CN115233011A - Method for adding trace metal elements to high-temperature alloy in controlled release manner based on efficient solid-liquid reaction - Google Patents
Method for adding trace metal elements to high-temperature alloy in controlled release manner based on efficient solid-liquid reaction Download PDFInfo
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Abstract
The invention relates to the technical field of metal smelting and casting, in particular to a method for adding trace metal elements to high-temperature alloy in a controlled release manner based on efficient solid-liquid reaction. The method comprises the following steps: (1) Melting the master alloy or different metal raw materials with determined components in a vacuum induction melting furnace to form a high-temperature alloy melt; (2) Releasing an additive containing a target element onto the melt surface; (3) After the surface of the melt is stabilized, maintaining the smelting atmosphere for refining to ensure that the target elements are applied to the melt according to the designed components; (4) And after refining, adjusting the temperature of the melt to the pouring temperature, and pouring. The invention is added in the form of additives in the form of metal oxides or carbonates, and the additives and the melt release trace elements in situ in the smelting process under the condition of controllable reaction process. The whole process is realized through a high-efficiency solid-liquid reaction form of the melt and the additive, the utilization efficiency of the raw materials is high, and the element content can be accurately controlled.
Description
Technical Field
The invention relates to the technical field of metal smelting and casting, in particular to a method for adding trace metal elements to high-temperature alloy in a controlled release manner based on efficient solid-liquid reaction.
Background
The high-temperature alloy is a metal material which takes iron, nickel and cobalt as bases, can work for a long time at a high temperature of more than 600 ℃ under the action of certain stress, has excellent high-temperature strength, good oxidation resistance and thermal corrosion resistance, good comprehensive properties such as creep property, fatigue property, fracture toughness and the like, is also called as super alloy, and is mainly applied to the fields of aerospace, energy, ships, electric power, metallurgy, automobiles and nuclear industry. In a modern aeroengine, the use amount of high-temperature alloy materials accounts for about 40-60% of the total mass of the engine, and the high-temperature alloy materials are mainly used for four hot end parts such as a combustion chamber, a guide blade, a turbine disc and the like, and parts with higher working temperature such as an engine casing, an annular piece, a tail nozzle and the like.
The high-temperature alloy is an indispensable key material for national defense weaponry and national economic construction, and the research and application level of the high-temperature alloy is an important mark for measuring the comprehensive strength of national material scientific development. The trace elements including rare earth elements (La, ce, Y and the like), zr and Hf have low content in the high-temperature alloy and have great influence on the performance of the high-temperature alloy, and the effective control of the trace elements in the high-temperature alloy is very important for breaking through the bottleneck problems of instable performance and low service life of the high-temperature alloy turbine blade in China.
The rare earth elements (La, ce, Y and the like) have great influence on the performance of the high-temperature alloy, and the performance of the high-temperature alloy can be greatly improved by adding a small amount of rare earth elements. The rare earth element has strong reactivity with nonmetal impurity elements such as ONS and the like which have great harm in the high-temperature alloy, and is very easy to generate corresponding rare earth oxide, rare earth sulfide, rare earth nitride and rare earth oxysulfide, so that the melt can be effectively purified in the smelting process, fine impurities can be effectively combined with O, N, S impurities in the alloy to form fine impurities, and the weakening effect of the elements such as oxygen, sulfur and the like on crystal boundaries is reduced. Meanwhile, rare earth elements are used as microalloying elements and are partially aggregated in a grain boundary, so that an effective grain boundary strengthening effect can be achieved. Most importantly, trace rare earth elements play an active element effect in the high-temperature alloy, so that the surface stability of the alloy can be effectively improved, and the oxidation resistance of the alloy is improved.
