CN110819817B - Basic slag system for aluminum-titanium-containing nickel-based high-temperature alloy and electroslag remelting method - Google Patents

Basic slag system for aluminum-titanium-containing nickel-based high-temperature alloy and electroslag remelting method Download PDF

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CN110819817B
CN110819817B CN201911148974.3A CN201911148974A CN110819817B CN 110819817 B CN110819817 B CN 110819817B CN 201911148974 A CN201911148974 A CN 201911148974A CN 110819817 B CN110819817 B CN 110819817B
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slag
tio
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titanium
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曾莉
徐芳泓
王岩
谷宇
张威
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Taiyuan Iron and Steel Group Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/16Remelting metals
    • C22B9/18Electroslag remelting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making alloys
    • C22C1/02Making alloys by melting
    • C22C1/023Alloys based on nickel

Abstract

The invention belongs to the technical field of electroslag remelting smelting, and particularly relates to a basic slag system and an electroslag remelting method for aluminum-containing titanium-nickel-based high-temperature alloyThe method is carried out. The basic slag system for the aluminum-titanium-containing nickel-based high-temperature alloy comprises the following components in percentage by weight: CaF240-50 percent of CaO, 13-24 percent of CaO, 4-10 percent of MgO and the balance of Al2O3And TiO2. The basic slag system for the aluminum-titanium-containing nickel-based high-temperature alloy disclosed by the invention enables the burning loss or the increment of elements to be effectively controlled according to the actual values of Al and Ti elements in an electrode blank, finally meets the standard requirement, and enables the surface quality of an electroslag ingot to be remarkably improved.

Description

Basic slag system for aluminum-titanium-containing nickel-based high-temperature alloy and electroslag remelting method
Technical Field
The invention belongs to the technical field of electroslag remelting smelting, and particularly relates to a basic slag system for an aluminum-titanium-containing nickel-based high-temperature alloy and an electroslag remelting method.
Background
Electroslag remelting is a process of melting, refining and solidifying and forming a metal consumable electrode in a crystallizer by using resistance heat generated by liquid slag. The electroslag steel has the advantages of pure metal, compact structure, uniform components, excellent performance and the like, and the electroslag remelting technology is an important means for producing special alloy materials from the generation to the present.
The production process of the electroslag remelting nickel-based superalloy has a series of advantages of strong impurity removing capability, strong S removing capability, improvement of cast ingot solidification structure and the like. For common-grade to high-end grade nickel-base superalloys, electroslag remelting may be used as the second or final manufacturing step. The nickel-based high-temperature alloys widely used at present all contain a certain amount of Al and Ti elements. Al and Ti are easy-to-burn elements, and burning behaviors are mutually restricted, especially when the ratio of Ti to Al in the alloy is large, Al and Ti in the electroslag remelting process are difficult to control, and electroslag ingot components are easy to be incompatible.
The actual contents of Al and Ti in the initial electrode blank also have an uncontrollable influence on the electroslag process. For example: adopting the same slag system, wherein Al in the initial electrode blank is 0.06 percent, Ti in the initial electrode blank is 1.2 percent, after electroslag remelting, Al in the electroslag ingot is 0.25 percent, Ti in the electroslag ingot is 0.54 percent, Al and Ti are sintered, and both Al and Ti are out of the standard range; when the initial electrode blank contains 0.21% of Al and 1.15% of Ti, after electroslag remelting, the electroslag ingot contains 0.15% of Al and 0.67% of Ti, which belong to the condition that Al and Ti are both sintered. Therefore, the tiny change of the actual content of Al and Ti in the initial electrode blank can produce completely different influences on the electroslag process, simultaneously, quite high requirements are put forward on the smelting component precision of the electrode blank, and the diameter size of the electroslag ingot can also produce influences on element burning loss, so the action mechanism is quite complex.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a basic slag system for an aluminum-titanium-containing nickel-based high-temperature alloy and an electroslag remelting method.
