CN112458326A - Zr-Ce-containing wrought high-temperature alloy and preparation method thereof - Google Patents

Zr-Ce-containing wrought high-temperature alloy and preparation method thereof Download PDF

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CN112458326A
CN112458326A CN202110114274.3A CN202110114274A CN112458326A CN 112458326 A CN112458326 A CN 112458326A CN 202110114274 A CN202110114274 A CN 202110114274A CN 112458326 A CN112458326 A CN 112458326A
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raw material
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zirconium
cerium
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CN112458326B (en
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杨树峰
杨曙磊
赵朋
刘威
贾雷
王宁
周杨
徐志强
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University of Science and Technology Beijing USTB
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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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/16—Remelting metals
    • C22B9/18—Electroslag remelting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C16/00—Alloys based on zirconium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention relates to a Zr-Ce-containing wrought high-temperature alloy and a preparation method thereof. The method comprises the following steps: preparing raw materials; carrying out vacuum induction melting on the raw materials according to melting, refining and pouring in sequence: in the refining period, refining the melt obtained by melting for 60-80 min, then adding a small amount of zirconium and cerium, continuously refining for 10-15 min, and detecting the burning loss amount of the zirconium and the cerium; then adding the rest zirconium and cerium and the burnt zirconium and cerium, and continuously refining for 10-15 min; in the casting period, casting the alloy melt obtained by refining to obtain a vacuum induction cast ingot; carrying out electroslag remelting on the vacuum induction cast ingot to obtain a Zr-Ce-containing wrought high-temperature alloy; the slag adopted by the electroslag remelting contains CaF2、CaO、Al2O3、TiO2、ZrO2And CeO2. The invention can be used for accurately controlling Zr and Ce elements in the alloyThe purity of the alloy and the uniformity of element distribution are improved.

Description

Zr-Ce-containing wrought high-temperature alloy and preparation method thereof
Technical Field
The invention belongs to the technical field of high-temperature alloy smelting, and particularly relates to a Zr-Ce-containing wrought high-temperature alloy and a preparation method thereof.
Background
Trace Zr (zirconium) and Ce (cerium) elements are added into the deformed high-temperature alloy, so that the durability of the alloy can be obviously improved. The Zr element is partially gathered in the crystal boundary, so that the crystal boundary defects are reduced, the crystal boundary bonding force is improved, and the crystal boundary diffusion rate is reduced, thereby slowing down the dislocation climb and strengthening the crystal boundary. The element Ce is used as a purifying agent, has the effects of deoxidation and desulfurization, and can reduce the harmful effects of oxygen and sulfur on grain boundaries, and in addition, the Ce can improve the oxidation resistance of the alloy and improve the surface activity. However, too much Zr increases the formation of harmful phases such as Lavese in the alloy, and too much Ce deteriorates the thermoplasticity of the alloy. Therefore, the accurate and reasonable control of the content of Zr and Ce elements provides a challenge for smelting the Zr-Ce-containing wrought superalloy.
At present, the smelting process of the wrought superalloy generally comprises vacuum induction smelting, electroslag remelting and vacuum consumable remelting, and high-quality alloy base metal is prepared through primary smelting, secondary smelting or tertiary smelting. For the smelting process for preparing the wrought high-temperature alloy by adopting the vacuum induction smelting and electroslag remelting duplex process, the Zr and Ce elements cannot be reasonably and accurately controlled, and the two factors are mainly as follows: firstly, vacuum induction melting is used as a one-step melting process of the alloy, so that impurity elements in an alloy melt are more, and the yield of Zr and Ce elements is low. Secondly, in electroslag remelting, Zr and Ce elements have higher activity and are easy to react with oxides in slag to cause element burning loss, so that the control of the Zr and Ce elements becomes more complex.
Chinese patent application CN103498066A discloses a vacuum induction melting process of Mg-containing high-temperature alloy, which provides a solution for controlling the Mg contentThe solution is decided. Chinese patent application CN109536733A discloses premelting slag for high-temperature alloy electroslag remelting, which provides a premelting slag containing ZrO2The pre-melted slag formula can reduce the burning loss of Zr element in electroslag remelting. However, for the deformed high-temperature alloy containing both Zr and Ce, at present, a smelting process for reasonably and accurately controlling the Zr and Ce contents and the alloy smelting quality still does not exist.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a Zr-Ce-containing wrought high-temperature alloy and a preparation method thereof. The preparation method of the Zr-Ce-containing wrought high-temperature alloy can be used for accurately controlling the contents of Zr and Ce elements in the alloy and improving the purity of the alloy and the uniformity of element distribution.
The invention provides in a first aspect a method for preparing a wrought Zr-Ce containing superalloy, said method comprising the steps of:
(1) providing raw materials for preparing a Zr-Ce-containing wrought superalloy, wherein the raw materials comprise a base element raw material and an adjusting element raw material, and the adjusting element raw material comprises a zirconium raw material and a cerium raw material;
(2) the raw materials are subjected to vacuum induction melting according to the following three processes in sequence:
and (3) material melting period: firstly, carrying out power transmission smelting on a matrix element raw material to obtain a molten material to be refined; the vacuum degree in the material melting period is 15-35 Pa;
and (3) refining period: the refining period sequentially comprises a refining early period, a refining middle period and a refining late period; refining the to-be-refined molten material for 60-80 min in the early refining stage to obtain an early-stage refined molten material; in the middle stage of refining, adding a zirconium raw material and a cerium raw material into the early-stage refining molten material and continuously refining for 10-15 min to obtain a middle-stage refining molten material, and detecting the burning loss amount of the zirconium raw material and the cerium raw material in the middle-stage refining molten material; in the later refining stage, adding a zirconium raw material and a cerium raw material into the middle-stage refining molten material and continuously refining for 10-15 min to obtain an alloy melt; in the middle stage of refining, the adding amount of the zirconium raw material is 5-20 wt.% of the target content of zirconium in the Zr-Ce containing wrought high-temperature alloy, and the adding amount of the cerium raw material is 5-20 wt.% of the target content of cerium in the Zr-Ce containing wrought high-temperature alloy; the total amount of the zirconium raw material added in the middle refining stage and the later refining stage is equal to the sum of the target content of zirconium in the Zr-Ce containing wrought superalloy and the burning loss amount of the zirconium raw material in the middle refining stage; the total amount of the cerium raw material added in the middle refining stage and the later refining stage is equal to the sum of the target content of cerium in the Zr-Ce-containing wrought superalloy and the burning loss amount of the cerium raw material in the middle refining stage;
and (3) pouring period: pouring the alloy melt under the protection of argon to obtain a vacuum induction cast ingot;
(3) carrying out electroslag remelting by taking the vacuum induction cast ingot as an electroslag remelting electrode to obtain a Zr-Ce-containing wrought high-temperature alloy; the slag adopted by the electroslag remelting comprises the following components in percentage by mass: CaF2，45~55%；CaO，15~22%；Al2O3，15~24%；TiO2，2~4%；ZrO2，0.5~4%；CeO2，0.5~4%。
Preferably, the electroslag remelting sequentially comprises primary electroslag remelting and secondary electroslag remelting; and after carrying out primary electroslag remelting on the electroslag remelting electrode to obtain a primary electroslag ingot, replacing the head and the tail of the ingot with the primary electroslag ingot to carry out secondary electroslag remelting to obtain the Zr-Ce-containing wrought high-temperature alloy.
