CN111118318A - Method for deoxidizing nickel-based superalloy - Google Patents
Method for deoxidizing nickel-based superalloy Download PDFInfo
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- CN111118318A CN111118318A CN202010094544.4A CN202010094544A CN111118318A CN 111118318 A CN111118318 A CN 111118318A CN 202010094544 A CN202010094544 A CN 202010094544A CN 111118318 A CN111118318 A CN 111118318A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/023—Alloys based on nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3033—Ni as the principal constituent
- B23K35/304—Ni as the principal constituent with Cr as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- 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
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/053—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 30% but less than 40%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- 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
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for deoxidizing a nickel-based superalloy, which comprises the following steps: selecting smelting raw materials; an Inconel690 alloy ingot is smelted by adopting a ZG-0.025 type vacuum induction smelting furnace, and the process parameters are as follows: vacuumizing to 0.01Pa, and 10-15 kW: 10-20 min; 20-25 kW until melting; refining for 10min under the condition that the vacuum degree is less than or equal to 0.1Pa, and electromagnetically stirring; reducing the vacuum power to 5kW, freezing, deflating, heating again, and repeating for 2-3 times; introducing high-purity argon in high vacuum, adjusting the temperature, adding deoxidizing elements, namely rare earth lanthanum and magnesium, electromagnetically stirring, adding microalloying elements, namely silicon, aluminum, titanium, niobium and molybdenum and volatile element manganese, and electromagnetically stirring; reducing power, pouring, cooling, taking out the cast ingot, and cutting off a dead head. The ingot obtained by the invention has compact internal structure, uniform chemical components, no shrinkage cavity and shrinkage porosity, and the oxygen content of the ingot is less than or equal to 10 ppm.
Description
Technical Field
The invention relates to the technical field of nickel-based superalloy deoxidation, in particular to a deoxidation method of vacuum induction melting, prefabrication of a magnesium oxide crucible and addition of rare earth lanthanum and magnesium.
Background
The nickel-based alloy has excellent corrosion resistance and high-temperature oxidation resistance, and is often used for equipment with harsh use conditions and high safety requirements. With the continuous and high-speed development of the economy of China, equipment manufacturing has already become the pillar industry of the economy of China, and the outstanding characteristics of the development of the equipment manufacturing industry are as follows: the parameters of the single machine equipment are higher and higher, the use conditions are more and more rigorous, and the requirements on the safety are higher and higher. Welding is a key manufacturing process in modern industry, and the quality of a welded joint is key to ensuring the safety of industrial equipment. In order to meet the increasing performance requirements of large-scale industrial equipment, the domestic demand for nickel-based welding materials is rapidly increased, and at present, the demand for the nickel-based welding materials is increased from 300-400 tons/year ten years ago to 3000-4000 tons/year, and the demand is increased by ten times.
The high sensitivity of welding cracks, the great influence of trace elements on the performance of joints and the high sensitivity of welding pores are important characteristics of nickel-based welding materials and are also technical keys for material development. The main means for solving the technical problems is to strictly control the gas content and the component fluctuation of the welding material and strictly limit the content of impurity elements, namely to develop a high-purity welding material, and technically, vacuum smelting and refining processes (such as AOD, VOD, ESR and the like) are usually adopted. Due to the demand, domestic top-level steel enterprises have the technical capability of producing nickel-based welding materials, do not care about the development of the nickel-based welding materials, and do not have related products; and although a few small-sized enterprises pay attention to the market of the nickel-based welding material, the qualified special nickel-based welding material is difficult to develop due to limited technical strength, so that the existing nickel-based welding material basically depends on import.
