CN112267029A - Smelting method for controlling element burning loss of nickel-based alloy electroslag ingot of high-aluminum titanium - Google Patents
Smelting method for controlling element burning loss of nickel-based alloy electroslag ingot of high-aluminum titanium Download PDFInfo
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Abstract
The invention provides a smelting method for controlling element burning loss of a high-aluminum titanium nickel-based alloy electroslag ingot, which adopts a mixture ratio of CaF265~72%，Al2O312~15%，CaO 12~15%，TiO21-5% of quaternary slag system, optimizes the electrical system of an electroslag remelting start stage, a smelting stage and a filling stage, and is suitable for smelting nickel-based high-temperature alloy electroslag ingots with the components of 13.0-16.0% of Co, 10.0-16.0% of Cr, 4.0-6.0% of W, 2.0-4.0% of Mo, 2.0-5.0% of Al, 1.5-3.7% of Ti, 0.7-1.5% of Nb, 0.01-0.015% of B, 0.005-0.045% of Zr, 0.02-0.05% of C and the balance of Ni and the diameter of 300-560 mm. The smelting method for controlling element burning loss of the high-aluminum-titanium nickel-based alloy electroslag ingot can be used for smelting high-aluminum-titanium nickel-based alloy electroslag ingotEffectively solves the problem of burning loss of aluminum and titanium elements at the head and the tail of the electroslag ingot.
Description
Technical Field
The invention belongs to the technical field of high-temperature alloy smelting, and particularly relates to a smelting method for controlling element burning loss of a high-aluminum-titanium nickel-based alloy electroslag ingot.
Background
The high-temperature alloy is a metal material which takes Fe, Ni and Co as matrixes and can work for a long time at a high temperature of more than 600 ℃ under the action of certain stress, and has the comprehensive properties of excellent high-temperature strength, good oxidation resistance, good hot corrosion resistance, good fatigue property, good fracture toughness and the like. Specifically, the nickel-based high-temperature alloy is prepared by taking Ni as a matrix and adding elements such as Co, Cr, W, Mo, Al, Ti, Nb, B, C, Zr and the like. Wherein, Al and Ti are important alloy elements in the nickel-base superalloy, and the Al and Ti elements and Ni element can form a strengthening phase gamma' phase with the chemical composition of Ni3(Al, Ti). For precipitation strengthening type nickel-base high-temperature alloy, the strengthening effect is mainly dependent on gamma' phase strengthening, and the strengthening effect is closely related to the content of Al and Ti elements in the alloy. The Al and Ti elements in the electroslag ingot are obviously burnt, so that on one hand, the mechanical property of the part is fluctuated, the technical index requirements cannot be met, and the qualification rate is influenced; on the other hand, the stability of batch quality is caused, and the service reliability is influenced. Therefore, the control of the contents of Al and Ti elements plays an important role in maintaining the properties of the nickel-base superalloy, particularly the precipitation-strengthened nickel-base superalloy.
Electroslag remelting is an important refining process of high-temperature alloy, and is a method for smelting by using resistance heat generated when current passes through slag as a heat source; the method aims to improve the metal purity, remove impurities, remove sulfur elements and improve the ingot casting crystal structure. The ingot for aerospace use with the high-quality high-temperature alloy with the diameter of less than 300mm can be prepared into a finished product ingot by adopting an electroslag remelting process. However, the ingot with the diameter of more than 300mm is remelted by electroslag, so that the burning loss of Al and Ti elements is more likely to occur. However, high Al and Ti alloys suffer from some degree of burnout during the electroslag remelting process, which in turn affects the consistency and stability of the alloy properties. The Al and Ti are active and easily-oxidized elements, the main component of the slag is a reducing oxide, and the Al and Ti elements and the oxide in the slag are subjected to reduction reaction in the remelting process, so that gradient change of the content of the Al and Ti elements occurs in the steel ingot along the longitudinal direction, and adverse effects such as mechanical property fluctuation, poor quality stability and the like are caused.
Therefore, there is a need to provide an improved technical solution to overcome the technical problems in the prior art.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a smelting method for controlling element burning loss of a high-aluminum-titanium nickel-based alloy electroslag ingot, which can effectively solve the problem of element burning loss of aluminum and titanium at the head and the tail of the electroslag ingot.
The first aspect of the invention provides a smelting method for controlling element burning loss of a nickel-based alloy electroslag ingot of high-aluminum titanium, which adopts a quaternary slag system to carry out electroslag remelting, wherein the quaternary slag system comprises CaF (calcium fluoride) in percentage by weight2 65～72％，Al2O3 12～15％，CaO 12～15％，TiO21-5%; the smelting method comprises a starting stage, a smelting stage and a filling stage. By the technical means, the proportion of the quaternary slag system is optimally designed, so that the slag system proportion is more suitable for smelting high-aluminum-titanium nickel-based high-temperature alloy electroslag ingots, and the element burning loss of aluminum and titanium can be effectively controlled.
Preferably, a smelting electrode and slag of the quaternary slag system are filled in an electroslag remelting furnace, and a nickel-based alloy electroslag ingot with high aluminum and titanium is prepared through the starting stage, the smelting stage and the filling stage; the starting stage adopts current control, and the current control adopts a stepless speed change mode to improve the current intensity: the initial current is 5000-10000A, the current is increased at the speed of 1000-3000A/min until the current intensity is 12000-17000A, and then the current is maintained for 10-30 min; and reducing the current to 10000-14000A at a speed of 100-300A/min. By the technical means, the electrical system of the electroslag ingot smelting starting stage is optimized, lower initial current is set and then is increased in a stepless speed change mode, the initial current is increased to a certain power and then is reduced in the stepless speed change mode, and the electroslag ingot smelting starting stage is started after moderate current is achieved. By adopting the electric system, the stability of the power of the initial stage of electroslag ingot smelting can be improved, and the burning loss of aluminum and titanium elements can be effectively avoided.