Preferably, the base element raw materials include a chromium raw material, a nickel raw material, a cobalt raw material, a tungsten raw material, a molybdenum raw material and electrode carbon; the adjusting element raw materials also comprise an aluminum raw material, a titanium raw material and a boron raw material; in the material melting period, firstly, feeding electricity to the nickel raw material, the cobalt raw material, the tungsten raw material, the molybdenum raw material and the electrode carbon contained in the matrix element raw material for melting to obtain a fully-melted first melt material, then adding the chromium raw material contained in the matrix element raw material into the first melt material, melting and stirring for 15-20 min to obtain a melt material to be refined; and in the middle refining stage, adding an aluminum raw material, a titanium raw material and a boron raw material which are contained in the adjusting element raw materials into the early-stage refining molten material.
Preferably, the slag comprises components in percentage by massComprises the following steps: CaF2，49~53%；CaO，16~20%；Al2O3，18~23%；TiO2，4%；ZrO2，1.2~2.4%；CeO2，0.8~1.6%。
Preferably, ZrO contained in the slag2The mass percentage of the components is determined by the following formula:
Figure 665045DEST_PATH_IMAGE001
wherein the content of the first and second substances,
Figure 251885DEST_PATH_IMAGE002
represents ZrO contained in the slag2The content of the components in percentage by mass,
Figure 475056DEST_PATH_IMAGE003
represents the target content of zirconium in the Zr-Ce containing wrought superalloy,
Figure 805543DEST_PATH_IMAGE004
represents a target content of cerium in the Zr-Ce-containing wrought superalloy;
CeO contained in the slag charge2The mass percentage of the components is determined by the following formula:
Figure 797769DEST_PATH_IMAGE005
wherein the content of the first and second substances,
Figure 821089DEST_PATH_IMAGE006
denotes CeO contained in the slag2The content of the components in percentage by mass,
Figure 531556DEST_PATH_IMAGE003
represents the target content of zirconium in the Zr-Ce containing wrought superalloy,
Figure 400155DEST_PATH_IMAGE004
indicates that the Zr-Ce-containing strain is highTarget content of cerium in the mild alloy.
Preferably, the electrode carbon is added at the upper limit of the composition range of the target carbon in the Zr — Ce containing wrought superalloy; and/or the casting temperature is higher than the melting point of the alloy melt by 80-120 ℃.
Preferably, the vacuum degree in the material melting period is 15-20 Pa; and/or the vacuum degree in the refining period is not more than 0.1 Pa.
Preferably, the granularity of the slag is 10-20 mm; and/or the amount of the slag adopted in each electroslag remelting is 5-7% of the mass of the vacuum induction cast ingot.
Preferably, the Zr-Ce-containing wrought superalloy is a Zr-Ce-containing GH4710 wrought superalloy.
The present invention provides in a second aspect a Zr-Ce containing wrought superalloy made by the method of the first aspect of the present invention.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the invention provides a smelting process of a Zr-Ce-containing wrought superalloy, and the preferred process route comprises vacuum induction smelting, primary electroslag remelting and secondary electroslag remelting, so that the vacuum induction smelting process is optimized, and reasonable electroslag remelting slag is provided; the method can be used for accurately controlling the contents of Zr and Ce elements in the alloy and improving the purity of the alloy and the uniformity of element distribution.
(2) In some preferred embodiments, the method provided by the invention can remove impurity elements in the alloy as much as possible in the melting period by optimizing charging, melting and stirring processes, so that the burning loss of active elements Zr and Ce is less.
(3) According to the method, a small amount of Zr and Ce is pre-added in the middle stage of refining, the burning loss condition of the furnace to the active elements Zr and Ce is judged, and then the active elements Zr and Ce are supplemented in the later stage of refining, so that the aim of accurately controlling the contents of the active elements Zr and Ce is fulfilled.
(4) The method of the invention is to smelt the Zr-Ce-containing wrought superalloy, and adopts a reactive element in the electroslag remelting processThe slag material for electroslag remelting with stable control of Zr and Ce, and in some preferred embodiments, the preferable component proportioning range of the slag material and ZrO contained in the slag material are given2And CeO2The mass percentage content determination formula enables oxides in the slag and easily-oxidizable elements (such as Zr, Ce, Al, Ti and the like) in the alloy to be better kept in a thermodynamic equilibrium state during electroslag remelting, so that oxidation-reduction reaction of the oxides in the slag and the easily-oxidizable elements is more effectively prevented, and burning loss of the easily-oxidizable elements can be effectively avoided.
(5) In some preferred embodiments of the present invention, a set of twice electroslag remelting process is provided, wherein after the vacuum induction ingot is subjected to once electroslag remelting to obtain a once electroslag ingot, the once electroslag ingot is subjected to second electroslag remelting; the invention finds that twice electroslag remelting can effectively ensure the uniformity of alloy components along the height direction of an ingot, and more importantly, can effectively remove impurity elements and inclusions in the alloy, thereby effectively preventing burning loss of active elements Zr and Ce.
