CN112359251A - Preparation method and application of nickel-chromium-tungsten intermediate alloy - Google Patents
Preparation method and application of nickel-chromium-tungsten intermediate alloy Download PDFInfo
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- CN112359251A CN112359251A CN202011240648.8A CN202011240648A CN112359251A CN 112359251 A CN112359251 A CN 112359251A CN 202011240648 A CN202011240648 A CN 202011240648A CN 112359251 A CN112359251 A CN 112359251A
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
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- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
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- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
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Abstract
The invention belongs to the field of high-temperature alloy master alloy purification smelting and casting, and particularly relates to a preparation method and application of a nickel-chromium-tungsten intermediate alloy for high-W nickel-based high-temperature alloy smelting. Cr and W are subjected to vacuum induction melting and a proper amount of Al simple substance is added for pre-alloying treatment to prepare Ni-Cr-W three-principal-element master alloy, and then master alloy is prepared through the master alloy. The components of the intermediate alloy can be flexibly designed according to the Cr/W ratio in the master alloy, and the aim of not adding Cr and W simple substances during smelting of the master alloy is achieved. The method is suitable for smelting most of high-W nickel-based high-temperature alloy master alloys, can improve the homogenization degree of elements easy to segregate such as Cr, W and the like while ensuring the purity degree of the alloys, reduces the burning loss rate of the volatile elements, greatly improves the metallurgical quality of the master alloys, and has obvious economic benefit.
Description
Technical Field
The invention belongs to the field of high-temperature alloy master alloy purification smelting and casting, and particularly relates to a preparation method and application of a nickel-chromium-tungsten intermediate alloy for high-W nickel-based high-temperature alloy smelting.
Background
The nickel-based high-temperature alloy is mainly used for manufacturing hot end parts of engines in the fields of aviation, aerospace, ships and the like, and the alloy is required to have excellent high-temperature oxidation resistance, corrosion resistance and high-temperature mechanical property. Wherein Cr in the alloy can form an oxide film on the surface of the part during the service period of the part, and the high-temperature oxidation resistance of the part is improved, so that a large amount of Cr elements are often added in the nickel-based high-temperature alloy during component design, and the average Cr content in most of the nickel-based high-temperature alloys is higher than 8 wt%. However, Cr element is easy to form brittle CrN particles during alloy smelting, the melting point of the CrN particles is about 1770 ℃ and higher than that of a nickel-based alloy, so that CrN in a master alloy is difficult to eliminate during remelting and casting, and nitride particles in a casting are easy to become crack sources during service of the alloy, and the high-temperature mechanical properties of the alloy are seriously influenced, so that the gas content in the master alloy is generally controlled at a low level. Common methods for reducing the gas content of the master alloy include increasing the refining temperature during the smelting of the master alloy, selecting a Cr simple substance with lower gas content, preparing a high Cr intermediate alloy and the like. But the overhigh refining temperature can increase the burning loss rate of elements with higher vapor pressure, such as Al, Ti and the like, and is not beneficial to component control, and can cause the crucible to decompose and reduce the purity of the alloy; at present, degassed Cr with low gas content is high in price, and the large-scale replacement of electrolytic Cr and common Cr inevitably increases the manufacturing cost of the master alloy, so that the large-scale production is not facilitated; the high Cr intermediate alloy prepared by vacuum smelting can effectively reduce the gas content in the simple substance Cr, and the Cr and the matrix elements form short-range ordered arrangement by pre-alloying treatment, thereby being beneficial to the homogenization of alloy components.
W has excellent solid solution strengthening capacity, can greatly improve the high-temperature mechanical property of the alloy, and has lower price compared with noble metals such as Re, Ru and the like. Therefore, the high-W nickel-based alloy has a very great development potential and is gradually emphasized by material research workers in various countries in recent years, representative high-W alloys in China include K416B, K419, K465 and the like, and the average W content is more than 10%. However, the diffusion coefficient of the element W is low, and the melting point of the element W is higher than that of most elements in the master alloy, so that the simple substance W is easy to be incompletely cleaned during smelting, a large amount of W-rich phase is further formed, and the element W is easy to generate serious segregation behavior during solidification, so that the concentration distribution of W is uneven, and the use of the element W in the fixed-length cutting of the alloy is not facilitated. By preparing the W-containing high-temperature alloy, the W and the matrix element can form a solid solution with a lower melting point through pre-alloying, which is beneficial to smelting and refining and homogenizing alloy components.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a preparation method and application of a nickel-chromium-tungsten intermediate alloy.