Preferably, the melting speed is controlled in the melting stage, the melting speed is 3.5-5.5 kg/min, the melting speed is reduced after 300-550 kg of the electrode remains, and the melting speed is adjusted at a speed of 0.5-1.5kg/min/h to 3.0-4.5 kg/min and then is maintained. By the technical means, the electrical system of the electroslag ingot smelting stage is optimized, the stability of the smelting stage can be improved by controlling the smelting speed, the smelting speed is reduced by adopting a stepless speed change mode at the later stage of the smelting stage, the power caused by greatly reducing the smelting speed after entering the filling stage can be greatly reduced, and further the burning loss of aluminum and titanium elements is avoided.
Preferably, the filling stage adopts melting speed control, and the melting speed is continuously reduced; and starting filling after 100-300 kg of the electrode is remained, adjusting the melting speed in the filling process according to the speed of 0.5-2.0kg/min/h until the melting speed is kept 2.0kg/min, and stopping melting after 15-45 kg of the electrode is remained. By adopting the technical means, the melting speed is reduced in a stepless speed change mode in the filling stage, and the burning loss of the aluminum and titanium elements caused by the fluctuation of the melting speed in the filling stage process can be avoided.
Preferably, the high-aluminum titanium nickel-based superalloy comprises the following components in percentage by weight: 13.0 to 16.0 Co, 10.0 to 16.0 Cr, 4.0 to 6.0W, 2.0 to 4.0 Mo, 2.0 to 5.0 Al, 1.5 to 3.7 Ti, 0.7 to 1.5 Nb, 0.01 to 0.015B, 0.005 to 0.045 Zr, 0.02 to 0.05C, and the balance Ni. By the technical means, the alloy components are suitable for the slag system proportion and the smelting method provided by the invention, and the high-performance nickel-based high-temperature alloy electroslag ingot for aerospace and gas turbines can be prepared.
Preferably, the diameter of the high-aluminum-titanium nickel-based superalloy electroslag ingot is 300-560 mm. By the technical means, the diameter of the alloy electroslag ingot is suitable for the slag system proportion and the smelting method provided by the invention. The electroslag ingot with the diameter meeting the requirement of high-performance nickel-based high-temperature alloy parts for aerospace and gas turbines can be prepared.
Preferably, in the smelting process by adopting the smelting method, the loss amount of the Al element is 3-6%, and the increase amount of the Ti element is 1-10%. By the technical means, the component uniformity of the head and the tail of the high-aluminum-titanium nickel-based high-temperature alloy electroslag ingot can be effectively controlled, and the quality stability of parts made of the electroslag ingot is ensured.
The second aspect of the invention provides a high-aluminum titanium nickel-based alloy prepared by the smelting method.
In a third aspect, the invention provides the application of the high-aluminum titanium nickel-based alloy in the fields of aerospace and energy.
The beneficial effects created by the invention are as follows:
the invention provides an optimized electroslag proportioning and smelting method of a quaternary slag system, which mainly adjusts Al in electroslag2O3With TiO2The reasonable proportion and the optimization of smelting process parameters inhibit the burning loss of Al and Ti elements in the smelting process of the 300-560 mm high-aluminum titanium nickel-based alloy electroslag ingot, and further improve the component uniformity of the electroslag ingot.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to these drawings without inventive effort.
FIG. 1 is a schematic view of an electroslag remelting process; wherein, 1 is an electrode, 2 is an electroslag ingot filling end (head), 3 is electroslag, 4 is an electroslag ingot, and 5 is an electroslag ingot starting end (tail).
Detailed Description
The experimental methods of the following examples, which are not specified under specific conditions, are generally determined according to national standards. If there is no corresponding national standard, it is carried out according to the usual international standards, to the conventional conditions or to the conditions recommended by the manufacturer.
The features mentioned with reference to the invention or the features mentioned with reference to the embodiments can be combined. All the features disclosed in this specification may be combined in any combination, and each feature disclosed in this specification may be replaced by alternative features serving the same, equivalent or similar purpose. Thus, unless expressly stated otherwise, the features disclosed are merely generic examples of equivalent or similar features.
In the present invention, all the technical features mentioned herein and preferred features may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, unless otherwise specified, the metallurgical electrode mentioned herein includes, but is not limited to, an electrode obtained by vacuum induction melting of a nickel-based superalloy component of high aluminum titanium.
In the present invention, unless otherwise specified, the initial weight of the smelting electrode mentioned herein includes, but is not limited to, 1500-2500 kg.
The electroslag remelting smelting method is suitable for smelting high-Ti and high-Al nickel-based high-temperature alloys, and particularly is suitable for electroslag ingots with the diameter of 300-560 mm of the high-Al and high-Al nickel-based high-temperature alloys. Since Ti and Al are easily oxidizable elements, they are easily reacted with oxides in electroslag, as shown in formula (1), resulting in burning loss of the elements. When TiO is present2When the content is too high, the formula (1) proceeds rightwards, and the phenomenon of Al burning and Ti increasing occurs; when Al is present2O3When the content is too high, the formula (1) proceeds to the left, and the burning of Ti to increase Al occurs.
4[Al]+3(TiO2)＝2(Al2O3)+3[Ti]Formula (1)
Aiming at the composition characteristics of the high-aluminum titanium of the alloy applicable to the invention, the smelting method of the invention is used for treating CaF2-Al2O3-CaO-TiO2Al in quaternary slag system2O3And TiO2The proportion of the alloy is optimized, and Al and Ti elements of the alloy electroslag ingot are effectively controlled to be burnt and damaged by combining with the optimization and adjustment of an electrical system in an electroslag remelting process.
The inventor designs a CaF through a large amount of experiments2-Al2O3-CaO-TiO2A large number of experimental demonstrations show that the quaternary slag has the following technical characteristics in smelting:
(1) adding a relatively high amount of CaF2The melting point, viscosity and surface tension of the electroslag are reduced, and a small current can be input in the starting stage, so that element burning loss is avoided;
(2) CaO with relatively low content is added, so that the reduction of electroslag resistivity is avoided, and a certain S removal effect is ensured;
(3) adding proper amount of Al2O3The conductivity is reduced, the specific resistance is improved, the power consumption is reduced, the production efficiency is improved, and the melting point and the viscosity are increased and the Al is increased due to burning Ti when the additive is added too high;
(4) adding proper amount of TiO2Can play a role in avoiding burning loss of Al and Ti elements, TiO2Too high will cause the increase of Ti by burning Al, otherwise, it will cause the increase of Al by burning Ti.