In one aspect, the invention provides a basic slag system for an aluminum-titanium-containing nickel-based superalloy, comprising, by weight: CaF240-50 percent of CaO, 13-24 percent of CaO, 4-10 percent of MgO and the balance of Al2O3And TiO2
The basic slag system comprises the following components in percentage by weight: CaF243-47%, CaO 16-20%, MgO 5-8% and the rest Al2O3And TiO2Wherein, TiO2≤10%。
The basic slag system comprises the following components in percentage by weight: CaF245 percent of CaO, 18 percent of MgO, 6 percent of MgO and the balance of Al2O3And TiO2Wherein, TiO2≤10%。
The basic slag system described above, said TiO2The content calculation method is as follows:
TiO2content (%) - (D)i×0.9/400)×(2.5×ln(100×(Al/Ti)))/Ti(%)
Wherein D isiThe diameter of the cross section of the electroslag ingot is mm;
al is the actual content of aluminum in the electrode blank,%;
ti is the actual content of titanium in the electrode blank.
In the basic slag system, the content of titanium in the electrode blank is more than 4 times of the content of aluminum.
The basic slag system as described above, when said TiO2When the calculated content of (A) is more than 10%, the TiO2The content value of (A) is 10%.
As described aboveThe basic slag system of (A), said Al2O3And TiO2The equivalent grain diameter is less than or equal to 2 mm.
In the basic slag system, the diameter of the electroslag ingot is more than or equal to 400 mm.
In another aspect, the invention provides an electroslag remelting method, wherein the basic slag system for the aluminum-titanium-containing nickel-base superalloy is prepared in a slag preparation stage.
The technical scheme of the invention has the following beneficial effects:
(1) the basic slag system and the electroslag remelting method for the aluminum-titanium-containing nickel-based high-temperature alloy are suitable for the alloy with a larger Ti/Al content ratio (Ti/Al is more than or equal to 4.0) of an electrode blank;
(2) the basic slag system for the aluminum-titanium-containing nickel-based high-temperature alloy disclosed by the invention has the advantages that according to the actual values of Al and Ti elements in an electrode blank, the burning loss or the increment of the elements are effectively controlled, the standard requirements are finally met, and the surface quality of an electroslag ingot is obviously improved;
(3) the basic slag system for the aluminum-titanium-containing nickel-based high-temperature alloy has good fluidity and proper viscosity, and ensures that an electroslag ingot has good ingot surface quality;
(4) the basic slag system for the aluminum-titanium-containing nickel-based high-temperature alloy has higher density, and metal molten drops pass through the slag system in the electroslag remelting process, so that impurities are removed.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to fully understand the objects, features and effects of the invention. The process of the present invention employs conventional methods or apparatus in the art, except as described below. The following noun terms have meanings commonly understood by those skilled in the art unless otherwise specified.
A basic slag system for aluminum-titanium-containing nickel-base superalloy comprises the following components in percentage by weight: CaF240-50 percent of CaO, 13-24 percent of CaO, 4-10 percent of MgO and the balance of Al2O3And TiO2
The aluminum-containing titanium-nickel-based superalloyPreferably, CaF based on the weight percentage of the basic slag system243-47%, CaO 16-20%, MgO 5-8% and the rest Al2O3And TiO2Wherein, TiO2≤10%。
The basic slag system for the aluminum-titanium-containing nickel-based superalloy is more preferably, the basic slag system for the aluminum-titanium-containing nickel-based superalloy comprises the following components in percentage by weight: CaF245 percent of CaO, 18 percent of MgO, 6 percent of MgO and the balance of Al2O3And TiO2Wherein, TiO2≤10%。
The basic slag system for the aluminum-titanium-containing nickel-based high-temperature alloy is a five-element system, and the base slag system comprises the following components in parts by weight:
CaF2: as an adjuvant, the melting point, viscosity and surface tension of the slag can be reduced, but the CaF is comparable to other components2The conductivity of (2) is higher;
CaO: the slag alkalinity is increased by adding CaO into the slag, the desulfurization efficiency is improved, and the conductivity of the slag can be reduced by adding CaO;
MgO: the slag contains proper MgO, so that a layer of semi-solidified film can be formed on the surface of the slag pool, the hydrogen absorption of the slag pool can be prevented, and the transmission of the oxygen supply to the metal molten pool by the valence oxide in the slag can be prevented, so that the contents of oxygen, hydrogen and nitrogen in the ingot can be reduced, and meanwhile, the heat loss of the surface of the slag to the atmosphere radiation can be reduced by the solidified film;
Al2O3: can obviously reduce the electrical conductivity of the slag, reduce the power consumption and improve the productivity, but Al in the slag2O3The increase will increase the melting temperature and viscosity of the slag and will reduce the desulfurization effect of the slag, and in addition, the remelting process will be difficult to establish and stabilize;
TiO2: with Al in the slag system2O3And Al and Ti form a certain equilibrium relation, e.g. without TiO2Ti and Al in the electrode blank2O3The reaction makes the burning loss of Ti uncontrollable and Al2O3The excessive Al content is caused by the massive reduction of Al. Thus TiO2The amount of addition is particularly critical.