Drawings
FIG. 1 is a flow chart of the preparation in some embodiments of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides in a first aspect a method for preparing a wrought Zr-Ce containing superalloy, said method comprising the steps of:
(1) providing raw materials for preparing a Zr-Ce-containing wrought superalloy, wherein the raw materials comprise a base element raw material and an adjusting element raw material, and the adjusting element raw material comprises a zirconium raw material and a cerium raw material; in the invention, the Zr-Ce-containing wrought superalloy refers to a wrought superalloy containing trace elements of Zr and Ce at the same time; the invention has no special requirements on the raw materials, and the raw materials commonly used for preparing the wrought superalloy and the component proportion of each raw material are adopted; in the present invention, as an example, a GH4710 wrought superalloy containing Zr — Ce is taken, the base element raw material includes, for example, a chromium raw material, a nickel raw material, a cobalt raw material, a tungsten raw material, a molybdenum raw material, and electrode carbon (carbon raw material), and the adjusting element raw material includes, for example, an easily-burnt-out element raw material, an aluminum raw material, a titanium raw material, a boron raw material, a zirconium raw material, and a cerium raw material, and is used for ensuring the yield of elements; the composition range of each matrix element raw material of the GH4710 wrought superalloy conforms to the composition range regulation of GH4710 in the Standard of Classification and code of GB/T14992-2005 high temperature alloy and intermetallic compound high temperature material.
(2) The raw materials are subjected to vacuum induction melting according to the following three processes in sequence:
melting period (also referred to as melting period): firstly, carrying out electric smelting (namely electric smelting) on a base element raw material to obtain a molten material to be refined; the vacuum degree in the material melting period is 15-35 Pa (such as 15, 20, 25, 30 or 35 Pa); the vacuum degree of the melting period is controlled to be 15-35 Pa, so that the sputtering caused by the overhigh vacuum degree can be prevented, and the volatilization removal of impurity elements in the melting period can be ensured; in the invention, other process conditions related to the electric power transmission smelting in the material melting period are the existing electric power transmission smelting process conditions for preparing GH4710 alloy;
and (3) refining period: the refining period sequentially comprises a refining early period, a refining middle period and a refining late period; in the early stage of refining, refining the molten material to be refined for 60-80 min (60, 65, 70, 75 or 80 min) to obtain an early stage refining molten material; in the middle stage of refining, adding a zirconium raw material and a cerium raw material into the early-stage refining molten material and continuously refining for 10-15 min (for example, 10, 11, 12, 13, 14 or 15 min) to obtain a middle-stage refining molten material, and detecting the burning loss amount of the zirconium raw material and the cerium raw material in the middle-stage refining molten material; in the later stage of refining, adding a zirconium raw material and a cerium raw material into the middle-stage refining molten material, and continuously refining for 10-15 min (for example, 10, 11, 12, 13, 14 or 15 min) to obtain an alloy melt; in the middle refining stage, the zirconium raw material is added in an amount of 5-20 wt.% (e.g., 5, 10, 15 or 20 wt.%), preferably 10wt.% of the target content of zirconium in the Zr-Ce containing wrought superalloy, and the cerium raw material is added in an amount of 5-20 wt.% (e.g., 5, 10, 15 or 20 wt.%), preferably 10wt.% of the target content of cerium in the Zr-Ce containing wrought superalloy; the total amount of the zirconium raw material added in the middle refining stage and the later refining stage is equal to the sum of the target content of zirconium in the Zr-Ce containing wrought superalloy and the burning loss amount of the zirconium raw material in the middle refining stage; the total amount of the cerium raw material added in the middle refining stage and the later refining stage is equal to the sum of the target content of cerium in the Zr-Ce-containing wrought superalloy and the burning loss amount of the cerium raw material in the middle refining stage; in the present invention, when the amount of the added zirconium raw material is 10wt.% of the target content of zirconium in the Zr-Ce containing wrought superalloy in the middle stage of refining, and the amount of the added cerium raw material is 10wt.% of the target content of cerium in the Zr-Ce containing wrought superalloy, that is, in the later stage of refining, the amount of the added zirconium raw material is the sum of 90wt.% of the target content of zirconium in the Zr-Ce containing wrought superalloy and the amount of burnout of the zirconium raw material in the middle stage of refining, and the amount of the added cerium raw material is the sum of 90wt.% of the target content of cerium in the Zr-Ce containing wrought superalloy and the amount of burnout of the cerium raw material in the middle stage of refining; in the invention, the process conditions of the early refining stage, the middle refining stage and the later refining stage are the same, the refining conditions of the existing GH4710 alloy preparation are adopted, and the temperature of the whole refining stage can be 1450-1550 ℃, for example; in the present invention, the unit wt.% represents a mass percentage content; the refining period of the vacuum induction melting sequentially comprises a refining early period, a refining middle period and a refining later period, the refining time is prolonged, namely the stirring time during refining is prolonged, the stirring during refining is enhanced, the burning loss condition of active elements in the furnace is judged by pre-adding a small amount of Zr and Ce in the refining middle period, and then the active elements Zr and Ce are added in the refining later period, so that the aim of accurately controlling the contents of the active elements Zr and Ce is fulfilled;
and (3) pouring period: and pouring the alloy melt under the protection of argon to obtain a vacuum induction cast ingot.
(3) Carrying out electroslag remelting by taking the vacuum induction cast ingot as an electroslag remelting electrode to obtain a Zr-Ce-containing wrought high-temperature alloy; the slag charge (also called as an anti-burning loss slag system) comprises the following components in percentage by mass: CaF2(calcium fluoride), 45-55% (e.g., 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, or 55%); CaO (calcium oxide), 15-22% (e.g., 15%, 16%, 17%, 18%, 19%, 20%, 21%, or 22%); al (Al)2O3(alumina), 15-24% (e.g., 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, or 24%); TiO 22(titanium dioxide), 2-4% (e.g. 2%, 3% or 4%); ZrO (ZrO)2(zirconium dioxide), 0.5-4% (e.g., 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, or 4%); CeO (CeO)2(ceria), 0.5-4% (e.g., 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, or 4%); before the vacuum induction ingot is used as an electroslag remelting electrode to carry out electroslag remelting, the method also comprises the steps of cutting off a dead head of the vacuum induction melting ingot, turning, removing surface impurities, welding an auxiliary electrode, baking for 2-3 hours, removing moisture and processing oil stains, and charging into a furnace for centering; the electroslag remelting slag capable of stably controlling the active elements Zr and Ce is adopted in the electroslag remelting process, so that oxides in slag and easily-oxidizable elements in alloy keep a thermodynamic equilibrium state during electroslag remelting, oxidation-reduction reaction of the oxides in the slag and the easily-oxidizable elements is prevented, and burning loss of the easily-oxidizable elements is avoided.