Further experimental demonstration proves that the alloy suitable for the quaternary slag adopted by the invention comprises the following components in percentage by weight: 13.0 to 16.0 Co, 10.0 to 16.0 Cr, 4.0 to 6.0W, 2.0 to 4.0 Mo, 2.0 to 5.0 Al, 1.5 to 3.7 Ti, 0.7 to 1.5 Nb, 0.01 to 0.015B, 0.005 to 0.045 Zr, 0.02 to 0.05C, and the balance Ni. The Al and Ti content in the alloy is high, and the problem of uneven Al and Ti at the head and the tail easily occurs in the electroslag ingot smelting process. The electroslag remelting smelting condition applicable to the invention is that the initial weight of a smelting electrode is 1500-2500 kg, and the diameter of an electroslag ingot is 300-560 mm.
The inventor finds that a smelting method for controlling element burning loss of a nickel-based alloy electroslag ingot of high-aluminum titanium is developed through further experimental demonstration, comprises the steps of filling a smelting electrode and slag of a quaternary slag system into an electroslag remelting furnace, and preparing the electroslag ingot through a starting stage, a smelting stage and a filling stage, wherein the smelting method comprises the following steps:
step one, adopting current control in a starting stage, wherein the current control adopts a stepless speed change mode to improve the current intensity: the initial current is 5000-10000A, the current is increased at the speed of 1000-3000A/min until the current intensity is 12000-17000A, and then the current is maintained for 10-30 min; reducing the current to 10000-14000A according to the speed of 100-300A/min; the starting stage keeps lower current and current increasing speed so as to control power to inhibit the Al from increasing Ti.
Step two, controlling the melting speed in the melting stage, wherein the melting speed is 3.5-5.5 kg/min, reducing the melting speed (the initial weight of the electrode, including but not limited to 1500-2500 kg) after 300-550 kg of smelting electrode is remained, adjusting the melting speed at the speed of 0.5-1.5kg/min/h, and keeping the melting speed after 3.0-4.5 kg/min; the smelting stage is controlled according to the smelting speed, so that the stability of the smelting process can be improved, and the metallurgical quality of the electroslag ingot can be improved.
Step three, adopting melting speed control in the filling stage, and continuously reducing the melting speed; and starting filling after 100-300 kg of smelting electrode is remained, adjusting the melting speed according to the speed of 0.5-2.0kg/min/h in the filling process until the melting speed is kept after 2.0kg/min, and stopping smelting after 15-45 kg of smelting electrode is remained.
The inventor discovers through a large amount of experimental demonstration, research and development analysis that the weight of the electrode is gradually reduced along with smelting, the weight of the electroslag ingot is gradually increased, and in order to avoid large fluctuation of power in a filling stage, the smelting method reduces the smelting speed to a filling steady-state smelting speed at a constant speed in the later stage of the smelting stage; the melting speed is also reduced at a constant speed during the filling phase to the end of the melting. By adopting the smelting method, the large change of the smelting power in the filling stage can be avoided, and further, the burning loss degree of Al and Ti elements of the electroslag ingot in the filling stage is inhibited.
In order to make the technical means, the original characteristics, the achieved purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments, but the invention includes but is not limited to the embodiments.
Comparative example 1, a smelting method for controlling element burning loss of a nickel-based alloy electroslag ingot of high-aluminum titanium this comparative example mainly introduces a smelting method for controlling element burning loss of a nickel-based alloy electroslag ingot of high-aluminum titanium, and the specific smelting method and parameters include:
(1) the high-aluminum-titanium nickel-based high-temperature alloy comprises the following components in percentage by weight:
ni is taken as a matrix, Co 16.0, Cr 10.0, W6.0, Mo 2.0, Al 5.0, Ti 1.5, Nb 1.5, B0.01, Zr 0.005 and C0.05; according to the composition and weight percentage of the nickel-based high-temperature alloy of high aluminum and titanium, a vacuum induction smelting furnace is adopted to smelt and refine a metal raw material or a return material, then a vacuum induction ingot is cast (specific technical parameters refer to CN111235434A), and then the surface of the vacuum induction ingot is machined to obtain an electrode D1 (the initial weight of the electrode is 2000kg) for electroslag remelting.
(2) Diameter of electroslag ingot: 510 mm;
(3) electrode diameter: 430 mm;
(4) electrode length: 2500 mm;
(5) the slag charge adopts five-element slag: the five-element slag comprises 50 percent of CaF in percentage by weight2、22％Al2O3、20％CaO、5％MgO、3％TiO2；
(6) The key smelting parameters are as follows:
1) in the starting stage, an electrode D1 and slag which are prepared and remelted by electroslag are filled in an electroslag remelting furnace, and the current is reduced in a grading way by adopting current control: the initial current is 6000A, the melting speed is 12000A in 0-5min, 10000A in 5-10min and 9000A in 10-20 min;
2) the melting stage adopts melting speed control, and the melting speed is unchanged: the melting speed is 5.0 kg/min;
3) and the filling stage adopts melting speed control, and the melting speed is reduced in stages: and (3) starting to fill the electrode after 200kg of the electrode is remained, wherein the filling process is carried out for 0-15min, the melting speed is set to be 3.5kg/min, the melting speed is set to be 2.0kg/min after 15-30min, and the melting is stopped after 30kg of the electrode is remained, so that the electroslag ingot is obtained.