The basic slag system for the aluminum-titanium-containing nickel-based superalloy plays a synergistic role in the electroslag remelting process, and particularly, CaF2CaO and MgO are basic compositions of the slag system, so that the slag system has proper melting point, resistivity, viscosity and the like, and basic applicability to the nickel-based alloy. Al (Al)2O3And TiO2The addition of (A) mainly plays a certain thermodynamic equilibrium relationship with Al and Ti elements in a slag system, if TiO is not added2Ti and Al in the electrode blank2O3The reaction makes the burning loss of Ti uncontrollable and Al2O3The excessive Al content is caused by the massive reduction of Al. Al (Al)2O3And TiO2The method mainly plays a role in effectively controlling the burning loss of aluminum and titanium elements.
Preferably, the TiO is2The content calculation method is as follows:
TiO2content (%) - (D)i×0.9/400)×(2.5×ln(100×(Al/Ti)))/Ti(%)
Wherein D isiThe diameter of the cross section of the electroslag ingot is mm;
al is the actual content of aluminum in the electrode blank,%;
ti is the actual content of titanium in the electrode blank.
Wherein, the electroslag ingot is cylindrical.
Preferably, the content of titanium in the electrode blank is more than 4 times of the content of aluminum, and can be expressed as Ti/Al ≥ 4.0, wherein Ti/Al is the content of titanium in the electrode blank divided by the content of aluminum, and more preferably, the content of titanium in the electrode blank is 4 times to 20 times of the content of aluminum.
If the titanium content in the electrode blank is less than 4 times the aluminum content, Al, which is not suitable for the basic slag system of the present invention2O3And TiO2The Al and Ti elements in the slag system can not form a thermodynamic equilibrium relationship, and the surface quality of the electroslag ingot is deteriorated.
Preferably, when said TiO is2When the calculated content of (A) is more than 10%, the TiO2The content value of (A) is 10%. In the basic slag system of the aluminum-containing titanium-nickel-based high-temperature alloy, TiO2In the content ofLess than 10%, thereby realizing effective control of Al and Ti burning loss and achieving the expected target. However, when TiO2When the content of (A) is 10%, the burning loss control effect reaches a maximum limit value, and when TiO is further added2When the amount is contained, the surface quality of the electroslag ingot is rapidly deteriorated.
Preferably, the Al is2O3And TiO2The equivalent particle size is less than or equal to 2mm, wherein the equivalent particle size is a geometric equivalent particle size.
Because of the influence of size effect, the solidification process of the electroslag ingot is related to the size of the electroslag ingot, when the diameter of the cross section of the electroslag ingot is less than 400mm, a slag system is not accurately controlled, and qualified electroslag ingot can be obtained by randomly allocating one slag system according to the basic slag system proportion limited by the invention.
However, when the diameter of the cross section of the electroslag ingot is more than or equal to 400mm, the preferable basic slag system proportion of the invention is needed.
