04-16 | 2020-07-10 | 江苏星火特钢有限公司 | Slag system for electroslag remelting high-temperature alloy and use method |
| CN111394591B (en) * | 2020-04-16 | 2022-03-15 | 江苏星火特钢集团有限公司 | Slag system for electroslag remelting high-temperature alloy and use method |
| CN113584381A (en) * | 2021-07-05 | 2021-11-02 | 重庆材料研究院有限公司 | High-strength copper-containing Ni-Fe-Cr-based age hardening type corrosion-resistant alloy and electroslag remelting method thereof |
| CN113584381B (en) * | 2021-07-05 | 2023-03-07 | 重庆材料研究院有限公司 | High-strength copper-containing Ni-Fe-Cr-based age-hardening corrosion-resistant alloy and electroslag remelting method thereof |
| CN115287463A (en) * | 2022-06-15 | 2022-11-04 | 东北大学 | Slag system for electroslag remelting N06625 nickel-based alloy welding material, preparation method and use method |
| CN115287463B (en) * | 2022-06-15 | 2024-05-17 | 东北大学 | Slag system for electroslag remelting N06625 nickel-based alloy welding material, preparation method and use method |
| CN117305611A (en) * | 2023-11-27 | 2023-12-29 | 成都先进金属材料产业技术研究院股份有限公司 | Nickel-copper alloy electroslag remelting method |
| CN117305611B (en) * | 2023-11-27 | 2024-03-26 | 成都先进金属材料产业技术研究院股份有限公司 | Nickel-copper alloy electroslag remelting method |
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