The contents of Al and Ti elements in the electrode, the start end and the filling end of the electroslag ingot adopted in the smelting method described in comparative example 1 were measured to obtain the measured results shown in table 1: as can be seen from Table 1, the Al element content in the smelting front electrode D1 was 4.92%, and the Ti element content was 1.48%; after smelting, the Al element at the starting end of the electroslag ingot in the comparative example 1 is obviously burnt, and the content of the Al element is 4.65 percent; burning loss of Al element at the filling end of the electroslag ingot is caused, the content of the Al element is 4.78 percent, and the difference value of the Al element content at the head and the tail of the electroslag ingot reaches 0.13 percent; the content of Ti element at the starting end of the electroslag ingot treated by the smelting method according to the comparative example is obviously increased, and the content of Ti element is 1.62 percent; the Ti content of the filling end is slightly increased, the Ti content is 1.50%, and the difference of the Ti content of the head and the tail of the electroslag ingot is 0.12%. Therefore, the slag system proportion and the smelting method in the comparative example 1 are not ideal, and the obvious product defect of Al burning and Ti increasing, namely the problem of burning loss of Al elements and Ti elements, occurs in the remelting process of the electroslag ingot.
TABLE 1 actual measurement results of Al and Ti element contents of the electrode, start end and filling end of comparative example 1
| Element(s) | VIM electrode (D1) | Electroslag ingot starting end | Electroslag ingot filling end |
| Al | 4.92％ | 4.65％ | 4.78％ |
| Ti | 1.48％ | 1.62％ | 1.50％ |
Comparative example 2, a smelting method for controlling element burning loss of a nickel-based alloy electroslag ingot of high-aluminum titanium this comparative example mainly introduces a smelting method for controlling element burning loss of a nickel-based alloy electroslag ingot of high-aluminum titanium, and the specific smelting method and parameters include:
(1) the high-aluminum-titanium nickel-based high-temperature alloy comprises the following components in percentage by weight:
ni matrix, Co 13.0, Cr 16.0, W4.0, Mo 4.0, Al 2.1, Ti 3.7, Nb 0.7, B0.015, Zr 0.045 and C0.02; according to the composition and weight percentage of the nickel-based high-temperature alloy of high aluminum and titanium, a vacuum induction smelting furnace is adopted to smelt and refine a metal raw material or a return material, then a vacuum induction ingot is cast (specific technical parameters refer to CN111235434A), and then the surface of the vacuum induction ingot is machined to obtain an electrode D2 (the initial weight of the electrode is 2000kg) for electroslag remelting.
(2) Diameter of electroslag ingot: 430 mm;
(3) electrode diameter: 340 mm;
(4) electrode length: 2500 mm;
(2) diameter of electroslag ingot: 510 mm;
(3) electrode diameter: 430 mm;
(4) electrode length: 2500 mm;
(5) the slag charge adopts five-element slag: the five-element slag system comprises 50 percent of CaF in percentage by weight2、22％Al2O3、20％CaO、5％MgO、3％TiO2；
(6) The key smelting parameters are as follows:
1) in the starting stage, an electrode D2 and slag which are prepared and remelted by electroslag are filled in an electroslag remelting furnace, and the current is reduced in a grading way by adopting current control: the initial current is 6000A, the melting speed is 12000A in 0-5min, 10000A in 5-10min and 9000A in 10-20 min;
2) the melting stage adopts melting speed control, and the melting speed is unchanged: the melting speed is 5.0 kg/min;
3) and the filling stage adopts melting speed control, and the melting speed is reduced in stages: and (3) starting to fill the electrode after 200kg of the electrode is remained, wherein the filling process is carried out for 0-15min, the melting speed is set to be 3.5kg/min, the melting speed is set to be 2.0kg/min after 15-30min, and the melting is stopped after 30kg of the electrode is remained, so that the electroslag ingot is obtained.
The contents of Al and Ti elements in the electrode, the start end and the filling end of the electroslag ingot adopted in the smelting method described in comparative example 2 were measured to obtain the measured results shown in table 2: as can be seen from Table 2, the Al element content and the Ti element content in the pre-smelting electrode D2 were 2.25% and 3.68%, respectively; comparative example 2 the Al element at the start end of the electroslag ingot is obviously burned away, and the Al element content is reduced to 1.94%; burning loss of Al at the filling end of the electroslag ingot is also generated, the content of Al element is reduced to 2.14%, and the difference value of Al elements at the head and the tail of the electroslag ingot reaches 0.2%; comparative example 2 the content of Ti element at the start end of the electroslag ingot is increased significantly to 3.8%; the Ti content of the filling end of the electroslag ingot is slightly increased to 3.69%, and the element content of the head-tail difference of the electroslag ingot reaches 0.11%. Therefore, the slag system proportion and the smelting method of the comparative example 2 are not ideal, and the obvious product defect of Al burning and Ti increasing, namely the problem of burning loss of Al and Ti elements, is caused in the electroslag ingot remelting process.
TABLE 2 actual measurement results of Al and Ti contents of the electrode, start end and filling end of the electroslag ingot of comparative example 2
| Element(s) | VIM electrode (D2) | Electroslag ingot starting end | Electroslag ingot filling end |
| Al | 2.25％ | 1.94％ | 2.14％ |
| Ti | 3.68％ | 3.80％ | 3.69％ |
Example 1 smelting method for controlling element burning loss of high-aluminum titanium nickel-based alloy electroslag ingot
The embodiment mainly introduces a smelting method for controlling element burning loss of a high-aluminum titanium nickel-based alloy electroslag ingot. Fig. 1 is a schematic diagram of an electroslag remelting process, wherein electroslag generates slag heat resistance under the action of current, an electrode 1 immersed in the electroslag remelting process is melted, the melted metal is collected into molten drops and drops to pass through a layer of electroslag 3, and the molten drops enter a crystallizer to be solidified into an electroslag ingot 4, the bottom of the electroslag ingot is an electroslag ingot starting end (tail) 5, and the head of the electroslag ingot is an electroslag ingot filling end (head) 2, when the slag system proportion and the smelting process of the electroslag 3 (i.e. slag materials mentioned herein) are unreasonable, the Ti and Al elements at the head and the tail (i.e. 2 and 5 in the drawing) of the electroslag ingot can generate great difference, and the composition uniformity of the electroslag ingot 4 is not facilitated.