In another aspect, the invention provides an electroslag remelting method, wherein the electroslag remelting method is used for preparing the basic slag system for the aluminum-titanium-containing nickel-base superalloy in the slag preparation stage
The electroslag remelting method of the present invention is performed by a conventional production process, and the present invention is not limited specifically herein.
Preferably, in the electroslag remelting method, the melting speed is controlled to be 6-8 Kg/min.
The basic slag system for the aluminum-titanium-containing nickel-based high-temperature alloy and the electroslag remelting method effectively control the burning loss or the increasing amount of elements according to the actual values of Al and Ti elements in an electrode blank, finally meet the standard requirements, and obviously improve the surface quality of an electroslag ingot.
Examples
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental procedures, in which specific conditions are not specified, in the following examples were carried out according to conventional methods and conditions.
Example 1
The 825 alloy is smelted by using an electroslag remelting furnace with a 4-ton ingot type (the diameter is 500 mm). The alloy electrode blank contains Ni-42%, Cr-22%, Mo-3%, Cu-2%, Al-0.07%, Ti-1.13%, and the balance Fe, and the ratio of Ti/Al in the electrode blank is 16.14.
In slag system, CaF245 percent, CaO 18 percent and MgO 6 percent. TiO in slag system2The content (%)/1.13 ═ 4.534% was (500 × 0.9/400) × (2.5 × ln (100 × (0.07/1.13))/4.5%. Al in the slag system2O3The content is 31% -4.5% ═ 26.5%. The final basic slag system is CaF2:Al2O3:CaO:MgO:TiO245:26.5:18:6: 4.5. After electroslag remelting, the actual measurement of Al in an electroslag ingot is 0.1 percent (standard requirement is less than or equal to 0.2 percent), the actual measurement of Ti is 1.02 percent (standard requirement is less than or equal to 0.6 percent and less than or equal to 1.2 percent), the standard requirement is met, and the surface quality of the electroslag ingot is excellent.
Example 2
The 825 alloy is smelted by using an electroslag remelting furnace with a 4-ton ingot type (the diameter is 500 mm). The alloy electrode blank contains Ni-42.3%, Cr-22.1%, Mo-2.8%, Cu-2.1%, Al-0.25%, Ti-1.01% and Fe for the rest, and the ratio of Ti/Al in the electrode blank is 4.0.
In slag system, CaF245 percent, CaO 18 percent and MgO 6 percent. TiO in slag system2The content (%)/1.01 ═ 8.933% was (500 × 0.9/400) × (2.5 × ln (100 × (0.25/1.01)))/8.9%. Al in the slag system2O3The content is 31% -8.9% ═ 22.1%. The final basic slag system is CaF2:Al2O3:CaO:MgO:TiO245:22.1:18:6: 8.9. After electroslag remelting, the actual measurement of Al in an electroslag ingot is 0.18 percent (the standard requirement is less than or equal to 0.2 percent), the actual measurement of Ti is 0.98 percent (the standard requirement is less than or equal to 0.6 percent and less than or equal to 1.2 percent), the standard requirement is met, and the surface quality of the electroslag ingot is excellent.
Example 3
An alloy 825 is smelted by adopting an electroslag remelting furnace with a 6-ton ingot type (the diameter is 600 mm). The alloy electrode blank contains Ni-42.1%, Cr-21.8%, Mo-2.9%, Cu-2.2%, Al-0.17%, Ti-1.12% and Fe for the rest, and the ratio of Ti/Al in the electrode blank is 6.59.
In slag system, CaF245 percent, CaO 18 percent and MgO 6 percent. TiO in slag system2Content (%) - (600 × 0.9/400) × (2.5 × ln (100 × (0.17 ^ er)1.12))/1.12-8.194%, taking 8.2%. Al in the slag system2O3The content is 31% -8.2% ═ 22.8%. The final basic slag system is CaF2:Al2O3:CaO:MgO:TiO245:22.8:18:6: 8.2. After electroslag remelting, the actual measurement of Al in an electroslag ingot is 0.15 percent (the standard requirement is less than or equal to 0.2 percent), the actual measurement of Ti is 1.09 percent (the standard requirement is less than or equal to 0.6 percent and less than or equal to 1.2 percent), the standard requirement is met, and the surface quality of the electroslag ingot is excellent.