Hf is mainly dissolved in a gamma' phase in the high-temperature alloy, and the solubility of Hf in Ni3Al can reach 7at%. Thus, 90% of the Hf element is present in γ ' (containing γ + γ ' eutectic), and the addition of a certain amount of Hf may increase the amount of γ ' in the superalloy, further enhancing its precipitation strengthening effect. Meanwhile, hf is also a strong carbide forming element, can prevent the precipitation of massive carbides along the crystal, causes the precipitation of fine, dispersed and irregular secondary HfC carbides, promotes the distribution to be changed from a continuous net shape into a discrete block shape, and improves the plasticity of the alloy. Hf combines with trace elements represented by S in the alloy to form a fine inclusion, and a stable sulfide is generated to avoid the possibility of brittle fracture caused by sulfur segregation on grain boundaries.
The solubility of gamma and gamma' phases of Zr in the high-temperature alloy is very low, and the Zr is mainly distributed at the grain boundary in a form of second phase precipitation, so that the Zr has the functions of strengthening the grain boundary, improving the high-temperature strength, notch sensitivity, plasticity, creep deformation and the like. The addition of a proper amount of Zr in the high-temperature alloy plays an important role in realizing the performance of different alloys, causes the Zr to exist in a grain boundary mainly in a carbide form, can effectively inhibit the diffusion of the grain boundary and eliminate the possibility of existence of grain boundary vacancies, and achieves the possibility of strengthening crystallization and reducing intergranular fracture. Meanwhile, zr mainly exists in the form of carbide, sulfide or carbon sulfide, so that the harmful effect of sulfur on the alloy in the crystal segregation boundary can be greatly reduced. Meanwhile, hf, zr and S have strong chemical and physical properties, so that the separation of an oxide film caused by the diffusion of sulfur to the surface in the service process of the alloy can be greatly reduced, and the oxidation resistance of the high-temperature alloy can be improved.
The rare earth elements, hf, zr and other trace elements greatly improve the performance of the high-temperature alloy, and the content of the elements in the high-temperature alloy is generally low. Because the content of the elements is very low and the control range is very narrow, the precise control of the trace element components is difficult, and the realization of the design performance and the release of the potential of the alloy are greatly influenced. In the process of smelting the high-temperature alloy, because the trace addition is usually far lower than 1% of the melt amount, and simultaneously the density of trace alloy element simple substances or alloys is lower than that of the melt, because the process of melting the elements into the melt is generally an exothermic reaction, if the trace elements or the alloys are directly added, the heat effect generated in the smelting process can bring about strong splashing, and the loss of raw materials is caused while the component control is difficult. Meanwhile, because the elements have high activity, the phenomena of oxygen absorption and moisture absorption are easy to occur in the preservation process, so that the raw materials are invalid.
Disclosure of Invention
The invention aims to provide a method for adding trace metal elements to a high-temperature alloy in a controlled release manner based on an efficient solid-liquid reaction, and solves the problems of low control precision of the trace elements, limited utilization rate of trace element raw materials and the like caused by actions such as common splashing and the like of adding the trace elements in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for adding trace metal elements to a high-temperature alloy in a controlled release manner based on high-efficiency solid-liquid reaction comprises the following steps:
(1) Melting the master alloy or different metal raw materials with determined components in a vacuum induction melting furnace to form a high-temperature alloy melt;
(2) Releasing an additive containing the target element onto the melt surface;
(3) After the surface of the melt is stabilized, maintaining the smelting atmosphere for refining to ensure that the target elements are applied to the melt according to the designed components;
(4) And after refining, adjusting the temperature of the melt to the pouring temperature, and pouring.
In the method for adding trace metal elements to the high-temperature alloy in a controlled release manner based on the efficient solid-liquid reaction, in the step (1), the master alloy is a nickel-based, cobalt-based or iron-based high-temperature alloy, and different metal raw materials refer to single substances and alloys of one or more than two elements of Ni, fe, co, cr, W, mo, ti, al, V, C, B, ta, re, nb, ru and Pt contained in the high-temperature alloy.
According to the method for adding trace metal elements to the high-temperature alloy in a controlled release manner based on the efficient solid-liquid reaction, the master alloy or different metal raw materials contain a part of target elements: one or more than two of rare earth elements, hf and Zr, and relevant elements are supplemented by additives; or the master alloy or different metal raw materials do not contain the target element, the additive containing the target element is completely added, and one or more of rare earth element, hf and Zr are added into the high-temperature alloy melt at one time through the additive.