A smelting method for controlling element burning loss of a nickel-based alloy electroslag ingot of high-aluminum titanium comprises the following specific smelting methods and parameters:
(1) the high-aluminum-titanium nickel-based high-temperature alloy comprises the following components in percentage by weight:
ni matrix, Co 16.0, Cr 10.0, W6.0, Mo 2.0, Al 4.8, Ti 1.5, Nb 1.5, B0.01, Zr 0.005 and C0.05; according to the composition and weight percentage of the nickel-based high-temperature alloy of high aluminum and titanium, a vacuum induction smelting furnace is adopted to cast a metal raw material or a return material into a vacuum induction ingot after smelting and refining treatment (specific technical parameters refer to CN111235434A), and then the surface of the vacuum induction ingot is machined to prepare an electrode S1 (the initial weight of the electrode is 2000kg) for electroslag remelting.
(2) Diameter of electroslag ingot: 430 mm;
(3) electrode diameter: 340 mm;
(4) electrode length: 2500 mm;
(5) the slag charge adopts quaternary slag: the quaternary slag system comprises 70 percent of CaF in percentage by weight2、14％Al2O3、14％CaO、2％TiO2；
(6) Charging the prepared electroslag remelting electrode S1 and slag in an electroslag remelting furnace, and preparing an electroslag ingot through a starting stage, a smelting stage and a filling stage; the key smelting parameters are as follows:
1) in the starting stage, current control is adopted, and the current control adopts a stepless speed change mode to improve the current intensity: the initial current is 6000A, the current is increased at the speed of 2000A/min to the maximum of 15000A, and then the current is maintained for 20 min; reducing the current to 10000A at the speed of 250A/min;
2) the melting speed control is adopted in the melting stage, and the melting speed is reduced in advance: the melting speed is 5.0kg/min, the melting speed is reduced after 350kg of the electrode S1 is remained, the melting speed is adjusted at the speed of 0.5kg/min/h until 3.5 kg/min;
3) the filling stage adopts melting speed control, and melting is continuously reduced: and (3) starting filling after 200kg of the electrode S1 is remained, adjusting the melting speed according to the speed of 1.5kg/min/h in the filling process until the melting speed is kept after 2.0kg/min, and stopping melting after 30kg of the electrode S1 is remained to obtain the high-aluminum-titanium nickel-based alloy electroslag ingot.
The actual measurement of the Al and Ti contents of the electrode, the start end and the filling end of the high-aluminum titanium nickel-based alloy electroslag ingot in the smelting method described in example 1 is performed to obtain the actual measurement results shown in table 3: the Al element content in the smelting front electrode S1 is 4.92%, and the Ti element content is 1.48%; the burning loss of the Al element at the starting end of the nickel-based alloy electroslag ingot of high-aluminum titanium treated by the smelting method in the embodiment 1 is small, and the content of the Al element is 4.79 percent; the burning loss of Al element at the filling end of the treated high-aluminum-titanium nickel-based alloy electroslag ingot is small, and the content of the Al element is 4.78%; the difference of the Al element contents at the head and the tail of the nickel-based alloy electroslag ingot of the treated high-aluminum titanium is 0.01 percent. The increase of the Ti element content at the starting end of the nickel-based alloy electroslag ingot of high-aluminum titanium treated by the smelting method in example 1 is small, the Ti element content is 1.49%, the increase of the Ti element content at the filling end of the nickel-based alloy electroslag ingot of high-aluminum titanium treated by the smelting method is small, the Ti element content is 1.50%, and the difference of the Ti element content at the head and the tail of the nickel-based alloy electroslag ingot of high-aluminum titanium treated by the smelting method is 0.01%. Therefore, in the embodiment 1, the degree of Al burning and Ti increasing in the process of smelting the nickel-based alloy electroslag ingot of high-aluminum titanium is obviously reduced by optimizing the slag system proportion and the smelting method.
Table 3 actual measurement results of Al and Ti element contents of electrode, start end and pack end of electroslag ingot in example 1
Example 2 smelting method for controlling element burning loss of high-aluminum titanium nickel-based alloy electroslag ingot
The embodiment mainly introduces a smelting method for controlling element burning loss of a high-aluminum titanium nickel-based alloy electroslag ingot. Fig. 1 is a schematic diagram of an electroslag remelting process, wherein electroslag generates slag heat resistance under the action of current, an electrode 1 immersed in the electroslag remelting process is melted, the melted metal is collected into molten drops and drops to pass through a layer of electroslag 3, and the molten drops enter a crystallizer to be solidified into an electroslag ingot 4, the bottom of the electroslag ingot is an electroslag ingot starting end (tail) 5, and the head of the electroslag ingot is an electroslag ingot filling end (head) 2, when the slag system proportion and the smelting process of the electroslag 3 (i.e. slag materials mentioned herein) are unreasonable, the Ti and Al elements at the head and the tail (i.e. 2 and 5 in the drawing) of the electroslag ingot can generate great difference, and the composition uniformity of the electroslag ingot 4 is not facilitated.
A smelting method for controlling element burning loss of a nickel-based alloy electroslag ingot of high-aluminum titanium comprises the following specific smelting methods and parameters:
(1) the high-aluminum-titanium nickel-based high-temperature alloy comprises the following components in percentage by weight:
ni matrix, Co 13.0, Cr 16.0, W4.0, Mo 4.0, Al 2.1, Ti 3.7, Nb 0.7, B0.015, Zr 0.045 and C0.02; according to the composition and weight percentage of the nickel-based high-temperature alloy of high aluminum and titanium, a vacuum induction smelting furnace is adopted to cast a metal raw material or a return material into a vacuum induction ingot after smelting and refining treatment (specific technical parameters refer to CN111235434A), and then the surface of the vacuum induction ingot is machined to prepare an electrode S1 (the initial weight of the electrode is 2000kg) for electroslag remelting.