Example 4
An alloy 825 is smelted by adopting an electroslag remelting furnace with a 6-ton ingot type (the diameter is 600 mm). The alloy electrode blank contains Ni-39.8%, Cr-21.5%, Mo-2.9%, Cu-2.6%, Al-0.17%, Ti-1.12% and the balance Fe, and the ratio of Ti/Al in the electrode blank is 6.59.
In slag system, CaF243 percent of CaO, 16 percent of CaO and 8 percent of MgO. TiO in slag system2The content (%)/1.12 ═ 8.194% was (600 × 0.9/400) × (2.5 × ln (100 × (0.17/1.12))/8.2%. Al in the slag system2O3The content is 34% -8.2% ═ 25.8%. The final basic slag system is CaF2:Al2O3:CaO:MgO:TiO243:25.8:16:8: 8.2. After electroslag remelting, the actual measurement of Al in an electroslag ingot is 0.16 percent (the standard requirement is less than or equal to 0.2 percent), the actual measurement of Ti is 1.01 percent (the standard requirement is more than or equal to 0.6 percent and less than or equal to 1.2 percent), the standard requirement is met, and the surface quality of the electroslag ingot is excellent.
Example 5
An alloy 825 is smelted by adopting an electroslag remelting furnace with a 6-ton ingot type (the diameter is 600 mm). The alloy electrode blank contains Ni-40.5%, Cr-21.1%, Mo-2.8%, Cu-2.2%, Al-0.17%, Ti-1.12% and Fe for the rest, and the ratio of Ti/Al in the electrode blank is 6.59.
In slag system, CaF247 percent of CaO, 20 percent of CaO and 5 percent of MgO. TiO in slag system2The content (%)/1.12 ═ 8.194% was (600 × 0.9/400) × (2.5 × ln (100 × (0.17/1.12))/8.2%. Al in the slag system2O3The content is 28% -8.2% ═ 19.8%. The final basic slag system is CaF2:Al2O3:CaO:MgO:TiO247:19.8:20:5: 8.2. After electroslag remelting, 0.14 percent (less than or equal to 0.2 percent of standard requirement) of Al in an electroslag ingot is actually measured, and 0 percent of Ti is actually measured.98 percent (Ti is more than or equal to 0.6 percent and less than or equal to 1.2 percent according to the standard requirement), meets the standard requirement, and has excellent surface quality of the electroslag ingot.
Comparative example 1
The 825 alloy is smelted by using an electroslag remelting furnace with a 4-ton ingot type (the diameter is 500 mm). The alloy electrode blank contains Ni-41%, Cr-22%, Mo-3%, Cu-2%, Al-0.07%, Ti-1.13%, and the balance Fe, and the ratio of Ti/Al in the electrode blank is 16.14.
In slag system, CaF245 percent, CaO 18 percent and MgO 6 percent. TiO in slag system2The content (%)/1.13 ═ 4.534% was (500 × 0.9/400) × (2.5 × ln (100 × (0.07/1.13)))/but TiO was2The content value is 12%. Al in the slag system2O3The content is 31% -12% ═ 19%. The final basic slag system is CaF2:Al2O3:CaO:MgO:TiO245:19:18:6: 12. After electroslag remelting, 0.25% of Al (standard requirement is less than or equal to 0.2%) and 1.09% of Ti (standard requirement is less than or equal to 0.6% and less than or equal to 1.2%) are actually measured in an electroslag ingot, and the electroslag ingot has poor surface quality.
Comparative example 2
The 825 alloy is smelted by using an electroslag remelting furnace with a 4-ton ingot type (the diameter is 500 mm). The alloy electrode blank contains Ni-42.3%, Cr-22.1%, Mo-2.8%, Cu-2.1%, Al-0.25%, Ti-1.01% and Fe for the rest, and the ratio of Ti/Al in the electrode blank is 4.0.