In the method for adding trace metal elements to the high-temperature alloy in the controlled release manner based on the efficient solid-liquid reaction, in the step (2), the additive containing the target elements comprises oxides, carbonates or the combination of the oxides and the carbonates containing the target elements.
The method for adding the trace metal elements to the high-temperature alloy in the controlled release manner based on the efficient solid-liquid reaction specifically comprises the following steps: 1) Additive for adding La element: laH 2 、La 2 O 3 、La 2 (CO 3 ) 3 ·xH 2 O、La(OH) 3 、LaC 2 One or more than two of the above; 2) Additive for adding Y element: y is 2 O 3 、Y 2 (CO 3 ) 2 、Y(OH) 3 、YH 3 、YC 2 One or more than two of the above; 3) Additive added with Ce element: ce 2 O 3 、CeO 1.72 、CeO 1.83 、CeO 2 、Ce 2 (CO 3 ) 2 、Ce(OH) 3 、CeC 2 One or more than two of the above; 4) Additive for adding Zr element: zrH 2 、ZrO 2 、Zr(OH) 4 、ZrC、Zr(CO 3 ) 2 、Zr(CH 3 COO) 4 One or more than two of the above; 5) Additive for adding Hf element: hfH 2 、HfO 2 、H 4 HfO 4 、HfC 2 、HfO 2 ·CO 2 ·xH 2 One or more than two of O; the addition of one element is realized by utilizing the combination of different substances in the elements and sequentially adding one or more than two trace elements through the combination of different additives.
In the step (2), the additive is added in a solid state form and keeps in a solid state in the smelting process, the release of the target element is realized in a solid-liquid reaction form with a melt, and the solid state form is powder with different particle sizes, blocks with different shapes or a combination of the powder and the blocks; the particle size of the powder is 0.01 mu m-5 mm, and the block shape comprises a spherical shape, a rod shape or a porous framework shape.
According to the method for adding trace metal elements to the high-temperature alloy controlled release based on the efficient solid-liquid reaction, the powder additive is directly added into a melt to carry out in-situ solid-liquid reaction after being mixed; the block additive is subjected to a molding-sintering process to maintain the shape and strength, and the process for preparing the block additive comprises the following steps: molding under the pressure of 5-200 MPa, and sintering and molding at the temperature of 1300-1700 ℃ for 0.5-10 h.
In the step (3), the smelting atmosphere refers to an inert atmosphere with the air pressure of 1000-100000 Pa or a vacuum atmosphere with the air pressure of 0.001-50000 Pa, the refining temperature is 1400-1700 ℃, and the refining time is 1-300 min.
In the method for adding trace metal elements to the high-temperature alloy in the controlled release manner based on the efficient solid-liquid reaction, in the step (4), the pouring temperature refers to the temperature of the melt in the actual pouring process within the range of 1350-1500 ℃.
The design idea of the invention is as follows:
firstly, melting the high-temperature alloy, releasing an additive (hydride, carbide, oxide, hydroxide, carbonate or a mixture thereof) containing a target element onto the surface of a melt, and maintaining a certain melt temperature and atmosphere conditions to perform a controlled-release reaction of the trace elements. And after the reaction is finished, adjusting the temperature to the casting temperature for casting, wherein the microelement additive and the high-temperature alloy melt are in a solid-liquid reaction form, and the additive keeps a solid state in the whole reaction process until the reaction is finished and the target content of microelements are all blended into the alloy melt. The additive does not affect the casting process and the alloy quality (O, N and other impurity elements). The invention achieves the controllable release of the trace elements by regulating the solid-liquid reaction of the trace element additive and the melt, achieves the stable, efficient and uniform addition of the trace elements into the high-temperature alloy melt by conditioning the reaction factors such as the composition and the form of the additive, the reaction temperature, the reaction vacuum degree and the like, realizes the controlled addition of the trace elements such as rare earth elements, zr, hf and the like in the high-temperature alloy with the content precision of 0.001wt%, and further releases beneficial trace elements to the maximum extent to improve the performance of the high-temperature alloy.