The technical solution adopted by the invention is as follows:
the preparation method of the nickel-chromium-tungsten intermediate alloy comprises the following components in percentage by weight: 15-20 parts of Cr, 20-25 parts of W, 1-2 parts of Al and the balance of Ni;
the preparation method comprises the following steps:
(1) mixing Ni, Cr, W and Al according to the Cr/W ratio in the master alloy and satisfying the formula (1);
in the formula, XNiRepresents the atomic fraction (at.%) of Ni, XCrRepresents the atomic fraction (at.%) of Cr, XWAtomic fraction (at.%) representing W;
(2) putting Ni, Cr and W into a crucible, putting the Cr and W in the center of the crucible, and surrounding the crucible by a Ni plate;
(3) the Ni, Cr and W in the crucible are dissolved and cleaned in a vacuum induction furnace until the vacuum degree is stabilized to 10-2Carrying out high-temperature refining at a temperature below Pa for 5-30 min, wherein the high-temperature refining temperature is higher than that of a liquid phaseLine 80-100 ℃;
(4) after the high-temperature refining is finished, power is cut off and the temperature is reduced to +/-10 ℃ of a liquidus line of the alloy, power supply is recovered and heat preservation is carried out, at the moment, an Al simple substance is added into the crucible, and after the surface of the melt is stable, the melt is kept stand for 1-5 min;
(5) increasing the temperature of the melt to 10-30 ℃ higher than the liquidus line, carrying out low-temperature refining for 5-40 min, and then increasing the temperature of the melt by 10 ℃ for casting;
(6) and after the intermediate alloy ingot is cooled, cutting off a dead head or removing a primary shrinkage cavity part, and polishing the surface to be bright for later use.
The application of the nickel-chromium-tungsten intermediate alloy and the method for smelting the master alloy by using the nickel-chromium-tungsten intermediate alloy comprise the following steps:
(1) calculating and cutting a nickel-chromium-tungsten intermediate alloy block according to the designed addition mass of Cr and W in the master alloy, wherein the cutting principle is that no Cr and W element simple substances are added during the smelting of the master alloy;
(2) supplementing other simple substance raw materials in the master alloy;
(3) loading the nickel-chromium-tungsten intermediate alloy and other simple substances except Al and Ti into a crucible, wherein the furnace burden in the crucible comprises the following steps from bottom to top: nickel layer → Ni-Cr-W intermediate alloy block layer → other simple substance raw material layer except Al, Ti and Ni → nickel layer;
(4) and smelting the master alloy, and casting the master alloy into a master alloy ingot to obtain the product master alloy.
The application of the nickel-chromium-tungsten intermediate alloy comprises the following components in percentage by weight: 9-13% of Co, 1.5-2.5% of Mo, 5-6% of Al, 5-10% of Cr, 9-11% of W, 0.1-0.2% of C, 1-3% of Ti, 0.5-3% of Nb, 0.1% of B, 0.1% of Zr and the balance of Ni.
The application of the nickel-chromium-tungsten intermediate alloy comprises the steps of smelting a master alloy, namely high-temperature refining → standing → low-temperature refining → casting.
The application of the nickel-chromium-tungsten intermediate alloy comprises the following steps of high-temperature refining: the raw material in the crucible is put in a vacuum induction furnace until the vacuum degree is stabilized to 10-2And (3) carrying out high-temperature refining below Pa, wherein the refining temperature is 80-100 ℃ higher than the liquidus, and the high-temperature refining time is 3-40 min.
