EP3797898B1 - A mould flux and the use thereof - Google Patents

A mould flux and the use thereof Download PDF

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Publication number
EP3797898B1
EP3797898B1 EP19199984.6A EP19199984A EP3797898B1 EP 3797898 B1 EP3797898 B1 EP 3797898B1 EP 19199984 A EP19199984 A EP 19199984A EP 3797898 B1 EP3797898 B1 EP 3797898B1
Authority
EP
European Patent Office
Prior art keywords
mould flux
mould
present
sio
flux
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP19199984.6A
Other languages
German (de)
French (fr)
Other versions
EP3797898A1 (en
Inventor
Bertil WALDÈN
Manas Paliwal
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Alleima AB
Original Assignee
Sandvik Materials Technology AB
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Filing date
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Application filed by Sandvik Materials Technology AB filed Critical Sandvik Materials Technology AB
Priority to EP19199984.6A priority Critical patent/EP3797898B1/en
Publication of EP3797898A1 publication Critical patent/EP3797898A1/en
Application granted granted Critical
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/10—Supplying or treating molten metal
    • B22D11/108—Feeding additives, powders, or the like
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/10—Handling in a vacuum
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0037—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 by injecting powdered material
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0075—Treating in a ladle furnace, e.g. up-/reheating of molten steel within the ladle