According to some preferred embodiments, the electroslag remelting comprises, in order, a primary electroslag remelting and a secondary electroslag remelting; after the vacuum induction cast ingot is subjected to primary electroslag remelting to obtain a primary electroslag ingot, replacing the head and the tail of the ingot with the primary electroslag ingot to perform secondary electroslag remelting to obtain a Zr-Ce-containing wrought high-temperature alloy; specifically, the primary electroslag remelting is, for example, to perform argon filling, arc striking, slag adding and slagging in batches (for example, in the slagging period of single electroslag remelting, adopted slag materials are added in 3-4 times in sequence), smelting, performing heat sealing on a top, performing furnace cooling for 5-10 hours, demolding, and taking ingots to prepare primary electroslag ingots; the secondary electroslag remelting comprises the steps of polishing a primary electroslag ingot, replacing the head and the tail of the ingot, welding an auxiliary electrode, baking, charging, smelting, wherein slag used for secondary electroslag remelting is the same as slag used for primary electroslag remelting, and after smelting is finished, the ingot is taken by furnace cooling, drilling cuttings and components are detected; the secondary electroslag remelting is the same as the slagging process of the primary electroslag remelting, and the process conditions of arc striking, stable smelting, thermal capping and the like related to the primary electroslag remelting and the secondary electroslag remelting adopt the electroslag remelting condition commonly adopted by the existing smelting deformation high-temperature alloy; preferably, the vacuum induction ingot is firstly subjected to primary electroslag remelting to obtain a primary electroslag ingot, and then the primary electroslag ingot is subjected to secondary electroslag remelting; the invention finds that twice electroslag remelting can effectively ensure the uniformity of alloy components along the height direction of an ingot, and more importantly, can effectively remove impurity elements and inclusions in the alloy, thereby effectively preventing burning loss of active elements Zr and Ce.
According to some preferred embodiments, the base element raw material includes a chromium raw material (Cr), a nickel raw material (Ni), a cobalt raw material (Co), a tungsten raw material (W), a molybdenum raw material (Mo), and electrode carbon (C); in the present invention, the nickel raw material is, for example, a nickel plate, the chromium raw material is, for example, a chromium block, the cobalt raw material is, for example, a cobalt plate, the tungsten raw material is, for example, a tungsten bar, and the molybdenum raw material is, for example, a molybdenum block, and in the present invention, the electrode carbon is, for example, a carbon powder or a carbon block; the adjusting element raw materials also comprise an aluminum raw material (Al), a titanium raw material (Ti) and a boron raw material (B); in the present invention, the aluminum material is, for example, an aluminum block, the titanium material is, for example, titanium sponge, the boron material is, for example, a boron block, the zirconium material is, for example, zirconium sponge, and the cerium material is, for example, cerium particles; in the material melting period, a nickel raw material, a cobalt raw material, a tungsten raw material, a molybdenum raw material and electrode carbon which are contained in the matrix element raw material are subjected to power transmission melting to obtain a fully-melted first melt material, then a chromium raw material contained in the matrix element raw material is added into the first melt material, and the mixture is stirred for 15-20 min (for example, 15, 16, 17, 18, 19 or 20 min) after being melted down (namely, completely melted), so that a melt material to be refined is obtained; in the middle stage of refining, adding an aluminum raw material, a titanium raw material and a boron raw material which are included in the adjusting element raw material into the early-stage refining molten material; when the material is charged, the material is preferably charged with the matrix element raw materials such as Ni, Mo, Co and the like, and the chromium is added after the material is completely melted, because the solubility of the impurity element N in the melting material can be improved by the chromium, and the denitrification in the melting period is facilitated by the addition of the chromium; the chromium raw material is added and melted down, and then the mixture is stirred for 15-20 min, so that the carbon-oxygen reaction can be promoted, and the gas is fully degassed; according to the invention, by optimizing the charging, melting and stirring processes, impurity elements in the alloy can be removed as much as possible in the melting period, and the burning loss of active elements Zr and Ce can be reduced.
According to some preferred embodiments, the slag comprises the following components in percentage by mass: CaF249-53% (e.g., 49%, 50%, 51%, 52%, or 53%); CaO, 16-20% (e.g., 16%, 17%, 18%, 19%, or 20%); al (Al)2O318-23% (e.g., 18%, 19%, 20%, 21%, 22%, or 23%); TiO 22，4%；ZrO21.2-2.4% (e.g., 1.2%, 1.5%, 1.8%, 2%, 2.4%); CeO (CeO)20.8-1.6% (e.g., 0.8%, 1.2%, or 1.6%); the invention optimizes the component proportion range of the slag, and is more beneficial to keeping the oxide in the slag and the easily-oxidized element in the alloy in a thermodynamic equilibrium state during electroslag remelting, thereby more effectively preventing the oxide in the slag and the easily-oxidized element from generating redox reaction and effectively avoiding burning loss of the easily-oxidized element.
According to some preferred embodiments, the ZrO contained in the slag is2The mass percentage of the components is determined by the following formula:
Figure 512468DEST_PATH_IMAGE007
wherein the content of the first and second substances,
Figure 441109DEST_PATH_IMAGE002
to representZrO contained in the slag2The content of the components in percentage by mass,
Figure 904452DEST_PATH_IMAGE003
represents the target content of zirconium in the Zr-Ce containing wrought superalloy,
Figure 780004DEST_PATH_IMAGE004
represents a target content of cerium in the Zr-Ce-containing wrought superalloy;
in the above-mentioned formula,
Figure 137036DEST_PATH_IMAGE008
the preceding coefficient may be, for example, 2%, 2.5%, 3%, 3.5%, or 4%, and in some more preferred embodiments, 3%;
CeO contained in the slag charge2The mass percentage of the components is determined by the following formula:
Figure 439841DEST_PATH_IMAGE009
wherein the content of the first and second substances,
Figure 187217DEST_PATH_IMAGE006
represents ZrO contained in the slag2The content of the components in percentage by mass,
Figure 663198DEST_PATH_IMAGE003
represents the target content of zirconium in the Zr-Ce containing wrought superalloy,
Figure 208492DEST_PATH_IMAGE004
represents a target content of cerium in the Zr-Ce-containing wrought superalloy;
in the above-mentioned formula,
Figure 619882DEST_PATH_IMAGE010
the coefficient of the preceding may be, for example, 2%, 2.5%, 3%, 3.5% or 4%, and in some more preferred embodiments, 3%.