Another characteristic of the nickel-based welding material is that the joint quality and the stability of the welding process are closely related, and the technical development trend is that the ratio of automatic welding is higher and higher, which not only requires that the welding material (such as a welding wire) meets the corresponding component requirements, but also requires that the welding wire has excellent process properties, such as the stability of the surface state, the geometric dimension and the physical properties of the welding wire. These requirements place higher demands on the manufacturing process of the welding wire, and new demands on the aspects of the surface roughness control, the surface coating of the welding wire, the wire drawing process and the like are placed. The technology is mastered by a few large international companies, so that products can smoothly enter the Chinese market; there is no related production experience in China, and in order to realize the localization of the nickel-based welding material, the key technology needs to be mastered through development and development.
The harm of oxygen in the nickel-based alloy is mainly reflected by: (1) the dissolved oxygen existing in the alloy melt oxidizes the added alloy elements, increases the element burning loss and improves the inclusion content. (2) In the solidification process, the separated oxygen reacts with carbon in the melt to generate carbon monoxide, so that air holes and porosity are formed in the cast ingot. (3) The oxygen precipitated by the temperature reduction oxidizes the alloying elements in the steel to form the endogenous inclusions. (4) Oxygen energy separated out in the form of ferrous oxide and ferrous sulfide form a low-melting-point eutectic substance in the solidification process, and the low-melting-point eutectic substance is distributed along a grain boundary, so that hot brittleness in steel ingot hot processing is caused. The shape, quantity, size and distribution of the inclusions have obvious influence on the processing performance and the service performance of the steel. Therefore, the control and reduction of the content of oxygen element are the key points of the vacuum smelting related technology and the nickel-based welding material technology, and the method is carried out aiming at the technical problem.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for deoxidizing a nickel-based superalloy, which can obtain a compact alloy ingot with ultralow oxygen content.
The invention is realized by the following technical scheme:
a method of deoxidizing a nickel-base superalloy, comprising:
(1) selecting smelting raw materials including pure iron, aurora nickel, metal chromium, metal molybdenum, silicon, metal manganese, metal niobium and titanium, pickling and derusting the surface of the pure iron, drying the raw materials, and drying an ingot mold, a heat preservation cap and a pouring cup at high temperature;
(2) an Inconel690 alloy ingot is smelted by adopting a ZG-0.025 type vacuum induction smelting furnace, and the process parameters are as follows: vacuumizing to 0.01Pa, and 10-15 kW: 10-20 min; 20-25 kW until melting; refining for 10min under the condition that the vacuum degree is less than or equal to 0.1Pa, and electromagnetically stirring; reducing the vacuum power to 5kW, freezing, deflating, heating again, and repeating for 2-3 times; introducing high-purity argon in high vacuum, adjusting the temperature, adding deoxidizing elements, namely rare earth lanthanum and magnesium, electromagnetically stirring, adding microalloying elements, namely silicon, aluminum, titanium, niobium and molybdenum and volatile element manganese, and electromagnetically stirring; reducing power, pouring, cooling, taking out the cast ingot, and cutting off a dead head.
The nickel-based high-temperature alloy comprises the following chemical components in percentage by weight: c is less than or equal to 0.03, Si is less than or equal to 0.50, Mn is less than or equal to 1.0, P is less than or equal to 0.005, S is less than or equal to 0.005, Cr: 28.0-31.5, Fe: 8.0-12.0, Mo is less than or equal to 0.5, Co is less than or equal to 0.10, Cu is less than or equal to 0.10, Ti is less than or equal to 1.0, Al is less than or equal to 1.1, Nb: 0.5-1.0, others are less than or equal to 0.5, Ni: a substrate.
The sum of the contents of the rare earth lanthanum and the magnesium in the nickel-based superalloy ingot is less than or equal to 0.02 percent by mass fraction.
The method is characterized in that a prefabricated magnesium oxide crucible is adopted in the smelting process, rare earth lanthanum and magnesium are added in the later stage of refining to greatly deoxidize, the electromagnetic stirring effect is utilized to further fully deoxidize, and the deoxidizing reaction is carried out on the interface between the inner surface of the crucible and the alloy liquid and the inner part and the upper surface of the alloy liquid.