The invention has the following characteristics and beneficial effects:
(1) The reaction is stable and controllable: the addition of the trace elements is realized through the solid-liquid reaction between the solid compounds (hydrides, carbides, oxides, hydroxides and carbonates) of the target trace elements and the high-temperature alloy liquid melt, no obvious thermal effect exists in the reaction process, the splashing caused by directly adding a very small amount of trace element simple substances and alloys is avoided, and the control of the release rate of the trace elements can be realized through the changes of the reaction temperature, the reaction time, the vacuum degree and the additives. The melt liquid level in the whole reaction process is stable and controllable, and the influence on refractory materials and equipment is small.
(2) The control precision is high: the invention realizes the controlled release of the target trace element by an in-situ reaction mode, and does not directly blend the alloy component into the melt, so the problems of splashing and the like caused by adding the alloy component are effectively avoided, the interface reaction of the additive and the melt can be effectively regulated and controlled by the dosage and the form of the additive, the high-precision control of the trace element with the level of 0.001wt% is realized, and the strengthening effect of the trace element on the alloy performance is released to the maximum extent.
(3) Can realize the control of various trace elements at the same time: through different additive proportions and adjustment of interface reaction behavior of the additive and a melt, the invention can realize simultaneous regulation and control of various trace elements such as common rare earth elements, zr, hf and the like in the high-temperature alloy.
(4) The raw material utilization rate is high: because the invention adopts the controllable solid-liquid reaction mode to release the target trace elements in situ, the physical loss caused by splashing is avoided, and the utilization rate of the raw materials is close to 100 percent. Meanwhile, compared with the trace element simple substance and the trace element alloy, the project adopts the compound such as oxide with lower cost as the raw material, and the trace element adding cost can be greatly reduced from the aspects of raw material cost and utilization rate.
(5) The practicality is wider: the invention can be used for adding various trace elements such as rare earth elements, zr, hf and the like in a high-temperature alloy system, and can also be used for adding trace elements in high-carbon cast iron, cast steel, special steel, magnesium alloy and aluminum alloy systems.
Detailed Description
In the specific implementation process, the method for adding trace metal elements to the high-temperature alloy in a controlled release manner based on the efficient solid-liquid reaction specifically comprises the following steps of:
(1) Melting the mother alloy or different metal raw materials with determined components into a melt in a vacuum induction melting furnace;
(2) Releasing additives containing target elements in a certain form and specification onto the surface of the melt;
(3) After the surface of the melt is stable, reaction conditions such as a certain smelting atmosphere, the melt temperature and the like are kept, and a refining process is carried out for a period of time to ensure that the target elements are applied to the melt according to the designed components;
(4) And after refining, adjusting the temperature of the melt to the pouring temperature, and pouring according to certain requirements.
In the step (1), the master alloy comprises nickel-base, cobalt-base and iron-base high-temperature alloys, and the different metal raw materials refer to simple substances and alloys of various elements contained in the high-temperature alloys such as Ni, fe, co, cr, W, mo, ti, al, V, C, B, ta, re, nb, ru, pt and the like. The mother alloy or different metal raw materials can contain rare earth elements, hf and Zr, and related elements are supplemented by utilizing the technology of the invention; or may be added entirely by the present invention without the target element.