The relationship between the high-temperature refining time t and the charging mass m of the nickel-chromium-tungsten intermediate alloy is as follows: when the mass of the charging material is less than or equal to 10kg, refining for 3-5 min; when the mass of the charging material is less than or equal to 25kg and 10kg, refining for 5-10 min; when the mass of the charged material is less than or equal to 50kg and 25kg, refining for 10-20 min; when the mass of the charged material is less than or equal to 200kg and 50kg, refining for 20-30 min; when the mass of the charging material is more than 200kg, the refining time is 30-40 min.
The application of the nickel-chromium-tungsten intermediate alloy comprises the following steps of: and after the high-temperature refining is finished, stopping power and cooling to +/-10 ℃ of a phase line of the alloy, recovering power supply and preserving heat, adding Al and Ti simple substances into the crucible at the moment, and standing for 1-5 min after the surface of the melt is stable.
The application of the nickel-chromium-tungsten intermediate alloy comprises the following steps of low-temperature refining: and (3) increasing the temperature of the melt to be 10-30 ℃ higher than the liquidus line, and carrying out low-temperature refining for 5-60 min.
The application of the nickel-chromium-tungsten intermediate alloy has the following relationship between the low-temperature refining time t and the charging mass m: when the mass of the charging material is less than or equal to 10kg, refining for 5-10 min; when the mass of the charged material is less than or equal to 25kg and 10kg, refining for 10-20 min; when the mass of the charged material is less than or equal to 50kg and 25kg, refining for 20-30 min; when the mass of the charged material is less than or equal to 200kg and 50kg, refining for 30-40 min; when the mass of the charging material is more than 200kg, the refining time is 40-60 min.
The application of the nickel-chromium-tungsten intermediate alloy comprises the following steps: after low-temperature refining, the temperature of the melt is increased by 10 ℃ for casting.
The design idea of the invention is as follows:
the invention prepares the Ni-Cr-W three-principal-element master alloy by carrying out vacuum induction melting on Cr and W and adding a proper amount of Al simple substance for prealloying treatment, and then prepares the master alloy by the master alloy. The components of the intermediate alloy can be flexibly designed according to the Cr/W ratio in the master alloy, and the aim of not adding Cr and W simple substances during smelting of the master alloy is achieved. Because the elementary substances Cr and W are purified and alloyed once when the master alloy is smelted, the gas content of the master alloy can be kept at a lower level, and the Cr and W in the master alloy can form a solid solution of Ni, so that the homogenization of the components of the Cr and W is facilitated, the smelting time of the master alloy can be shortened, the burning loss behavior of other volatile elements during smelting is effectively improved, and the component control of the master alloy is facilitated.
When the Ni-Cr-W intermediate alloy is designed, the atomic fractions (at.%) of Ni, Cr and W need to satisfy the following conditions:
meanwhile, the Cr/W ratio in the master alloy is equal to that in the target master alloy, and Al element with the concentration not higher than 2 at% can be added when the master alloy is designed, wherein the Al element is introduced for improving the degassing and impurity removal level during the smelting of the master alloy, and Al is one of important main elements in the nickel-based high-temperature alloy, so that the new impurity is not required to be introduced.
The invention has the advantages and positive effects that:
compared with the prior art, the purity of the master alloy is improved, O, N, S is controlled at a lower level, the uniformity of Cr and W elements is improved, the melting point of the intermediate alloy is similar to that of the master alloy, the smelting time is shortened, the burning loss of volatile elements is reduced, and the control of components is facilitated. The invention is suitable for smelting most of nickel-based high-temperature alloys with high W content, can freely adjust the components of the intermediate alloy according to the Cr/W ratio in the master alloy, and has the advantages of flexibility, changeability and strong practicability.
Drawings
FIG. 1 is a schematic view of charging when master alloys are smelted using master alloys. In the figure, 1, a nickel layer, 2, a Ni-Cr-W intermediate alloy block layer, 3, another simple substance raw material layer, 4 and a nickel layer.