The invention also providesDetermining the amount of ZrO contained in the slag2、CeO2The formula of the mass percentage content is a formula originally created by the inventor through a large number of creative experiments, and the invention preferably determines ZrO contained in the slag through the two formulas2、CeO2The invention discovers that the ZrO of the optimized component proportion2、CeO2The addition of the active elements Zr and Ce can effectively prevent the burning loss caused by the reaction of the active elements Zr and Ce with the oxide in the slag, thereby better achieving the purpose of accurately controlling the contents of the active elements Zr and Ce; in addition, the invention finds that the two formulas can be used for designing different applicable slag systems according to different alloys, and has important significance.
According to some preferred embodiments, the electrode carbon is added (dosed) at the upper limit of the composition range of the target carbon in the Zr — Ce containing wrought superalloy; in the invention, the electrode carbon is added to remove impurity oxygen in raw materials through carbon-oxygen reaction in the vacuum induction melting process, and the electrode carbon is preferably added according to the upper limit of the component range of target carbon in the Zr-Ce-containing wrought superalloy, so that the impurity element oxygen in the alloy can be removed as much as possible, and the burning loss of Zr and Ce is reduced; and/or the casting temperature is higher than the melting point of the alloy melt by 80-120 ℃.
According to some preferred embodiments, the vacuum degree in the material melting period is 15-20 Pa; and/or the vacuum degree in the refining period is not more than 0.1 Pa.
According to some preferred embodiments, the slag has a particle size of 10 to 20 mm; and/or the amount of the slag adopted in each electroslag remelting is 5-7% of the mass of the vacuum induction cast ingot; in some preferred embodiments of the invention, 65kg of slag is required for every 1000kg of said vacuum induction ingot for every electroslag remelting.
According to some preferred embodiments, the Zr-Ce containing wrought superalloy is a Zr-Ce containing GH4710 wrought superalloy (abbreviated as Zr-Ce containing GH4710 alloy).
The present invention provides in a second aspect a Zr-Ce containing wrought superalloy made by the method of the first aspect of the present invention.
The invention will be further illustrated by way of example, but the scope of protection is not limited to these examples.
Example 1
This example provides a method for preparing a GH4710 alloy containing Zr — Ce, the target content values of each component in the GH4710 alloy are shown in table 1 below.
Figure 651292DEST_PATH_IMAGE011
The preparation method comprises the following steps:
firstly, equipment and material preparation: the raw materials were prepared in the target composition ratio using a 1t vacuum induction furnace, wherein the electrode carbon (C) was prepared in accordance with 0.1% of the total mass of the GH4710 alloy containing Zr-Ce, and the sponge zirconium and cerium particles were prepared in accordance with 110% of the target content value, i.e., the preparation amount of the sponge zirconium was 3.3% of the total mass of the GH4710 alloy containing Zr-Ce, and the preparation amount of the cerium particles was 2.2% of the total mass of the GH4710 alloy containing Zr-Ce.
The material melting period: firstly adding a nickel plate, a cobalt plate, a tungsten bar, electrode carbon and a molybdenum block at a certain proportion, vacuumizing to 20Pa, powering on for smelting to obtain a fully-molten first melt, then adding a chromium block into the first melt, melting down, and stirring for 15min to obtain a melt to be refined.
Refining and pouring: vacuumizing to 0.05Pa, and refining the molten material to be refined for 65min in the early stage of refining to obtain the early-stage refined molten material; in the middle stage of refining, all aluminum blocks, titanium sponge and boron blocks, sponge zirconium and cerium particles with target component content of 10% (namely the addition amount of the sponge zirconium is 0.3 wt% of GH4710 alloy containing Zr-Ce, and the addition amount of the cerium particles is 0.2 wt% of GH4710 alloy containing Zr-Ce) are filled in the refining molten material in the previous stage, refining is carried out for 10min, a middle-stage refining molten material is obtained, and the burning loss rates of Zr and Ce are respectively 20% and 60% (namely the burning loss amounts of the Zr and Ce in the middle stage of refining are respectively 0.06% and 0.12% of the total mass of the GH4710 alloy containing Zr-Ce); in the later stage of refining, adding 92% of sponge zirconium and 96% of cerium particles (namely the addition of the sponge zirconium is 2.76 wt% of GH4710 alloy containing Zr-Ce, and the addition of the cerium particles is 1.92 wt% of GH4710 alloy containing Zr-Ce), refining for 10min, stopping power and keeping the temperature for 25-30 min, introducing argon, starting pouring, wherein the pouring temperature is 1460 ℃, cooling the furnace for 8 hours, and demolding to obtain the vacuum induction cast ingot.
Preparing an electroslag remelting electrode and preparing slag: cutting off a dead head of the vacuum induction cast ingot, turning, welding an auxiliary electrode, and baking for 3 hours for later use; according to mass percent, CaF2：52%；Al2O3：23%；CaO：18%；TiO2：4%；ZrO2：1.8%；CeO2: 1.2 percent of slag is prepared, the consumption of the slag adopted by the primary electroslag remelting and the secondary electroslag remelting is 6.5 percent of the mass of the vacuum induction ingot, namely, 65kg of slag is required to be adopted when every 1000kg of the vacuum induction ingot is subjected to electroslag remelting.
Primary electroslag remelting: charging into a furnace for centering, arcing the steel fragments (fragments of the smelted alloy), equally dividing the adopted slag into 3 parts, sequentially adding into melting slag, smelting, stabilizing the smelting voltage to 45V, ensuring the average smelting rate to be 5.8kg/min, carrying out hot capping, cooling the furnace for 5 hours, and demoulding to obtain the primary electroslag ingot.
Sixthly, remelting electroslag for the second time: polishing and welding the primary electroslag ingot, replacing the head and the tail of the ingot, then loading the ingot into a furnace for centering, arcing the steel fragments, equally dividing the adopted slag into 3 parts, sequentially adding the 3 parts for slagging, smelting, keeping the stable smelting voltage at 45V, keeping the average smelting speed at 5.8kg/min, carrying out heat sealing, carrying out furnace cooling for 5 hours, and demoulding to obtain a GH4710 alloy ingot containing Zr-Ce (GH 4710 alloy containing Zr-Ce); drilling cuttings at the head, middle and tail positions of a GH4710 alloy ingot containing Zr-Ce, wherein the specific positions are 50mm away from the head of the ingot, the middle of the ingot and 50mm away from the tail of the ingot, and detecting the Zr, Ce, N and O contents at the head, middle and tail positions of the GH4710 alloy, wherein the results are shown in Table 2.