In the step (2), the additive containing the target oxide includes an oxide containing a target trace element, a carbonate, and a combination thereof. The method specifically comprises the following steps: 1) Additive for adding La element: laH 2 、La 2 O 3 、La 2 (CO 3 ) 3 ·xH 2 O、La(OH) 3 、LaC 2 (ii) a 2) Additive for adding Y element: y is 2 O 3 、Y 2 (CO 3 ) 2 、Y(OH) 3 、YH 3 、YC 2 (ii) a 3) Additive added with Ce element: ce 2 O 3 、CeO 1.72 、CeO 1.83 、CeO 2 、Ce 2 (CO 3 ) 2 、Ce(OH) 3 、CeC 2 (ii) a 4) Additive for adding Zr element: zrH 2 、ZrO 2 、Zr(OH) 4 、ZrC、Zr(CO 3 ) 2 、Zr(CH 3 COO) 4 (ii) a 5) Additive for adding Hf element: hfH 2 、HfO 2 、H 4 HfO 4 、HfC、HfO 2 ·CO 2 ·xH 2 And (O). The addition of one element can be realized by utilizing the combination of different substances in the elements, and the sequential addition of a plurality of trace elements can be realized by the combination of different additives.
The invention utilizes the solid-liquid reaction of the additive and the high-temperature alloy melt to release target trace elements in situ, wherein the additive comprises hydride, carbide, hydroxide, carbonate and acetate of different target elements. The reactions for releasing trace elements are mainly classified into the following three reactions according to the form of additives:
1) In-situ decomposition reaction: the additive in the form of solid hydride and carbide takes high-temperature melt as an energy source, then the in-situ decomposition reaction is carried out on the surface of the high-temperature melt, the active metal component obtained by decomposition enters the melt to achieve the original reaction controlled release effect, and the reaction is carried out according to the equations (1) and (2). The generated hydrogen is discharged from the melt along with an exhaust system, so that the components of the melt cannot be interfered, and the generated carbon is used as a necessary strengthening element in the high-temperature alloy;
MeH x →Me+x/2H 2 ↑ (1)
MeC x →Me+xC (2)
2) In-situ reduction reaction: the additive in the form of solid oxide can be reacted by active components of Al, C and the like in the high-temperature alloy melt, the target trace elements are quickly released into the melt through the controllable solid-liquid reaction according to the equations (3), (4) and (5), wherein the generated CO is discharged from the melt along with an exhaust system, the components of the melt cannot be interfered, and the generated Al 2 O 3 Or the composite oxide is attached to the surface of the melt in the form of solid slag, so that the components of the melt and the subsequent pouring process are not interfered;
MeO+C→Me+CO↑ (3)
MeO+Al→Me+Al 2 O 3 (4)
MeO+Al→Me+MeO·Al 2 O 3 (5)
3) In-situ decomposition-reduction reaction: the solid additives in the form of hydroxide and carbonate undergo decomposition reaction (according to formulas (6) and (7)) under the action of high-temperature melt to generate high-activity metal oxide and CO 2 、H 2 The O removes the melt along with the exhaust system, and does not interfere with the components of the melt; then the high-temperature alloy melt is reacted by active components such as Al, C and the like in the high-temperature alloy melt (carried out according to formulas (3), (4) and (5)), target trace elements are quickly released into the melt through the controllable solid-liquid reaction according to the formulas (3), (4) and (5), the generated CO is discharged from the melt along with an exhaust system, the components of the melt cannot be interfered, and the generated Al 2 O 3 Or the composite oxide is attached to the surface of the melt in the form of solid slag, so that the components of the melt and the subsequent pouring process cannot be interfered;
MeCO 3 →MeO+CO 2 ↑ (6)
Me(OH) 2 →MeO+H 2 O↑ (7)
certain forms and specifications mean that the additive is added in a solid state and remains in a solid state during the melting process, and the release of the target element is realized in a solid-liquid reaction form with the melt. The concrete forms comprise powders with different particle sizes and blocks with different shapes and the combination thereof. The particle size of the powder is 0.01-5 mm, and the block shape includes sphere, rod, porous skeleton, etc.
The powder additive is mixed and directly added into the melt to carry out in-situ solid-liquid reaction; the block needs to undergo a certain molding-sintering process to maintain a certain shape and strength. The process for preparing the blocky additive comprises the following steps: molding under the pressure of 5-200 MPa, and sintering and molding at 1300-1700 ℃ for 0.5-10 h. The trace element additive may comprise powders and chunks and combinations thereof.