Detailed Description
In the specific implementation process, the invention adopts vacuum smelting to prepare the intermediate alloy ingot, the prepared intermediate alloy ingot is cut off a dead head and polished to remove the surface oxide skin, then the intermediate alloy ingot with the corresponding weight is weighed by taking the designed addition of the W element as a standard, and is added into a crucible along with other main elements to carry out master alloy smelting, thereby obtaining the master alloy ingot with the corresponding components.
The nickel-chromium-tungsten intermediate alloy comprises the following components in percentage by weight: 15-20% of Cr, 20-25% of W, 1-2% of Al and the balance of Ni. The preparation method of the nickel-chromium-tungsten intermediate alloy comprises the following steps:
(1) preparing raw materials of Ni, Cr, W, Al and the like according to the Cr/W ratio in the master alloy and meeting the formula (1);
in the formula, XNiRepresents the atomic fraction (at.%) of Ni, XCrRepresents the atomic fraction (at.%) of Cr, XWRepresents the atomic fraction (at.%) of W.
(2) Putting Ni, Cr and W into a crucible, putting Cr and W in the center of the crucible, and surrounding the crucible by a Ni plate, wherein the Ni plate has the following functions: the refractory elements are placed in a high-temperature area, so that the refractory metals can be conveniently melted and alloyed, and the phenomenon of macrosegregation of the intermediate alloy during smelting is effectively avoided;
(3) the Ni, Cr and W in the crucible are dissolved and cleaned in a vacuum induction furnace until the vacuum degree is stabilized to 10-2Carrying out high-temperature refining at the temperature of 80-100 ℃ higher than the liquidus line after Pa for 5-30 min, wherein the refining temperature is as follows: the method has the advantages that gas elements such as O, N and the like in the metal raw material are effectively removed, the generated low-melting-point slag is volatilized and removed, in addition, the uniformity of alloy components is improved under the action of high temperature and electromagnetic stirring, and the purposes of purifying and homogenizing the alloy melt are achieved;
(4) after the high-temperature refining is finished, power is cut off and the temperature is reduced to +/-10 ℃ of a phase line of the alloy liquid, power supply is recovered and heat is preserved, at the moment, an Al simple substance is added into the crucible, and after the surface of the melt is stable, the melt is kept stand for 1-5 min, and the high-temperature refining furnace has the following functions: the splashing of the Al simple substance which is violently reacted with the high-temperature melt during the adding period is reduced, and the control precision of the alloy components is improved; meanwhile, the floating of nonmetallic inclusion is facilitated in the standing process, and the purity of the melt is improved;
(5) and (2) increasing the temperature of the melt to 10-30 ℃ higher than the liquidus line for low-temperature refining for 5-40 min, and then increasing the temperature of the melt by 10 ℃ for casting, wherein the method has the following functions: the principle that the solubility of gas is reduced along with the reduction of temperature is utilized to further degas, which is beneficial to the full floating of nonmetallic inclusions and improves the purity of the melt; meanwhile, the proper casting temperature can ensure the surface smoothness and the internal no shrinkage cavity of the alloy cast ingot, and the metallurgical quality of the cast ingot is improved;
(6) and after the intermediate alloy ingot is cooled, cutting off a dead head (or removing a primary shrinkage cavity part) and polishing the surface for later use.
The components and contents of the product master alloy are as follows in percentage by weight: 9-13% of Co, 1.5-2.5% of Mo, 5-6% of Al, 5-10% of Cr, 9-11% of W, 0.1-0.2% of C, 1-3% of Ti, 0.5-3% of Nb, 0.1% of B, 0.1% of Zr and the balance of Ni. The method for smelting the master alloy by using the nickel-chromium-tungsten intermediate alloy comprises the following steps:
(1) calculating and cutting a proper nickel-chromium-tungsten intermediate alloy block according to the designed addition mass of Cr or W in the master alloy, wherein the cutting principle is that elementary substances such as Cr, W and the like are not added during the smelting of the master alloy;
(2) supplementing other simple substance raw materials in the master alloy;
(3) as shown in fig. 1, a nickel-chromium-tungsten intermediate alloy and other simple substances are loaded into a crucible, and the furnace burden in the crucible comprises the following materials in sequence from bottom to top: nickel layer 1 → Ni-Cr-W intermediate alloy bulk layer 2 → other elemental material layer 3 (e.g. Co, C, Nb, etc.) other than Al, Ti → nickel layer 4, which functions as: the high-temperature induction zone is fully utilized to fully melt and alloy the refractory metal, the C element is used for degassing the alloy melt, and the degassing efficiency and the component homogenization degree are improved under the action of electromagnetic stirring;
(4) and smelting the master alloy, and casting the master alloy into a master alloy ingot to obtain the product master alloy.