The invention has the advantages that:
(1) the special smelting process and the prefabricated magnesium oxide crucible are adopted, carbon is pre-deoxidized, rare earth lanthanum and magnesium are added in the later period of refining, and the method can greatly deoxidize and has very important effect on obtaining Inconel690 low-content oxygen.
(2) The Inconel690 with ultralow oxygen content reduces the amount of oxide inclusions in the ingot and greatly improves the mechanical properties of the nickel-based alloy.
(3) The Inconel690 nickel-based welding material with ultralow oxygen content can be applied to important fields such as nuclear power and the like, and plays a role in promoting domestic welding materials.
(4) The Inconel690 nickel-based alloy deoxidation method is relatively low in cost and relatively easy to realize, and further plays a reference role in obtaining ultra-low oxygen content for other nickel-based alloys.
Detailed Description
Example (b):
selecting smelting raw materials including pure iron, aurora nickel, metal chromium, metal molybdenum, metal manganese, niobium and titanium, pickling and derusting the surface of the pure iron, drying the raw materials, adding the raw materials into a crucible, and drying the ingot mold, a heat preservation cap and a pouring cup at high temperature and putting the ingot mold, the heat preservation cap and the pouring cup into a hearth. An Inconel690 alloy ingot is smelted by adopting a ZG-0.025 type vacuum induction smelting furnace, and the process parameters are as follows: vacuumizing to 0.01Pa, 12 kW: 15 min; 22kW until melting; refining for 10min under the vacuum degree of 0.1Pa, and electromagnetically stirring; pre-deoxidizing by using carbon in the raw material; reducing the vacuum power to 5kW, freezing, deflating, heating again, and repeating for 3 times; introducing high-purity argon in high vacuum, adjusting the temperature, adding deoxidizing elements of rare earth lanthanum (0.01%) and magnesium (0.01%), electromagnetically stirring, adding microalloying elements of aluminum, titanium, niobium and molybdenum and volatile element of manganese, and electromagnetically stirring; reducing power, pouring, cooling, taking out the cast ingot, and cutting off a dead head. And (3) removing oxide skin on the surface of the cast ingot by a mechanical processing vehicle to obtain a smooth surface cast ingot, analyzing chemical elements, and finally forging and drawing the cast ingot into a welding wire with a certain specification.
The oxygen element analysis adopts an infrared absorption method (national standard GB/T11261-.
The chemical composition of the nickel-base superalloy ingot obtained in this example in wt% (mass fraction) is as follows: o: 0.0008, La: 0.0041, Mg: 0.005, S: 0.0010, P: 0.0015, N: 0.0015, H: 0.0002, C: 0.011, Si: 0.12, Mn: 0.71, Cr: 29.45, Fe: 9.78, Mo: 0.37, Co: 0.01, Cu: 0.005, Ti: 0.82, Al:0.75, Nb: 0.73, Ni: a substrate.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims.
Claims (3)
1. A method of deoxidizing a nickel-base superalloy, comprising:
(1) selecting smelting raw materials including pure iron, aurora nickel, metal chromium, metal molybdenum, silicon, metal manganese, metal niobium and titanium, pickling and derusting the surface of the pure iron, drying the raw materials, and drying an ingot mold, a heat preservation cap and a pouring cup at high temperature;
(2) an Inconel690 alloy ingot is smelted by adopting a ZG-0.025 type vacuum induction smelting furnace, and the process parameters are as follows: vacuumizing to 0.01Pa, and 10-15 kW: 10-20 min; 20-25 kW until melting; refining for 10min under the condition that the vacuum degree is less than or equal to 0.1Pa, and electromagnetically stirring; reducing the vacuum power to 5kW, freezing, deflating, heating again, and repeating for 2-3 times; introducing high-purity argon in high vacuum, adjusting the temperature, adding deoxidizing elements, namely rare earth lanthanum and magnesium, electromagnetically stirring, adding microalloying elements, namely silicon, aluminum, titanium, niobium and molybdenum and volatile element manganese, and electromagnetically stirring; reducing power, pouring, cooling, taking out the cast ingot, and cutting off a dead head.