The additive is formed into a solid state and is added into the melt, the additive exists in a solid state in the whole smelting process, and is rapidly reduced along with the reaction until the additive disappears after the reaction is finished, so that the corrosion and the damage of the liquid desulphurization slag to the smelting crucible can be effectively avoided.
The certain smelting atmosphere is 1000-100000 Pa inert atmosphere such as argon and helium, and 0.001-50000 Pa vacuum atmosphere. The certain melt temperature refers to the melting temperature of 1400-1700 ℃. The refining for a period of time refers to the smelting time of 1-300 min.
The pouring temperature refers to the temperature of the melt in the actual pouring process within the range of 1350-1500 ℃.
The present invention will be described in further detail below with reference to examples.
Example 1
In this example, 200ppm of Ce element was added to 22Kg of Ni-based superalloy K465.
TABLE 1 original composition Table of K465 alloy
The specific process is as follows:
(1) Putting Ni, co, cr, W, mo, C and Nb raw materials into a crucible, vacuumizing, heating and smelting, cooling to 1420 ℃ after the materials are cleared, adding Al, ti, zr, ni-B and other materials into the melt, sampling after the liquid level of the melt is stable, and measuring the components as shown in Table 1;
(2) 5.6g of CeO 2 Adding the powder on the surface of the melt, wherein the particle size distribution of the powder is shown in Table 2;
TABLE 2 additive Split particle size distribution Table
| Particle size range/mesh | Mass fraction/(w.t.%) |
| +18 | 3 |
| 18～60 | 20 |
| 60～100 | 20 |
| 100～200 | 30 |
| 200～400 | 20 |
| -400 | 7 |
(3) Adjusting the temperature of the melt to 1570 ℃, keeping the vacuum degree, keeping the air pressure in the furnace at 0.5Pa, and refining for 20min;
(4) Adjusting the temperature to 1450 ℃, casting the melt into an alloy ingot, and after the alloy ingot is cooled, respectively sampling the upper part and the lower part of the alloy ingot to determine the components shown in table 3;
TABLE 3 refined K465 alloy composition Table
Example 2
In this example, 500ppm of Zr element was added to 450Kg of Ni-based superalloy K417G.
TABLE 4 K417G alloy raw Components TABLE
The specific process is as follows:
(1) Putting Ni, co, cr, mo and C raw materials into a crucible, vacuumizing, heating and smelting, cooling to 1400 ℃ after the materials are cleared, adding V-Al, ti, zr, ni-B and other materials into the melt, sampling after the liquid level of the melt is stable, and measuring the components as shown in Table 4;
(2) 218.8g ZrO 2 、85.0g ZrC、131.2g Zr(OH) 4 The powder mixture was added to the melt surface, and the particle size distribution of each powder was as shown in table 5;
TABLE 5 particle size distribution of additive powders
(3) Adjusting the temperature of the melt to 1520 ℃, maintaining the vacuum degree to ensure that the pressure in the furnace is 0.8Pa, and refining for 30min;
(4) Adjusting the temperature to 1450 ℃, casting the melt into an alloy ingot, and after the alloy ingot is cooled, respectively sampling the upper part and the lower part of the alloy ingot to determine components shown in table 6;
TABLE 6 refined K417G alloy composition Table
Example 3
In this example, 600ppm Hf and 100ppm Y were added to 2200Kg of Ni-base superalloy DD 5.