High-temperature refining: the raw material in the crucible is put in a vacuum induction furnace until the vacuum degree is stabilized to 10-2Carrying out high-temperature refining at the temperature of 80-100 ℃ higher than the liquidus line for 3-40 min after Pa, wherein the refining time is as follows: effectively removing O, N and other gas elements in the metal raw material, and enabling the generated low-melting-point slag to enterVolatilization is removed, and in addition, the uniformity of alloy components is improved under the action of high temperature and electromagnetic stirring, so that the purposes of purifying and homogenizing the alloy melt are achieved;
the relationship between the high-temperature refining time t and the charging mass m is as follows: when the mass of the charging material is less than or equal to 10kg, refining for 3-5 min; when the mass of the charging material is less than or equal to 25kg and 10kg, refining for 5-10 min; when the mass of the charged material is less than or equal to 50kg and 25kg, refining for 10-20 min; when the mass of the charged material is less than or equal to 200kg and 50kg, refining for 20-30 min; when the mass of the charging material is more than 200kg, the refining time is 30-40 min.
Standing: after the high-temperature refining is finished, power is cut off and the temperature is reduced to +/-10 ℃ of a phase line of the alloy, power supply is restored and heat is preserved, at the moment, Al and Ti simple substances are added into the crucible, and after the surface of the melt is stable, the melt is kept stand for 1-5 min, and the crucible has the following effects: the splashing of the Al simple substance which is violently reacted with the high-temperature melt during the adding period is reduced, and the control precision of the alloy components is improved; secondly, floating of nonmetallic inclusions is facilitated in the standing process, and the purity of the melt is improved;
low-temperature refining and casting: the melt temperature is increased to 10-30 ℃ higher than the liquidus line for low-temperature refining, then the melt temperature is increased by 10 ℃ for casting, the low-temperature refining time is 5-60 min, and the method has the following effects: further degassing is carried out by utilizing the principle that the gas solubility is reduced along with the reduction of the temperature, and simultaneously, the full floating of nonmetallic inclusions is facilitated, and the purity of the alloy melt is improved.
The relationship between the low-temperature refining time t and the charging mass m is as follows: when the mass of the charging material is less than or equal to 10kg, refining for 5-10 min; when the mass of the charged material is less than or equal to 25kg and 10kg, refining for 10-20 min; when the mass of the charged material is less than or equal to 50kg and 25kg, refining for 20-30 min; when the mass of the charged material is less than or equal to 200kg and 50kg, refining for 30-40 min; when the mass of the charging material is more than 200kg, the refining time is 40-60 min.
The intermediate alloy prepared by the invention can avoid the pollution of raw materials caused by the contact of a Cr element simple substance with air after long-term storage, improve the component uniformity of W in the W alloy, and the Al element added in the intermediate alloy has stronger degasification property, so that the gas content of the intermediate alloy can be reduced to a lower level, the purity of the raw materials is improved, and the intermediate alloy is suitable for scientific research and industrial production on various scales.
The present invention is described in detail below by way of examples:
example 1
In the embodiment, the smelting master alloy is K465, and the smelting mass is 10 kg.
Design composition of master alloy-1:
| element(s) | Content (wt.%) |
| Cr | 17.6 |
| W | 20.0 |
| Al | 1.00 |
| Ni | Bal. |
Preparation process of intermediate alloy (smelting in 10kg vacuum induction furnace with vacuum degree of 4X 10)-3Pa)：
High-temperature refining: refining at 1600 deg.C for 5 min;
secondly, after the temperature of the melt is reduced to 1530 ℃, adding an Al simple substance, and standing for 1min after the liquid level is stable;
③ refining at low temperature: refining temperature is 1540 ℃, and refining time is 5 min;
casting temperature: 1550 ℃.