2. The method of deoxidizing a nickel-base superalloy as in claim 1, wherein the nickel-base superalloy has a chemical composition in weight percent as follows: c is less than or equal to 0.03, Si is less than or equal to 0.50, Mn is less than or equal to 1.0, P is less than or equal to 0.005, S is less than or equal to 0.005, Cr: 28.0-31.5, Fe: 8.0-12.0, Mo is less than or equal to 0.5, Co is less than or equal to 0.10, Cu is less than or equal to 0.10, Ti is less than or equal to 1.0, Al is less than or equal to 1.1, Nb: 0.5-1.0, others are less than or equal to 0.5, Ni: a substrate.
3. The method of claim 1, wherein the ni-based superalloy ingot comprises 0.02% or less of the sum of the rare earth lanthanum and magnesium by mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202010094544.4A CN111118318A (en) | 2020-02-16 | 2020-02-16 | Method for deoxidizing nickel-based superalloy |
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| CN202010094544.4A CN111118318A (en) | 2020-02-16 | 2020-02-16 | Method for deoxidizing nickel-based superalloy |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112553403A (en) * | 2020-12-24 | 2021-03-26 | 广东石油化工学院 | Method for smelting and deoxidizing stainless steel welding material |
| CN112725659A (en) * | 2020-12-22 | 2021-04-30 | 丹阳市曙光镍材有限公司 | Nickel alloy casting process based on intermediate frequency furnace |
| CN113699399A (en) * | 2021-08-31 | 2021-11-26 | 山东瑞泰新材料科技有限公司 | Purifying smelting process of nickel-based high-temperature alloy without aluminum and titanium |
| CN114645161A (en) * | 2022-03-09 | 2022-06-21 | 中国地质大学（武汉） | High-oxidation-resistance nickel-based alloy block material and preparation method thereof |
| CN115305368A (en) * | 2022-07-20 | 2022-11-08 | 西安聚能高温合金材料科技有限公司 | Preparation method of Fe-Ni-Co-based high-temperature alloy GH907 alloy ingot |
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| CN103014388A (en) * | 2012-12-26 | 2013-04-03 | 中国科学院金属研究所 | Large-tonnage low-cost ultraclean melting method of producing Inconel690 alloy |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112725659A (en) * | 2020-12-22 | 2021-04-30 | 丹阳市曙光镍材有限公司 | Nickel alloy casting process based on intermediate frequency furnace |
| CN112553403A (en) * | 2020-12-24 | 2021-03-26 | 广东石油化工学院 | Method for smelting and deoxidizing stainless steel welding material |
| CN113699399A (en) * | 2021-08-31 | 2021-11-26 | 山东瑞泰新材料科技有限公司 | Purifying smelting process of nickel-based high-temperature alloy without aluminum and titanium |
| CN114645161A (en) * | 2022-03-09 | 2022-06-21 | 中国地质大学（武汉） | High-oxidation-resistance nickel-based alloy block material and preparation method thereof |
| CN114645161B (en) * | 2022-03-09 | 2022-11-29 | 中国地质大学（武汉） | High-oxidation-resistance nickel-based alloy block material and preparation method thereof |
| CN115305368A (en) * | 2022-07-20 | 2022-11-08 | 西安聚能高温合金材料科技有限公司 | Preparation method of Fe-Ni-Co-based high-temperature alloy GH907 alloy ingot |
| CN115305368B (en) * | 2022-07-20 | 2023-11-14 | 西安聚能高温合金材料科技有限公司 | Preparation method of Fe-Ni-Co-based superalloy GH907 alloy ingot |
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