(2) Diameter of electroslag ingot: 430 mm;
(3) electrode diameter: 340 mm;
(4) electrode length: 2500 mm;
(5) the slag charge adopts quaternary slag: the quaternary slag system comprises 70 percent of CaF in percentage by weight2、14％Al2O3、14％CaO、2％TiO2；
(6) Charging the prepared electroslag remelting electrode S1 and slag in an electroslag remelting furnace, and preparing an electroslag ingot through a starting stage, a smelting stage and a filling stage; the key smelting parameters are as follows:
1) in the starting stage, an electrode S2 and slag which are prepared and remelted by electroslag are filled in an electroslag remelting furnace, and current control is adopted, wherein the current control adopts a stepless speed change mode to improve the current intensity: the initial current is 6000A, the current is increased at the speed of 2000A/min to the maximum of 15000A, and then the current is maintained for 20 min; reducing the current to 10000A at the speed of 250A/min;
2) the melting speed control is adopted in the melting stage, and the melting speed is reduced in advance: the melting speed is 5.0kg/min, the melting speed is reduced after 350kg of the electrode S2 is remained, the melting speed is adjusted at the speed of 0.5kg/min/h until 3.5 kg/min;
3) the filling stage adopts melting speed control, and melting is continuously reduced: and (3) starting filling after 200kg of the electrode S2 is remained, adjusting the melting speed according to the speed of 1.5kg/min/h in the filling process until the melting speed is kept after 2.0kg/min, and stopping melting after 30kg of the electrode S2 is remained to obtain the high-aluminum-titanium nickel-based alloy electroslag ingot.
The actual measurement of the Al and Ti contents of the electrode, the start end and the filling end of the high-aluminum titanium nickel-based alloy electroslag ingot in the smelting method described in example 2, results of the actual measurement shown in table 4 are obtained: the Al element content of the smelting front electrode S2 was 2.25%, and the Ti element content was 3.68%. After the smelting method is carried out according to the embodiment 2, the burning loss of the Al element at the starting end of the nickel-based alloy electroslag ingot of the high-aluminum titanium is small, the content of the Al element is 2.11%, the burning loss of the Al element at the filling end of the nickel-based alloy of the high-aluminum titanium after the smelting method is carried out is small, the content of the Al element is 2.12%, and the difference value of the Al element content at the head and the tail of the nickel-based alloy electroslag ingot of the high-aluminum titanium after the smelting method is 0.01%; example 2 the increase of Ti element at the starting end of the high-aluminum titanium nickel-based alloy electroslag ingot is small, and the content of Ti element is 3.80%; the Ti element at the filling end of the nickel-based alloy electroslag ingot of the high-aluminum titanium is increased slightly, the content of the Ti element is 3.78 percent, and the difference value of the head and tail Ti elements of the nickel-based alloy electroslag ingot of the high-aluminum titanium after treatment is 0.02 percent. Therefore, in the embodiment 2, the degree of Al increase and Ti increase of the high-aluminum titanium nickel-based alloy electroslag ingot by burning Al is obviously reduced by optimizing the slag system proportion and the smelting method.
TABLE 4 actual measurement results of Al and Ti contents of the electrode, start end and filling end of electroslag ingot in example 2
| Element(s) | VIM electrode (S2) | Electroslag ingot starting end | Electroslag ingot filling end |
| Al | 2.25％ | 2.11％ | 2.12％ |
| Ti | 3.68％ | 3.80％ | 3.78％ |
Example 3 smelting method for controlling element burning loss of high-aluminum titanium nickel-based alloy electroslag ingot
The embodiment mainly introduces a smelting method for controlling element burning loss of a high-aluminum titanium nickel-based alloy electroslag ingot. Fig. 1 is a schematic diagram of an electroslag remelting process, wherein electroslag generates slag heat resistance under the action of current, an electrode 1 immersed in the electroslag remelting process is melted, the melted metal is collected into molten drops and drops to pass through a layer of electroslag 3, and the molten drops enter a crystallizer to be solidified into an electroslag ingot 4, the bottom of the electroslag ingot is an electroslag ingot starting end (tail) 5, and the head of the electroslag ingot is an electroslag ingot filling end (head) 2, when the slag system proportion and the smelting process of the electroslag 3 (i.e. slag materials mentioned herein) are unreasonable, the Ti and Al elements at the head and the tail (i.e. 2 and 5 in the drawing) of the electroslag ingot can generate great difference, and the composition uniformity of the electroslag ingot 4 is not facilitated.
A smelting method for controlling element burning loss of a nickel-based alloy electroslag ingot of high-aluminum titanium comprises the following specific smelting methods and parameters:
(1) the high-aluminum-titanium nickel-based high-temperature alloy comprises the following components in percentage by weight:
ni matrix, Co 14.0, Cr 12.0, W5.0, Mo 3.0, Al 2.0, Ti 2.0, Nb 1.0, B0.012, Zr 0.015 and C0.03; according to the composition and weight percentage of the nickel-based high-temperature alloy of high aluminum and titanium, a vacuum induction smelting furnace is adopted to cast a metal raw material or a return material into a vacuum induction ingot after smelting and refining treatment (specific technical parameters refer to CN111235434A), and then the surface of the vacuum induction ingot is machined to prepare an electrode S3 (the initial weight of the electrode is 2000kg) for electroslag remelting.