Definitions

  • the present disclosure relates to a mould flux and to a method of manufacturing a nickel-base alloy.
  • KR2019009901 relates to a flux to be employed by casting of steels, said flux comprising SiO 2 37.6-39.6 wt%, CaO 27.2-29.2 wt %, MgO 2.6-3.6 wt%, Al 2 O 3 1-3 wt %, Na 2 O 15.1-16.1 wt%, K 2 O 0.16-0.18 wt%, Fe 2 O 3 0.56-0.83 wt%, Li 2 O 2.57-2.85 wt%.
  • the present disclosure therefore provides a mould flux having a composition of, in weight% SiO 2 15-25; CaO 15-35; Al 2 O 3 1-7; Na 2 O 18-30; K 2 O 15-25; Fe 2 O 3 0-5; C 0-4; TiO 2 0-2; MnO 0-2; MgO 0-2; Li 2 O 0-10; and wherein the melting point of the mould flux is less than or equal to 1300°C.
  • Mould fluxes are synthetic slags constituted by a complex mix of oxides, minerals and carbonaceous materials.
  • the main oxides are silica (SiO 2 ), calcium oxide (CaO), sodium oxide (Na 2 O), alumina (Al 2 O 3 ) and magnesium oxide (MgO).
  • the liquid slag formed by the flux constitutes a barrier to avoid steel re-oxidation by contact with air and the entrapment of other gases, such as nitrogen.
  • the fluxes can be added through the top of the mould on the liquid steel, manually or automatically.
  • the mould flux is provided as a powder having the above-mentioned or below-mentioned composition. The flux will then melt in contact with the molten alloy.
  • the present composition limits the CaO content in the mould powder compared to conventional mould fluxes.
  • Perovskite phase formation is assumed to be as follows: SiO 2 +Ti ⁇ TiO 2 +Si.
  • TiO 2 may together with CaO form Perovskite as a solution of Ca 2 Ti 2 O 5 and Ca 2 Ti 2 O 6 .
  • CaO in the flux contributes to the formation of Perovskite.
  • the mould flux according to the present disclosure suppresses the formation of a Perovskite phase compared to mould fluxes of prior art.
  • At least a part of Na 2 O, SiO 2 and Al 2 O 3 present in the mould flux are in the form of Sodium Feldspar (Na 0.33 Al 0.35 Si 1.13 O 2.95 ).
  • at least 25%, or at least 40% of Na 2 O, SiO 2 and Al 2 O 3 present in the mould flux are in the form of Sodium Feldspar (Na 0.33 Al 0.35 Si 1.13 O 2.95 ).
  • at least 50%, or at least 90% of the Na 2 O present in the mould flux is in the form of Sodium Feldspar, (Na 0.33 Al 0.35 Si 1.13 O 2.95 ).
  • At least a part of K 2 O, SiO 2 and Al 2 O 3 present in the mould flux is present in the form of Potassium Feldspar (K 0.33 Al 0.35 Si 1.13 O 2.95 ).
  • at least 25%, or at least 40% of K 2 O, SiO 2 and Al 2 O 3 present in the mould flux is present in the form of Potassium Feldspar (K 0.33 Al 0.35 Si 1.13 O 2.95 ).
  • at least 50%, or at least 90%, of the K 2 O present in the mould flux is present in the form of Potassium Feldspar (K 0.33 Al 0.35 Si 1.13 O 2.95 ).
  • the content of Na 2 O in the mould flux is 18-25 weight%.
  • the content of K 2 O in the mould flux is 15-22 weight%.
  • the content of TiO 2 in the mould flux is >0.05 weight%.
  • the content of Li 2 O in the mould flux is >1.0 weight%.
  • the ratio of CaO and SiO 2 (CaO/SiO 2 )- is in the range of 3:4 to 4:3, such as 1:1. These oxides are important to control the viscosity and the melting point of the mould flux.
  • a CaO content greater than 35 weight% will promote the formation of Perovskite and CaO less than 15 % might induce high viscosity in the molten mould powder.
  • the content of SiO 2 should be controlled on the basis of CaO.
  • Na 2 O, K 2 O and Li 2 O will stabilize Ti in the melt and thereby as mentioned above will contribute to the prevention of Perovskite formation. This is best results are achieved when each of Na 2 O and K 2 O is present in an amount of 18-22 weight%, preferably around 20 weight%, in the mould mixture.
  • these alkali oxides promote the formation of Nepheline phase which is beneficial during casting. A very high content of these oxides will make the flux mould too fluid and a too low content would result in formation of Perovskite phase.
  • the objective of the present disclosure is also achieved by means of a method of moulding a piece of a Ni-base alloy wherein a mould flux as defined hereinabove or hereinafter is applied on a surface of the molten alloy during moulding thereof.
  • the Ni-base alloy comprises, in weight%: C ⁇ 0.05; Cr 17-23; Ni 35-63; Mo 2.5-9.5; Ti 0.3-3.0; Al 0-0.7; Si 0-0.5; Nb 0-4.5; Cu 0-3; Mn 0-0.1; S 0-0.003; P: 0-0.02; balance Fe.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Nonmetallic Welding Materials (AREA)
  • Treatment Of Steel In Its Molten State (AREA)