Example 2
Example 2 is essentially the same as example 1, except that:
the material melting period: adding a nickel plate, a chromium block, a cobalt plate, a tungsten bar, electrode carbon and a molybdenum block at a certain proportion at one time, vacuumizing to 20Pa, powering on to smelt, and stirring for 15min after melting down to obtain a molten material to be refined.
The contents of Zr, Ce, N and O in the head, the middle and the tail of the GH4710 alloy containing Zr-Ce obtained in the example were measured by drilling at the head, the middle and the tail of the GH4710 alloy, wherein the specific positions are 50mm from the head, the middle and the tail of the ingot, and the results are shown in Table 2.
Example 3
Example 3 is essentially the same as example 1, except that:
preparing an electroslag remelting electrode and preparing slag: cutting off a dead head of the vacuum induction cast ingot, turning, welding an auxiliary electrode, and baking for 3 hours for later use; according to mass percent, CaF2：52%；Al2O3：21.5%；CaO：18%；TiO2：4%；ZrO2：2.7%；CeO2: 1.8 percent of slag is prepared, the consumption of the slag adopted by the primary electroslag remelting and the secondary electroslag remelting is 6.5 percent of the mass of the vacuum induction ingot, namely, 65kg of slag is required to be adopted when every 1000kg of the vacuum induction ingot is subjected to electroslag remelting.
Drilling cuttings at the head, the middle and the tail of the GH4710 alloy containing Zr-Ce obtained in the embodiment are drilled at the positions 50mm away from the head of an ingot, at the middle of the ingot and at the position 50mm away from the tail of the ingot,
the Zr content, the Ce content, the N content and the O content of the head position, the middle position and the tail position of the GH4710 alloy are detected, and the results are shown in Table 2.
Example 4
Example 4 is essentially the same as example 1, except that:
firstly, equipment and material preparation: the raw materials were prepared in the target composition ratio using a 1t vacuum induction furnace, in which electrode carbon (C) was prepared in accordance with 0.04% of the total mass of the GH4710 alloy containing Zr-Ce, and zirconium sponge and cerium particles were prepared in accordance with 110% of the target content value, i.e., the preparation amount of zirconium sponge was 3.3% of the total mass of the GH4710 alloy containing Zr-Ce, and the preparation amount of cerium particles was 2.2% of the total mass of the GH4710 alloy containing Zr-Ce.
Drilling cuttings at the head, the middle and the tail of the GH4710 alloy containing Zr-Ce obtained in the embodiment are drilled at the positions 50mm away from the head of an ingot, at the middle of the ingot and at the position 50mm away from the tail of the ingot,
the Zr content, the Ce content, the N content and the O content of the head position, the middle position and the tail position of the GH4710 alloy are detected, and the results are shown in Table 2.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that:
refining and pouring: vacuumizing to 0.05Pa, refining the molten material to be refined for 65min, then filling all aluminum blocks, titanium sponge and boron blocks, and 100% of sponge zirconium and cerium (namely, the addition of the sponge zirconium is 3 wt% of GH4710 alloy containing Zr-Ce, and the addition of cerium particles is 2 wt% of GH4710 alloy containing Zr-Ce), refining for 15min, stopping power, preserving heat for 25-30 min, filling argon, starting pouring, wherein the pouring temperature is 1460 ℃, cooling the furnace for 8 hours, and demolding to obtain the vacuum induction cast ingot.
Drilling cuttings at the head, the middle and the tail of the GH4710 alloy containing Zr-Ce obtained by the comparative example are drilled at the specific positions of 50mm from the head of an ingot, 50mm from the middle of the ingot and 50mm from the tail of the ingot,
the Zr content, the Ce content, the N content and the O content of the head position, the middle position and the tail position of the GH4710 alloy are detected, and the results are shown in Table 2.
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that:
the electroslag remelting method comprises the following steps: during charging centering, after the steel fragment is subjected to arc striking, the amount of the adopted slag is 6.5 percent of the mass of the vacuum induction cast ingot, namely when every 1000kg of the vacuum induction cast ingot is subjected to electroslag remelting, 65kg of the slag is required to be adopted, the adopted slag is equally divided into 3 parts, slag melting is sequentially added, smelting is carried out, the stable smelting voltage is 45V, the average smelting rate is 5.8kg/min, the top is thermally sealed, the furnace is cooled for 5 hours, and demoulding is carried out, so that the GH4710 alloy containing Zr-Ce is obtained.
Drilling cuttings at the head, the middle and the tail of the GH4710 alloy containing Zr-Ce obtained by the comparative example, wherein the specific positions are 50mm away from the head of an ingot, the middle of the ingot and 50mm away from the tail of the ingot, and the Zr, Ce, N and O contents at the head, the middle and the tail of the GH4710 alloy are detected, and the results are shown in Table 2.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that:
the material melting period: firstly adding a nickel plate, a cobalt plate, a tungsten bar, electrode carbon and a molybdenum block at a certain proportion, vacuumizing to 0.05Pa, powering on for smelting to obtain a fully-molten first melt, then adding a chromium block into the first melt, melting down, and stirring for 15min to obtain a melt to be refined.
Drilling cuttings at the head, the middle and the tail of the GH4710 alloy containing Zr-Ce obtained by the comparative example, wherein the specific positions are 50mm away from the head of an ingot, the middle of the ingot and 50mm away from the tail of the ingot, and the Zr, Ce, N and O contents at the head, the middle and the tail of the GH4710 alloy are detected, and the results are shown in Table 2.
Comparative example 4
This comparative example provides a method of making a GH4710 alloy containing Zr-Ce, the target content values for each of the constituents in the GH4710 alloy being the same as those shown in table 1 in example 1.
The preparation method comprises the following steps:
firstly, equipment and material preparation: the raw materials were prepared in the target composition ratio using a 1t vacuum induction furnace, in which electrode carbon (C) was prepared in an amount of 0.04% by mass of the total Zr-Ce-containing GH4710 alloy, and zirconium sponge and cerium were prepared in an amount of 100% by mass of the target content value, i.e., the preparation amount of zirconium sponge was 3% by mass of the total Zr-Ce-containing GH4710 alloy, and the preparation amount of cerium particles was 2% by mass of the total Zr-Ce-containing GH4710 alloy.