The O content of the master alloy-1 was found to be 16ppm and the N content was found to be 3 ppm.
The master alloy comprises the following ingredients:
| element(s) | Content (wt.%) |
| Co | 9.5 |
| Mo | 1.8 |
| Al | 5.1 |
| Intermediate alloy | 50.0 |
| C | 0.15 |
| Ti | 2.5 |
| Nb | 1.0 |
| Ni | Bal. |
Master alloy smelting process (10kg vacuum induction furnace smelting, vacuum degree 2X 10)-3Pa)：
High-temperature refining: refining at 1500 deg.C for 5 min;
secondly, when the temperature of the melt is reduced to 1450 ℃, adding Al and Ti simple substances, and standing for 1min after the liquid level is stable;
③ refining at low temperature: refining at 1420 deg.C for 5 min;
casting temperature: 1430 ℃.
The alloy chemical composition of the product is measured as follows:
| element(s) | Content (wt.%) |
| Co | 9.48 |
| Mo | 1.82 |
| Al | 5.15 |
| Cr | 8.82 |
| W | 9.98 |
| C | 0.15 |
| Ti | 2.41 |
| Nb | 1.05 |
| Ni | Bal. |
The O content of the product was found to be 5ppm, the N content to be 2ppm and the S content to be 3 ppm.
Example 2
In the embodiment, the smelting master alloy is K465, and the smelting mass is 50 kg.
Design composition of master alloy-1:
| element(s) | Content (wt.%) |
| Cr | 17.6 |
| W | 20.0 |
| Al | 1.00 |
| Ni | Bal. |
Preparation process of intermediate alloy (smelting in 50kg vacuum induction furnace with vacuum degree of 8X 10)-3Pa)：
High-temperature refining: refining temperature is 1600 ℃, and refining time is 15 min;
secondly, after the temperature of the melt is reduced to 1530 ℃, adding an Al simple substance, and standing for 1min after the liquid level is stable;
③ refining at low temperature: refining at 1540 ℃ for 20 min;
casting temperature: 1550 ℃.
The content of O and the content of N in the master alloy-1 were found to be 18ppm and 3ppm, respectively.
The master alloy comprises the following ingredients:
| element(s) | Content (wt.%) |
| Co | 9.5 |
| Mo | 1.8 |
| Al | 5.1 |
| Intermediate alloy | 50.0 |
| C | 0.15 |
| Ti | 2.5 |
| Nb | 1.0 |
| Ni | Bal. |
Master alloy smelting process (50kg vacuum induction furnace smelting, 6X 10 vacuum degree)-3Pa)：
High-temperature refining: refining at 1500 deg.C for 15 min;
secondly, when the temperature of the melt is reduced to 1450 ℃, adding Al and Ti simple substances, and standing for 2min after the liquid level is stable;
③ refining at low temperature: refining at 1420 deg.C for 20 min;
casting temperature: 1430 ℃.
The cast product has the size phi of 80 mm multiplied by 900mm3The alloy chemical composition of the product is measured as follows:
the master alloy was measured to have an O content of 5ppm, an N content of 2ppm, and an S content of 3ppm, wherein the W content near the riser was 10.13 wt.%, and the W content at the bottom was 9.92 wt.%.
Example 3
In this example, the smelting master alloy is of grade K419, and the smelting mass is 50 kg.
Design composition of master alloy-1:
| element(s) | Content (wt.%) |
| Cr | 15.0 |
| W | 25.0 |
| Al | 1.00 |
| Ni | Bal. |
Preparation process of intermediate alloy (vacuum induction furnace smelting, vacuum degree 6X 10)-3Pa)：
High-temperature refining: refining at 1600 deg.C for 5 min;
secondly, after the temperature of the melt is reduced to 1530 ℃, adding an Al simple substance, and standing for 1min after the liquid level is stable;
③ refining at low temperature: refining temperature is 1540 ℃, and refining time is 5 min;
casting temperature: 1550 ℃.