In slag system, CaF245 percent, CaO 18 percent and MgO 6 percent. TiO in slag system2The content (%)/1.01 ═ 8.933% (500 × 0.9/400) × (2.5 × ln (100 × (0.25/1.01)))/1.01 ═ 8.933%, but TiO2The content value is 15%. Al in the slag system2O3The content is 31% -15% ═ 16%. The final basic slag system is CaF2:Al2O3:CaO:MgO:TiO245:16:18:6: 15. After electroslag remelting, 0.22% of Al (standard requirement is less than or equal to 0.2%) and 0.55% of Ti (standard requirement is less than or equal to 0.6% and less than or equal to 1.2%) are actually measured in an electroslag ingot, and the electroslag ingot has poor surface quality.
Comparative example 3
An alloy 825 is smelted by adopting an electroslag remelting furnace with a 6-ton ingot type (the diameter is 600 mm). The alloy electrode blank contains Ni-42.1%, Cr-21.8%, Mo-2.9%, Cu-2.2%, Al-0.17%, Ti-1.12% and Fe for the rest, and the ratio of Ti/Al in the electrode blank is 6.59.
In slag system, CaF243 percent of CaO, 16 percent of CaO and 8 percent of MgO. TiO in slag system2The content (%)/1.12 ═ 8.194% was (600 × 0.9/400) × (2.5 × ln (100 × (0.17/1.12)))/TiO, except that2The content value is 11%. Al in the slag system2O3The content is 34% -11% ═ 23%. The final basic slag system is CaF2:Al2O3:CaO:MgO:TiO243:23:16:8: 11. After electroslag remelting, 0.23% of Al (standard requirement is less than or equal to 0.2%) and 0.66% of Ti (standard requirement is less than or equal to 0.6% and less than or equal to 1.2%) are actually measured in an electroslag ingot, and the electroslag ingot has poor surface quality.
The present invention has been disclosed in the foregoing in terms of preferred embodiments, but it will be understood by those skilled in the art that these embodiments are merely illustrative of the present invention and should not be construed as limiting the scope of the present invention. It should be noted that all changes and substitutions equivalent to those of the embodiments are intended to be included within the scope of the claims of the present invention. Therefore, the protection scope of the present invention should be subject to the scope defined in the claims.

Claims (7)

1. A basic slag system for aluminum-containing titanium-nickel-base superalloy, comprising, by weight: CaF2 40-50 percent of CaO, 13-24 percent of CaO, 4-10 percent of MgO and the balance of Al2O3And TiO2
Wherein, the TiO is2The content of (b) is calculated by the following formula:
TiO2content (%) = (D)i×0.9/400)×(2.5×ln(100×(Al/Ti) ) )/Ti(%)
Wherein D isiThe diameter of the cross section of the electroslag ingot is mm;
al is the actual content of aluminum in the electrode blank,%;
ti is the actual content of titanium in the electrode blank,%;
wherein the content of titanium in the electrode blank is 4 to 20 times of the content of aluminum.
2. The basic slag system of claim 1, comprising, in weight percent: CaF2 43-47%, CaO 16-20%, MgO 5-8% and the rest Al2O3And TiO2Wherein, TiO2≤10%。
3. The basic slag system of claim 2, comprising, in weight percent: CaF245 percent of CaO, 18 percent of MgO, 6 percent of MgO and the balance of Al2O3And TiO2Wherein, TiO2≤10%。
4. The basic slag system of claim 1, wherein when the TiO is present2When the calculated content of (A) is more than 10%, the TiO2The content value of (A) is 10%.
5. The basic slag system of claim 1, wherein the Al is2O3And TiO2The equivalent grain diameter is less than or equal to 2 mm.
6. The basic slag system according to claim 1, wherein the diameter of the electroslag ingot is not less than 400 mm.
7. An electroslag remelting process, characterised in that a basic slag system for aluminium-titanium-containing nickel-base superalloys according to any of claims 1-6 is formulated in the slag preparation phase.
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