TABLE 7 original composition Table of DD5 alloy
The specific process is as follows:
(1) Placing Ni, co, cr, W, mo and C raw materials in a crucible, vacuumizing, heating for smelting, cooling to 1450 ℃ after the materials are cleared, adding Al, ta, zr, re, hf, ni-B and other materials into the melt, sampling after the liquid level of the melt is stable, and measuring the components as shown in Table 7;
(2) 1556.6g HfO 2 、267.0g HfH 4 、157.3g HfC、244.5g Y 2 O 3 、88.5g Y 2 (CO 3 ) 3 、57.8gY(OH) 3 、31.0gYC 2 The powder mixture was added to the melt surface, and the particle size distribution of each powder was as shown in table 8;
TABLE 8 additive Split particle size distribution Table
(3) Adjusting the temperature of the melt to 1550 ℃, keeping the vacuum degree, enabling the pressure in the furnace to be 0.3Pa, and refining for 80min;
(4) Adjusting the temperature to 1480 ℃, casting the melt into an alloy ingot, and after the alloy ingot is cooled, respectively sampling the upper part and the lower part of the alloy ingot to determine components shown in a table 9;
TABLE 9 list of components of DD5 alloy after refining
Example 4
In this example, 100ppm La, 100ppm Ce and 500ppm Zr were added to 22Kg of Ni-based superalloy K40M.
TABLE 10 original composition Table of K40M alloy
The specific process is as follows:
(1) Placing Ni, co, cr, W, mo and C raw materials in a crucible, vacuumizing, heating for smelting, cooling to 1420 ℃ after the materials are cleared, adding Al, ti, zr, ta, ni-B and other materials into the melt, sampling after the liquid level of the melt is stable, and measuring the components as shown in Table 10;
(2) 268.7gCeO 2 、102.5gCe 2 O 3 、68.3gCe(OH) 3 、115.0gCe 2 (CO 3 ) 3 、45.5gCeC 2 、256.6gLa 2 O 3 、230.7gLa 2 (CO 3 ) 3 、191.4gLa(OH) 3 、46.0gLaC 2 、1477.4gZrO 2 、660.2gZrC、254.8gZr(OH) 4 、223.6gZrH 2 、405.2gZr(CO 3 ) 2 、785.1gZr(CH 3 COO) 4 And uniformly mixing the powder. The granularity of each powder is ensured: 40-50% of 100-200 meshes, 40-50% of 200-400 meshes, and the mass fractions of +100 meshes and-400 meshes<5 percent. Forming the mixed powder into a plurality of cylinders with the diameter of 35 plus or minus 2mm and the height of 40 plus or minus 5mm under the pressure of 100MPa, and preserving the heat for 2 hours within the range of 1500 ℃ for sintering and molding. Finally, adding the sintered product to the surface of the melt;
(3) Adjusting the temperature of the melt to 1550 ℃, keeping the vacuum degree to ensure that the air pressure in the crucible is 0.006Pa, and refining for 80min;
(4) Adjusting the temperature to 1450 ℃, casting the melt into an alloy ingot, and after the alloy ingot is cooled, respectively sampling the upper part and the lower part of the alloy ingot to determine components shown in Table 11;
TABLE 11 refined K40M alloy composition Table
The results of the examples show that the invention develops a method for adding additives in the form of metal oxides or carbonates, and the additives release trace elements in situ with the melt under the condition of controllable reaction process in the smelting process. The whole process is realized through a high-efficiency solid-liquid reaction form of the melt and the additive, no splashing exists in the reaction process, the utilization efficiency of the raw materials is high, and the element content can be accurately controlled. Except the target trace elements, the additive has no influence on the content of harmful impurities such as oxygen, nitrogen and the like in the melt, and is a rapid, efficient and controllable trace element controlled release method. The invention uses solid oxide and other additives, and can realize the precise control of trace elements by utilizing the original reaction of the melt and the additives.
Claims (9)
1. A method for adding trace metal elements to a high-temperature alloy in a controlled release manner based on a high-efficiency solid-liquid reaction is characterized by comprising the following steps:
(1) Melting master alloy or different metal raw materials with determined components in a vacuum induction melting furnace to form a high-temperature alloy melt;
(2) Releasing an additive containing a target element onto the melt surface;
(3) After the surface of the melt is stabilized, maintaining the smelting atmosphere for refining to ensure that the target elements are applied to the melt according to the designed components;
(4) And after refining, adjusting the temperature of the melt to the pouring temperature, and pouring.