The O content of the master alloy 1 was found to be 19ppm, and the N content was found to be 4 ppm.
The master alloy comprises the following ingredients:
master alloy smelting process (50kg vacuum induction furnace smelting, vacuum degree 4X 10)-3Pa)：
High-temperature refining: refining at 1500 deg.C for 15 min;
secondly, when the temperature of the melt is reduced to 1450 ℃, adding Al and Ti simple substances, and standing for 1min after the liquid level is stable;
③ refining at low temperature: refining at 1420 deg.C for 20 min;
casting temperature: 1430 ℃.
The cast product has the size phi of 80 mm multiplied by 900mm3The alloy chemical composition of the product is measured as follows:
| element(s) | Content (wt.%) |
| Co | 12.08 |
| Mo | 2.02 |
| Al | 5.22 |
| Cr | 5.91 |
| W | 10.05 |
| C | 0.10 |
| Ti | 1.12 |
| Nb | 3.00 |
| B | 0.08 |
| Zr | 0.05 |
| Ni | Bal. |
The master alloy was measured to have an O content of 6ppm, an N content of 4ppm and an S content of 2ppm, wherein the W content near the riser and the bottom was measured to be 9.9 wt.% and 10.05 wt.%, respectively.
The embodiment result shows that the method is suitable for smelting most of high-W nickel-based high-temperature alloy master alloys, can improve the homogenization degree of elements easy to segregate such as Cr, W and the like while ensuring the purity degree of the alloys, reduces the burning loss rate of volatile elements, greatly improves the metallurgical quality of the master alloys, and has obvious economic benefit.
Claims (10)
1. The preparation method of the nickel-chromium-tungsten intermediate alloy is characterized in that the nickel-chromium-tungsten intermediate alloy comprises the following components in percentage by weight: 15-20 parts of Cr, 20-25 parts of W, 1-2 parts of Al and the balance of Ni;
the preparation method comprises the following steps:
(1) mixing Ni, Cr, W and Al according to the Cr/W ratio in the master alloy and satisfying the formula (1);
in the formula, XNiRepresents the atomic fraction (at.%) of Ni, XCrRepresents the atomic fraction (at.%) of Cr, XWAtomic fraction (at.%) representing W;
(2) putting Ni, Cr and W into a crucible, putting the Cr and W in the center of the crucible, and surrounding the crucible by a Ni plate;
(3) the Ni, Cr and W in the crucible are dissolved and cleaned in a vacuum induction furnace until the vacuum degree is stabilized to 10-2Carrying out high-temperature refining at the temperature of 80-100 ℃ higher than the liquidus line after Pa for 5-30 min;
(4) after the high-temperature refining is finished, power is cut off and the temperature is reduced to +/-10 ℃ of a liquidus line of the alloy, power supply is recovered and heat preservation is carried out, at the moment, an Al simple substance is added into the crucible, and after the surface of the melt is stable, the melt is kept stand for 1-5 min;
(5) increasing the temperature of the melt to 10-30 ℃ higher than the liquidus line, carrying out low-temperature refining for 5-40 min, and then increasing the temperature of the melt by 10 ℃ for casting;
(6) and after the intermediate alloy ingot is cooled, cutting off a dead head or removing a primary shrinkage cavity part, and polishing the surface to be bright for later use.
2. The use of the nickel-chromium-tungsten master alloy according to claim 1, wherein the method for smelting the master alloy by using the nickel-chromium-tungsten master alloy comprises the following steps:
(1) calculating and cutting a nickel-chromium-tungsten intermediate alloy block according to the designed addition mass of Cr and W in the master alloy, wherein the cutting principle is that no Cr and W element simple substances are added during the smelting of the master alloy;
(2) supplementing other simple substance raw materials in the master alloy;
(3) loading the nickel-chromium-tungsten intermediate alloy and other simple substances except Al and Ti into a crucible, wherein the furnace burden in the crucible comprises the following steps from bottom to top: nickel layer → Ni-Cr-W intermediate alloy block layer → other simple substance raw material layer except Al, Ti and Ni → nickel layer;
(4) and smelting the master alloy, and casting the master alloy into a master alloy ingot to obtain the product master alloy.