The material melting period: adding a nickel plate, a chromium block, a cobalt plate, a tungsten bar, electrode carbon and a molybdenum block at a certain proportion at one time, vacuumizing to 0.05Pa, powering on for smelting, and stirring for 15min after melting down to obtain a molten material to be refined.
Refining and pouring: vacuumizing to 0.05Pa, refining the molten material to be refined for 65min, then filling all aluminum blocks, titanium sponge and boron blocks, and 100% of sponge zirconium and cerium (namely, the addition of the sponge zirconium is 3 wt% of GH4710 alloy containing Zr-Ce, and the addition of cerium particles is 2 wt% of GH4710 alloy containing Zr-Ce), refining for 15min, stopping power, preserving heat, filling argon, starting pouring, cooling the pouring temperature at 1460 ℃, cooling the furnace for 8 hours, and demolding to obtain the vacuum induction cast ingot.
Preparing an electroslag remelting electrode and preparing slag: cutting off a dead head of the vacuum induction cast ingot, turning, welding an auxiliary electrode, and baking for 3 hours for later use; according to mass percent, CaF2：52.3%；Al2O3：23%；CaO：18%；TiO2：4%；ZrO2: 2.7 percent; preparing slag charge.
Charging into a furnace for centering, arcing the steel fragments, wherein the amount of the adopted slag is 6.5 percent of the mass of the vacuum induction cast ingot, namely, when every 1000kg of the vacuum induction cast ingot is subjected to electroslag remelting, 65kg of slag is required to be adopted, the adopted slag is equally divided into 3 parts, sequentially adding into slag for melting, stabilizing the melting voltage to be 45V, the average melting rate to be 5.8kg/min, carrying out heat capping, cooling in the furnace for 5 hours, and demoulding to obtain the 47GH 10 alloy containing Zr-Ce.
Drilling cuttings at the head, the middle and the tail of the GH4710 alloy containing Zr-Ce obtained by the comparative example, wherein the specific positions are 50mm away from the head of an ingot, the middle of the ingot and 50mm away from the tail of the ingot, and the Zr, Ce, N and O contents at the head, the middle and the tail of the GH4710 alloy are detected, and the results are shown in Table 2.
Comparative example 5
Comparative example 5 is substantially the same as comparative example 4 except that:
preparing an electroslag remelting electrode and preparing slag: cutting off a dead head of the vacuum induction cast ingot, turning, welding an auxiliary electrode, and baking for 3 hours for later use; according to mass percent, CaF2：52%；Al2O3：21.5%；CaO：18%；TiO2：4%；ZrO2：2.7%；CeO2: 1.8% preparing slag charge.
Drilling cuttings at the head, the middle and the tail of the GH4710 alloy containing Zr-Ce obtained by the comparative example, wherein the specific positions are 50mm away from the head of an ingot, the middle of the ingot and 50mm away from the tail of the ingot, and the Zr, Ce, N and O contents at the head, the middle and the tail of the GH4710 alloy are detected, and the results are shown in Table 2.
Table 2: the results of the tests of examples 1 to 4 and comparative examples 1 to 5 were compared.
Figure 540750DEST_PATH_IMAGE012
Figure 11657DEST_PATH_IMAGE013
Figure 984161DEST_PATH_IMAGE014
The results in table 2 show that the GH4710 alloy ingot containing Zr-Ce prepared by the preparation method of the present invention has high control precision of Zr and Ce content, uniform distribution, low oxygen and nitrogen content in the GH4710 alloy, and high purity of the alloy ingot; and the GH4710 alloy ingot containing Zr-Ce prepared by the comparative example has serious burning loss of Zr and Ce, and the burning loss amount is uncontrollable. As can be seen from the results in table 2, the preparation method in example 1 of the present invention has optimized process conditions, and the present invention finds that, compared with the prior art, the improvement of a single condition has no significant effect on the effects of simultaneously controlling the precision of Zr and Ce contents, the uniformity of element distribution and the purity of the alloy ingot in the prepared GH4710 alloy ingot containing Zr — Ce, compared with the prior art, in example 1 of the present invention.
The invention has not been described in detail and is in part known to those of skill in the art.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. A preparation method of a Zr-Ce-containing wrought superalloy, which is characterized by comprising the following steps:
(1) providing raw materials for preparing a Zr-Ce-containing wrought superalloy, wherein the raw materials comprise a base element raw material and an adjusting element raw material, and the adjusting element raw material comprises a zirconium raw material and a cerium raw material;
(2) the raw materials are subjected to vacuum induction melting according to the following three processes in sequence:
and (3) material melting period: firstly, carrying out power transmission smelting on a matrix element raw material to obtain a molten material to be refined; the vacuum degree in the material melting period is 15-35 Pa;
and (3) refining period: the refining period sequentially comprises a refining early period, a refining middle period and a refining late period; refining the to-be-refined molten material for 60-80 min in the early refining stage to obtain an early-stage refined molten material; in the middle stage of refining, adding a zirconium raw material and a cerium raw material into the early-stage refining molten material and continuously refining for 10-15 min to obtain a middle-stage refining molten material, and detecting the burning loss amount of the zirconium raw material and the cerium raw material in the middle-stage refining molten material; in the later refining stage, adding a zirconium raw material and a cerium raw material into the middle-stage refining molten material and continuously refining for 10-15 min to obtain an alloy melt; in the middle stage of refining, the adding amount of the zirconium raw material is 5-20 wt.% of the target content of zirconium in the Zr-Ce containing wrought high-temperature alloy, and the adding amount of the cerium raw material is 5-20 wt.% of the target content of cerium in the Zr-Ce containing wrought high-temperature alloy; the total amount of the zirconium raw material added in the middle refining stage and the later refining stage is equal to the sum of the target content of zirconium in the Zr-Ce containing wrought superalloy and the burning loss amount of the zirconium raw material in the middle refining stage; the total amount of the cerium raw material added in the middle refining stage and the later refining stage is equal to the sum of the target content of cerium in the Zr-Ce-containing wrought superalloy and the burning loss amount of the cerium raw material in the middle refining stage;
and (3) pouring period: pouring the alloy melt under the protection of argon to obtain a vacuum induction cast ingot;
(3) the vacuum induction cast ingot is used as an electroslag remelting electrode to carry out electroslag remelting to obtain the Zr-Ce-containing wrought high-temperature alloy(ii) a The slag adopted by the electroslag remelting comprises the following components in percentage by mass: CaF2，45~55%；CaO，15~22%；Al2O3，15~24%；TiO2，2~4%；ZrO2，0.5~4%；CeO2，0.5~4%。
2. The method of claim 1, wherein:
the electroslag remelting sequentially comprises primary electroslag remelting and secondary electroslag remelting; and after carrying out primary electroslag remelting on the electroslag remelting electrode to obtain a primary electroslag ingot, replacing the head and the tail of the ingot with the primary electroslag ingot to carry out secondary electroslag remelting to obtain the Zr-Ce-containing wrought high-temperature alloy.