(2) Diameter of electroslag ingot: 300 mm;
(3) electrode diameter: 340 mm;
(4) electrode length: 2500 mm;
(5) the slag charge adopts quaternary slag: the quaternary slag system comprises 65 percent of CaF in percentage by weight2、15％Al2O3、15％CaO、5％TiO2；
(6) Charging the prepared electroslag remelting electrode S1 and slag in an electroslag remelting furnace, and preparing an electroslag ingot through a starting stage, a smelting stage and a filling stage; the key smelting parameters are as follows:
1) in the starting stage, an electrode S3 and slag which are prepared and remelted by electroslag are filled in an electroslag remelting furnace, and current control is adopted, wherein the current control adopts a stepless speed change mode to improve the current intensity: the initial current is 5000A, the current is increased at the speed of 3000A/min to 12000A at most, and then the current is maintained for 30 min; reducing the current to 10000A at the speed of 100A/min;
2) the melting speed control is adopted in the melting stage, and the melting speed is reduced in advance: the melting speed is 3.5kg/min, the melting speed is reduced after 300kg of the electrode S3 is remained, the melting speed is adjusted at the speed of 0.5kg/min/h until the melting speed is maintained at 3.0 kg/min;
3) the filling stage adopts melting speed control, and melting is continuously reduced: and (3) filling the electrode S3 after 100kg of the electrode S3 is remained, adjusting the melting speed according to the speed of 0.5kg/min/h in the filling process until the melting speed is kept after 2.0kg/min, and stopping smelting after 15kg of the electrode S3 is remained to obtain the high-aluminum-titanium nickel-based alloy electroslag ingot.
The actual measurement of the Al and Ti contents of the electrode, the start end and the filling end of the high-aluminum titanium nickel-based alloy electroslag ingot in the smelting method described in example 3, results of the actual measurement shown in table 5 are obtained: as can be seen from table 5, the Al element content in the electrode S3 was 2.12%, and the Ti element content was 1.95%; the Al element burning loss of the starting end of the high-aluminum titanium nickel-based alloy electroslag ingot treated by the smelting method in the embodiment 3 is small, and the Al element content is 2.01 percent; the burning loss of Al element at the filling end of the treated nickel-based alloy electroslag ingot with high aluminum and titanium is less than 2.03 percent, and the difference value of Al element at the head and the tail of the nickel-based alloy electroslag ingot with high aluminum and titanium is 0.02 percent; the increase of Ti element at the starting end of the treated nickel-based alloy electroslag ingot with high aluminum and titanium is small, and the content of Ti element is 2.03 percent; the increase of Ti element at the filling end of the nickel-based alloy electroslag ingot of the high-aluminum titanium after the treatment is smaller, the content of Ti element is 2.01 percent, and the difference value of the Ti element at the head and the tail of the nickel-based alloy electroslag ingot of the high-aluminum titanium is 0.01 percent. In example 3, the degree of Al increase and Ti increase of the high-aluminum titanium nickel-based alloy electroslag ingot can be obviously reduced by optimizing the slag system proportion and the smelting method.
TABLE 5 actual measurement results of Al and Ti contents of the electrode, start end and filling end of electroslag ingot in example 3
| Element(s) | VIM electrode (S3) | Electroslag ingot starting end | Electroslag ingot filling end |
| Al | 2.12％ | 2.01％ | 2.03％ |
| Ti | 1.95％ | 2.03％ | 2.01％ |
Example 4 smelting method for controlling element burning loss of high-aluminum titanium nickel-based alloy electroslag ingot
The embodiment mainly introduces a smelting method for controlling element burning loss of a high-aluminum titanium nickel-based alloy electroslag ingot. Fig. 1 is a schematic diagram of an electroslag remelting process, wherein electroslag generates slag heat resistance under the action of current, an electrode 1 immersed in the electroslag remelting process is melted, the melted metal is collected into molten drops and drops to pass through a layer of electroslag 3, and the molten drops enter a crystallizer to be solidified into an electroslag ingot 4, the bottom of the electroslag ingot is an electroslag ingot starting end (tail) 5, and the head of the electroslag ingot is an electroslag ingot filling end (head) 2, when the slag system proportion and the smelting process of the electroslag 3 (i.e. slag materials mentioned herein) are unreasonable, the Ti and Al elements at the head and the tail (i.e. 2 and 5 in the drawing) of the electroslag ingot can generate great difference, and the composition uniformity of the electroslag ingot 4 is not facilitated.
A smelting method for controlling element burning loss of a nickel-based alloy electroslag ingot of high-aluminum titanium comprises the following specific smelting methods and parameters:
(1) the high-aluminum-titanium nickel-based high-temperature alloy comprises the following components in percentage by weight:
ni matrix, Co 16.0, Cr 10.0, W6.0, Mo 2.0, Al 5.0, Ti 1.5, Nb 1.5, B0.01, Zr 0.005 and C0.05; according to the composition and weight percentage of the nickel-based high-temperature alloy of high aluminum and titanium, a vacuum induction smelting furnace is adopted to cast a metal raw material or a return material into a vacuum induction ingot after smelting and refining treatment (specific technical parameters refer to CN111235434A), and then the surface of the vacuum induction ingot is machined to prepare an electrode S4 (the initial weight of the electrode is 2000kg) for electroslag remelting.
(2) Diameter of electroslag ingot: 560 mm;
(3) electrode diameter: 340 mm;
(4) electrode length: 2500mm
(5) The slag charge adopts quaternary slag: the quaternary slag system comprises 72 percent of CaF in percentage by weight2、12％Al2O3、12％CaO、4％TiO2；
(6) Charging the prepared electroslag remelting electrode S1 and slag in an electroslag remelting furnace, and preparing an electroslag ingot through a starting stage, a smelting stage and a filling stage; the key smelting parameters are as follows:
1) in the starting stage, an electrode S4 and slag which are prepared and remelted by electroslag are filled in an electroslag remelting furnace, and current control is adopted, wherein the current control adopts a stepless speed change mode to improve the current intensity: the initial current is 10000A, the current is increased at the speed of 1000A/min to 17000A at the maximum, and then the current is maintained for 10 min; reducing the current at a speed of 300A/min to 14000A;
2) the melting speed control is adopted in the melting stage, and the melting speed is reduced in advance: the melting speed is 5.5kg/min, the melting speed is reduced after 550kg of the electrode S4 is remained, the melting speed is adjusted at the speed of 1.5kg/min/h, and the melting speed is maintained after 4.5 kg/min;
3) the filling stage adopts melting speed control, and melting is continuously reduced: and (3) filling the electrode S4 after 300kg of the electrode S is remained, adjusting the melting speed according to the speed of 2.0kg/min/h in the filling process until the melting speed is kept after 2.0kg/min, and stopping smelting after 45kg of the electrode S is remained to obtain the high-aluminum-titanium nickel-based alloy electroslag ingot.