3. The use of a nickel chromium tungsten master alloy according to claim 2, characterized in that the composition and content of the product master alloy are as follows, in weight percent: 9-13% of Co, 1.5-2.5% of Mo, 5-6% of Al, 5-10% of Cr, 9-11% of W, 0.1-0.2% of C, 1-3% of Ti, 0.5-3% of Nb, 0.1% of B, 0.1% of Zr and the balance of Ni.
4. Use of a nickel chromium tungsten intermediate alloy according to claim 2, characterised in that the smelting of the master alloy comprises high temperature refining → standing → low temperature refining → casting.
5. Use of a nickel chromium tungsten master alloy according to claim 4, characterized in that the high temperature refining: the raw material in the crucible is put in a vacuum induction furnaceThe vacuum degree is stabilized to 10-2And (3) carrying out high-temperature refining below Pa, wherein the refining temperature is 80-100 ℃ higher than the liquidus, and the high-temperature refining time is 3-40 min.
6. The use of a nickel chromium tungsten master alloy according to claim 5, characterized in that the high temperature refining time t is related to the charge mass m as follows: when the mass of the charging material is less than or equal to 10kg, refining for 3-5 min; when the mass of the charging material is less than or equal to 25kg and 10kg, refining for 5-10 min; when the mass of the charged material is less than or equal to 50kg and 25kg, refining for 10-20 min; when the mass of the charged material is less than or equal to 200kg and 50kg, refining for 20-30 min; when the mass of the charging material is more than 200kg, the refining time is 30-40 min.
7. Use of a nickel chromium tungsten intermediate alloy according to claim 4, characterized in that the rest: and after the high-temperature refining is finished, stopping power and cooling to +/-10 ℃ of a phase line of the alloy, recovering power supply and preserving heat, adding Al and Ti simple substances into the crucible at the moment, and standing for 1-5 min after the surface of the melt is stable.
8. Use of a nickel chromium tungsten master alloy according to claim 4, characterized by low temperature refining: and (3) increasing the temperature of the melt to be 10-30 ℃ higher than the liquidus line, and carrying out low-temperature refining for 5-60 min.
9. The use of a nickel chromium tungsten master alloy according to claim 8, characterized in that the low temperature refining time t is related to the charge mass m as follows: when the mass of the charging material is less than or equal to 10kg, refining for 5-10 min; when the mass of the charged material is less than or equal to 25kg and 10kg, refining for 10-20 min; when the mass of the charged material is less than or equal to 50kg and 25kg, refining for 20-30 min; when the mass of the charged material is less than or equal to 200kg and 50kg, refining for 30-40 min; when the mass of the charging material is more than 200kg, the refining time is 40-60 min.
10. Use of a nickel chromium tungsten master alloy according to claim 4, characterized in that the casting: after low-temperature refining, the temperature of the melt is increased by 10 ℃ for casting.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113528924A (en) * | 2021-07-23 | 2021-10-22 | 承德天大钒业有限责任公司 | Nickel-niobium-chromium intermediate alloy and preparation method thereof |
| CN116990107A (en) * | 2023-06-08 | 2023-11-03 | 辽宁红银金属有限公司 | Cobalt-based superalloy standard sample and preparation method thereof |
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| CN110387488A (en) * | 2018-04-20 | 2019-10-29 | 北京科大京都高新技术有限公司 | A kind of heating furnace high temperature alloy |
| CN110735067A (en) * | 2019-11-28 | 2020-01-31 | 中国科学院金属研究所 | Purification smelting process of nickel-based high-temperature alloys rich in active elements |
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| CN116990107A (en) * | 2023-06-08 | 2023-11-03 | 辽宁红银金属有限公司 | Cobalt-based superalloy standard sample and preparation method thereof |
| CN116990107B (en) * | 2023-06-08 | 2024-05-24 | 辽宁红银金属有限公司 | Cobalt-based superalloy standard sample and preparation method thereof |
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