2. The method for adding trace metal elements to the superalloy in a controlled release manner based on the efficient solid-liquid reaction according to claim 1, wherein in the step (1), the master alloy is a nickel-based, cobalt-based or iron-based superalloy, and the different metal raw materials refer to a simple substance and an alloy thereof of one or more than two elements of Ni, fe, co, cr, W, mo, ti, al, V, C, B, ta, re, nb, ru and Pt contained in the superalloy.
3. The method for adding trace metal elements to the high-temperature alloy in a controlled release manner based on the efficient solid-liquid reaction as claimed in claim 2, wherein the master alloy or different metal raw materials contain a part of target elements: one or more than two of rare earth elements, hf and Zr, and relevant elements are supplemented by additives; or the master alloy or different metal raw materials do not contain the target element, the target element-containing additive is completely added, and one or more than two of rare earth elements, hf and Zr are added into the high-temperature alloy melt at one time through the additive.
4. The method for adding trace metal elements to superalloy with controlled release based on high efficiency solid-liquid reaction as claimed in claim 1, wherein in step (2), the additive containing target element comprises oxide, carbonate or their combination containing target element.
5. The method for adding trace metal elements to the high-temperature alloy in a controlled release manner based on the efficient solid-liquid reaction as claimed in claim 4, wherein the additive containing the target elements is specifically: 1) Additive for adding La element: laH 2 、La 2 O 3 、La 2 (CO 3 ) 3 ·xH 2 O、La(OH) 3 、LaC 2 One or more than two of (a); 2) Additive for adding Y element: y is 2 O 3 、Y 2 (CO 3 ) 2 、Y(OH) 3 、YH 3 、YC 2 One or more than two of the above; 3) Additive added with Ce element: ce 2 O 3 、CeO 1.72 、CeO 1.83 、CeO 2 、Ce 2 (CO 3 ) 2 、Ce(OH) 3 、CeC 2 One or more than two of the above; 4) Additive for adding Zr element: zrH 2 、ZrO 2 、Zr(OH) 4 、ZrC、Zr(CO 3 ) 2 、Zr(CH 3 COO) 4 One or more than two of the above; 5) Additive for adding Hf element: hfH 2 、HfO 2 、H 4 HfO 4 、HfC 2 、HfO 2 ·CO 2 ·xH 2 One or more than two of O; the addition of one element is realized by utilizing the combination of different substances in the elements and sequentially adding one or more than two trace elements through the combination of different additives.
6. The method for adding trace metal elements to the high-temperature alloy in a controlled release manner based on the efficient solid-liquid reaction is characterized in that in the step (2), the additives are added in a solid state form and keep the solid state in the smelting process, the release of the target elements is realized in a solid-liquid reaction form with the melt, and the solid state form is powder with different particle sizes, blocks with different shapes or a combination of the powder and the blocks; the particle size of the powder is 0.01 mu m-5 mm, and the block shape comprises a spherical shape, a rod shape or a porous framework shape.
7. The method for adding trace metal elements to the high-temperature alloy in the controlled release manner based on the efficient solid-liquid reaction as claimed in claim 6, wherein the powder additive is directly added into the melt to carry out the in-situ solid-liquid reaction after being mixed; the block additive is subjected to a molding-sintering process to maintain the shape and strength, and the process for preparing the block additive comprises the following steps: molding under the pressure of 5-200 MPa, and sintering and molding at the temperature of 1300-1700 ℃ for 0.5-10 h.
8. The method for adding trace metal elements to the high-temperature alloy in a controlled release manner based on the efficient solid-liquid reaction according to claim 1, wherein in the step (3), the smelting atmosphere refers to an inert atmosphere with the pressure of 1000-100000 Pa or a vacuum atmosphere with the pressure of 0.001-50000 Pa, the refining temperature is 1400-1700 ℃, and the refining time is 1-300 min.
9. The method for adding trace metal elements to the high-temperature alloy in a controlled release manner based on the efficient solid-liquid reaction according to claim 1, wherein in the step (4), the pouring temperature refers to the temperature of the melt in the actual pouring process within the range of 1350-1500 ℃.
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