The actual measurement of the Al and Ti contents of the electrode, the start end and the filling end of the high-aluminum titanium nickel-based alloy electroslag ingot adopted in the smelting method described in example 4 is carried out, and the actual measurement results shown in table 6 are obtained: as can be seen from Table 6, the Al element content in the pre-smelting electrode S4 was 5.18%, and the Ti element content was 1.38%; however, the high-aluminum titanium nickel-based alloy electroslag ingot treated by the smelting method in the embodiment 4 has small burning loss of the Al element at the starting end, and the content of the Al element is 5.01%; the Al element burning loss of the filling end of the nickel-based alloy of the high-aluminum titanium after the treatment is smaller, the Al element content is 5.04%, and the Al element difference value of the head and the tail of the nickel-based alloy electroslag ingot of the high-aluminum titanium is 0.03%; example 4 the increase of Ti element at the starting end of the high-aluminum titanium nickel-based alloy electroslag ingot is small, and the content of Ti element is 1.55%; the Ti at the filling end of the nickel-based alloy electroslag ingot with high aluminum content and titanium content is increased slightly, and the Ti content is 1.52%; the difference value of Ti elements at the head and the tail of the electroslag ingot is 0.03 percent. Therefore, in example 4, the degree of increasing Ti by burning Al in the high-aluminum titanium nickel-based alloy electroslag ingot is significantly reduced by optimizing the slag system ratio and the smelting method.
TABLE 6 actual measurement results of Al and Ti contents of the electrode, start end and filling end of the electroslag ingot of example 4
| Element(s) | VIM electrode (S4) | Electroslag ingot starting end | Electroslag ingot filling end |
| Al | 5.18％ | 5.01％ | 5.04％ |
| Ti | 1.38％ | 1.55％ | 1.52％ |
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The smelting method for controlling element burning loss of the nickel-based alloy electroslag ingot with high aluminum content and titanium content is characterized in that a quaternary slag system is adopted for electroslag remelting in the smelting method, and the slag composition and weight percentage of the quaternary slag system are CaF2 65~72%，Al2O3 12~15%，CaO 12~15%，TiO21-5%; the smelting method comprises a starting stage, a smelting stage and a filling stage.
2. The smelting method according to claim 1, wherein a smelting electrode and slag of the quaternary slag system are charged into an electroslag remelting furnace, and a nickel-based alloy electroslag ingot of high aluminum titanium is prepared through the starting stage, the smelting stage and the filling stage; the starting stage adopts current control, and the current control adopts a stepless speed change mode to improve the current intensity: the initial current is 5000-10000A, the current is increased at the speed of 1000-3000A/min until the current intensity is 12000-17000A, and then the current is maintained for 10-30 min; and reducing the current to 10000-14000A at a speed of 100-300A/min.
3. The smelting method according to claim 1, wherein the smelting stage is controlled by a smelting speed, the initial smelting speed is 3.5-5.5 kg/min, and the smelting speed is reduced after 300-550 kg of smelting electrodes remain: adjusting the melting speed at a speed of 0.5-1.5kg/min/h to 3.0-4.5 kg/min and keeping.
4. The smelting method according to claim 1, wherein the filling stage is controlled by using the smelting speed, the smelting speed is continuously reduced after 100-300 kg of smelting electrode is remained, the smelting speed is adjusted at a speed of 0.5-2.0kg/min/h until 2.0kg/min, and the smelting is stopped after 15-45 kg of smelting electrode is remained.
5. The smelting method according to claim 1, wherein the high-aluminum titanium nickel-based superalloy has a composition and weight percentage of: 13.0 to 16.0 Co, 10.0 to 16.0 Cr, 4.0 to 6.0W, 2.0 to 4.0 Mo, 2.0 to 5.0 Al, 1.5 to 3.7 Ti, 0.7 to 1.5 Nb, 0.01 to 0.015B, 0.005 to 0.045 Zr, 0.02 to 0.05C, and the balance Ni.
6. The smelting method according to claim 1, wherein the diameter of the high-aluminum-titanium nickel-based superalloy electroslag ingot is 300-560 mm.
7. The smelting method according to claim 1, wherein the loss amount of Al element is 1-6% and the increase amount of Ti element is 1-10% during the smelting process.
8. The smelting method according to claim 2, wherein the preparation method of the smelting electrode comprises: the composition of the high-Al-Ti-content Ni-based superalloy according to claim 5 is charged into a vacuum induction melting furnace, and melting and refining are performed.
9. A nickel-base superalloy of high aluminum titanium produced by the smelting method according to any one of claims 1 to 8.
10. Use of the high-al-ti ni-based superalloy according to claim 9 in aerospace and energy applications.
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| CN113444889A (en) * | 2021-05-19 | 2021-09-28 | 重庆材料研究院有限公司 | Method for uniformly distributing aluminum and titanium of nickel-based alloy electroslag ingot |
| CN113249619A (en) * | 2021-06-24 | 2021-08-13 | 北京科技大学 | Matrix component design method of delta-phase reinforced nickel-based superalloy |
| CN114317996A (en) * | 2021-12-08 | 2022-04-12 | 抚顺特殊钢股份有限公司 | Method for manufacturing low-gas-content high-titanium low-aluminum nickel-cobalt alloy electroslag remelting electrode |
| CN114317996B (en) * | 2021-12-08 | 2023-04-28 | 抚顺特殊钢股份有限公司 | Manufacturing method of low-gas-content high-titanium low-aluminum nickel cobalt alloy electroslag remelting electrode |
| CN115109937A (en) * | 2022-06-16 | 2022-09-27 | 山西太钢不锈钢股份有限公司 | Electroslag remelting method for effectively controlling N08810 aluminum-titanium component |
| CN115109937B (en) * | 2022-06-16 | 2023-09-05 | 山西太钢不锈钢股份有限公司 | Electroslag remelting method for effectively controlling N08810 aluminum titanium components |
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