3. The production method according to claim 1 or 2, characterized in that:
the matrix element raw materials comprise a chromium raw material, a nickel raw material, a cobalt raw material, a tungsten raw material, a molybdenum raw material and electrode carbon;
the adjusting element raw materials also comprise an aluminum raw material, a titanium raw material and a boron raw material;
in the material melting period, firstly, feeding electricity to the nickel raw material, the cobalt raw material, the tungsten raw material, the molybdenum raw material and the electrode carbon contained in the matrix element raw material for melting to obtain a fully-melted first melt material, then adding the chromium raw material contained in the matrix element raw material into the first melt material, melting and stirring for 15-20 min to obtain a melt material to be refined;
and in the middle refining stage, adding an aluminum raw material, a titanium raw material and a boron raw material which are contained in the adjusting element raw materials into the early-stage refining molten material.
4. The method of claim 1, wherein:
the slag comprises the following components in percentage by mass: CaF2，49~53%；CaO，16~20%；Al2O3，18~23%；TiO2，4%；ZrO2，1.2~2.4%；CeO2，0.8~1.6%。
5. The production method according to claim 1 or 4, characterized in that:
ZrO contained in the slag2The mass percentage of the components is determined by the following formula:
Figure 353451DEST_PATH_IMAGE001
wherein the content of the first and second substances,
Figure 332908DEST_PATH_IMAGE002
represents ZrO contained in the slag2The content of the components in percentage by mass,
Figure 909383DEST_PATH_IMAGE003
represents the target content of zirconium in the Zr-Ce containing wrought superalloy,
Figure 366909DEST_PATH_IMAGE004
represents a target content of cerium in the Zr-Ce-containing wrought superalloy;
CeO contained in the slag charge2The mass percentage of the components is determined by the following formula:
Figure 243598DEST_PATH_IMAGE005
wherein the content of the first and second substances,
Figure 659536DEST_PATH_IMAGE006
denotes CeO contained in the slag2The content of the components in percentage by mass,
Figure 254466DEST_PATH_IMAGE003
represents the target content of zirconium in the Zr-Ce containing wrought superalloy,
Figure 515683DEST_PATH_IMAGE004
representing said Zr-Ce-containingTarget content of cerium in the wrought superalloy.
6. The production method according to claim 1 or 2, characterized in that:
the electrode carbon is added in accordance with the upper limit of the composition range of the target carbon in the Zr-Ce-containing wrought superalloy; and/or
The casting temperature is 80-120 ℃ higher than the melting point of the alloy melt.
7. The production method according to claim 1 or 2, characterized in that:
the vacuum degree in the material melting period is 15-20 Pa; and/or
The vacuum degree in the refining period is not more than 0.1 Pa.
8. The method of claim 2, wherein:
the granularity of the slag is 10-20 mm; and/or
The amount of the slag adopted in each electroslag remelting is 5-7% of the mass of the vacuum induction cast ingot.
9. The production method according to claim 1 or 2, characterized in that:
the Zr-Ce-containing wrought high-temperature alloy is GH4710 wrought high-temperature alloy containing Zr-Ce.
10. The Zr-Ce containing wrought superalloy made by the method of any of claims 1-9.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113718138A (en) * 2021-11-03 2021-11-30 北京科技大学 Method for producing powder superalloy master alloy by VIDP + VHCC duplex and powder superalloy master alloy

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101487084A (en) * 2008-01-15 2009-07-22 浙江正达模具有限公司 Method for adding additive for electroslag remelting alloy tool and die steel
WO2015123918A1 (en) * 2014-02-18 2015-08-27 上海发电设备成套设计研究院 High-temperature nickel-based alloy for 700°c grade ultra-supercritical coal-fired power station and preparation thereof
SE539732C2 (en) * 2016-03-07 2017-11-14 Suzuki Garphyttan Ab Method of producing a cold drawn wire
CN108385010A (en) * 2018-04-04 2018-08-10 北京科技大学 A kind of cobalt base superalloy and preparation method thereof of low-density, high structure stability
CN110983113A (en) * 2019-12-31 2020-04-10 江苏新华合金有限公司 Cobalt-based high-temperature alloy wire and preparation method thereof
CN111187946A (en) * 2020-03-02 2020-05-22 北京钢研高纳科技股份有限公司 Nickel-based wrought superalloy with high aluminum content and preparation method thereof
CN111235434A (en) * 2020-03-02 2020-06-05 北京钢研高纳科技股份有限公司 Preparation method of nickel-based deformed superalloy wheel disc forging used at high temperature

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101487084A (en) * 2008-01-15 2009-07-22 浙江正达模具有限公司 Method for adding additive for electroslag remelting alloy tool and die steel
WO2015123918A1 (en) * 2014-02-18 2015-08-27 上海发电设备成套设计研究院 High-temperature nickel-based alloy for 700°c grade ultra-supercritical coal-fired power station and preparation thereof
SE539732C2 (en) * 2016-03-07 2017-11-14 Suzuki Garphyttan Ab Method of producing a cold drawn wire
CN108385010A (en) * 2018-04-04 2018-08-10 北京科技大学 A kind of cobalt base superalloy and preparation method thereof of low-density, high structure stability
CN110983113A (en) * 2019-12-31 2020-04-10 江苏新华合金有限公司 Cobalt-based high-temperature alloy wire and preparation method thereof
CN111187946A (en) * 2020-03-02 2020-05-22 北京钢研高纳科技股份有限公司 Nickel-based wrought superalloy with high aluminum content and preparation method thereof
CN111235434A (en) * 2020-03-02 2020-06-05 北京钢研高纳科技股份有限公司 Preparation method of nickel-based deformed superalloy wheel disc forging used at high temperature

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113718138A (en) * 2021-11-03 2021-11-30 北京科技大学 Method for producing powder superalloy master alloy by VIDP + VHCC duplex and powder superalloy master alloy

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