Description

    TECHNICAL FIELD
  • The present disclosure relates to a mould flux and to a method of manufacturing a nickel-base alloy.
    • BACKGROUND
  • When manufacturing nickel-base alloys, especially nickel-base alloys containing titanium, a problem has been noticed in connection to the Vacuum Arc Re-melting process (VAR) following the moulding of a piece of the alloy. as it has been seen that the arc may become unstable and, as a result thereof, the process sometimes stops. Such unwanted stops of the process are caused by the fact that a portion in the moulded piece has a substantially lower electric conductivity than the rest of the moulded piece, resulting in an unstable arc or extinction of the arc. It is therefore an aspect of the present disclosure to provide a solution or at least reduce the above-mentioned problem. KR2019009901 relates to a flux to be employed by casting of steels, said flux comprising SiO2 37.6-39.6 wt%, CaO 27.2-29.2 wt %, MgO 2.6-3.6 wt%, Al2O31-3 wt %, Na2O 15.1-16.1 wt%, K2O 0.16-0.18 wt%, Fe2O3 0.56-0.83 wt%, Li2O 2.57-2.85 wt%.
    • SUMMARY
  • The present disclosure therefore provides a mould flux having a composition of, in weight%
    SiO2 15-25;
    CaO 15-35;
    Al2O3 1-7;
    Na2O 18-30;
    K2O 15-25;
    Fe2O3 0-5;
    C 0-4;
    TiO2 0-2;
    MnO 0-2;
    MgO 0-2;
    Li2O 0-10;
    and wherein the melting point of the mould flux is less than or equal to 1300°C.
  • Mould fluxes are synthetic slags constituted by a complex mix of oxides, minerals and carbonaceous materials. The main oxides are silica (SiO2), calcium oxide (CaO), sodium oxide (Na2O), alumina (Al2O3) and magnesium oxide (MgO).
  • The liquid slag formed by the flux constitutes a barrier to avoid steel re-oxidation by contact with air and the entrapment of other gases, such as nitrogen. The fluxes can be added through the top of the mould on the liquid steel, manually or automatically.
  • According to one embodiment, the mould flux is provided as a powder having the above-mentioned or below-mentioned composition. The flux will then melt in contact with the molten alloy.
  • It has been found been surprisingly found that the use of the present mould flux when moulding Ni-base alloys, especially those nickel base alloys containing Ti will prevent or suppress the formation of portions of lower electric conductivity in the moulded piece, such that the above-mentioned problem during a subsequent VAR process is remedied.
  • When the nickel base alloy contains Ti, the presence of CaO in the mould flux and the Ti content in the nickel alloy will be responsible for the formation of Perovskite. Hence, the present composition limits the CaO content in the mould powder compared to conventional mould fluxes.
  • Additionally, if CaO content is lowered, then in order to control the various thermo-physical properties of mould powder such as melting point, density and viscosity, the content of SiO2 should be lowered as well.
  • Furthermore, it has been found that local portions in moulded pieces of a Ni-base alloy, especially those containing titanium have a lower electric conductivity than the rest of the piece. This is due to the fact that said portions comprise a Perovskite phase. The Perovskite phase formation is assumed to be as follows: SiO2+Ti→TiO2+Si. As a result, TiO2 may together with CaO form Perovskite as a solution of Ca2Ti2O5 and Ca2Ti2O6. As mentioned herein, CaO in the flux contributes to the formation of Perovskite. The mould flux according to the present disclosure suppresses the formation of a Perovskite phase compared to mould fluxes of prior art. A relatively low content of SiO2 in the present mould flux powder and a relatively high content of alkali oxides (Na2O and K2O), and possibly also the effect of Li2O and MgO, is assumed to suppress the formation of Perovskite.
  • According to one embodiment of the mould flux as defined hereinabove or hereinafter, at least a part of Na2O, SiO2 and Al2O3 present in the mould flux are in the form of Sodium Feldspar (Na0.33Al0.35Si1.13O2.95). According to further embodiments, at least 25%, or at least 40% of Na2O, SiO2 and Al2O3 present in the mould flux are in the form of Sodium Feldspar (Na0.33Al0.35Si1.13O2.95). According to further embodiments, at least 50%, or at least 90% of the Na2O present in the mould flux is in the form of Sodium Feldspar, (Na0.33Al0.35Si1.13O2.95).
  • According to one embodiment of the mould flux as defined hereinabove or hereinafter, at least a part of K2O, SiO2 and Al2O3 present in the mould flux is present in the form of Potassium Feldspar (K0.33Al0.35Si1.13O2.95). According to further embodiments at least 25%, or at least 40% of K2O, SiO2 and Al2O3 present in the mould flux is present in the form of Potassium Feldspar (K0.33Al0.35Si1.13O2.95). According to further embodiments, at least 50%, or at least 90%, of the K2O present in the mould flux is present in the form of Potassium Feldspar (K0.33Al0.35Si1.13O2.95).
  • According to one embodiment, the content of Na2O in the mould flux is 18-25 weight%.
  • According to one embodiment, the content of K2O in the mould flux is 15-22 weight%.
  • According to one embodiment, the content of TiO2 in the mould flux is >0.05 weight%.
  • According to one embodiment, the content of Li2O in the mould flux is >1.0 weight%.
  • According to one embodiment, the ratio of SiO2/(CaO+Al2O3)>1 .
  • According to one embodiment, the ratio of CaO and SiO2 (CaO/SiO2)- is in the range of 3:4 to 4:3, such as 1:1. These oxides are important to control the viscosity and the melting point of the mould flux. A CaO content greater than 35 weight% will promote the formation of Perovskite and CaO less than 15 % might induce high viscosity in the molten mould powder. The content of SiO2 should be controlled on the basis of CaO.
  • Na2O, K2O and Li2O will stabilize Ti in the melt and thereby as mentioned above will contribute to the prevention of Perovskite formation. This is best results are achieved when each of Na2O and K2O is present in an amount of 18-22 weight%, preferably around 20 weight%, in the mould mixture. In addition, these alkali oxides promote the formation of Nepheline phase which is beneficial during casting. A very high content of these oxides will make the flux mould too fluid and a too low content would result in formation of Perovskite phase.
  • The objective of the present disclosure is also achieved by means of a method of moulding a piece of a Ni-base alloy wherein a mould flux as defined hereinabove or hereinafter is applied on a surface of the molten alloy during moulding thereof.
  • According to one embodiment, the Ni-base alloy comprises, in weight%:
    C <0.05;
    Cr 17-23;
    Ni 35-63;
    Mo 2.5-9.5;
    Ti 0.3-3.0;
    Al 0-0.7;
    Si 0-0.5;
    Nb 0-4.5;
    Cu 0-3;
    Mn 0-0.1;
    S 0-0.003;
    P: 0-0.02;
    balance Fe.

Claims (14)

  1. A mould flux having a composition of, in weight%: SiO2 15-25; CaO 15-35; Al2O3 1-7; Na2O 18-30; K2O 15-25; Fe2O3 0-5; C 0-4; TiO2 0-2; MnO 0-2; MgO 0-2; Li2O 0-10;
    and wherein the melting point of the mould flux is less than or equal to 1300°C.
  2. The mould flux according to claim 1, wherein at least a part of Na2O, SiO2 and Al2O3 present in the mould flux is present in the form of Sodium Feldspar, Na0.33Al0.35Si1.13O2.95.
  3. The mould flux according to claim 1 or 2, wherein at least a part of K2O, SiO2 and Al2O3 present in the mould flux is present in the form of Potassium Feldspar, K0.33Al0.35Si1.13O2.95.
  4. The mould flux according to any one of claims 1-3, wherein at least 50% of the Na2O present in the mould flux is in the form of Sodium Feldspar, Na0.33Al0.35Si1.13O2.95.
  5. The mould flux according to any one of claims 1-4, wherein at least 50%, of the K2O present in the mould flux is present in the form of Potassium Feldspar, K0.33Al0.35Si1.13O2.95.
  6. The mould flux according to any one of claims 1-5, wherein the content of Na2O, in weight%, is 18-25.
  7. The mould flux according to any one of claims 1-6, wherein the content of K2O, in weight %, is 15-22.
  8. The mould flux according to any one of claims 1-7, wherein the content of TiO2 is >0.05 weight%.
  9. The mould flux according to any one of claims 1-8, wherein the content of Li2O is >1.0 weight%.
  10. The mould flux according to any one of claims 1-9, wherein SiO2/(CaO+Al2O3)>1.
  11. The mould flux according to any one of claims 1-10, wherein the ratio between CaO and SiO2 is in the range of 3:4 - 4:3.
  12. The mould flux according to any one of claims 1-11, wherein the mould flux is a powder having the composition according to any one of claims 1-11.
  13. A method of manufacturing a nickel-base alloy, wherein a mould flux according to any one of claims 1-12 is applied on a surface of the molten nickel-base alloy during moulding thereof.
  14. A method according to claim 13, wherein said Ni-base alloy comprises, in weight%: C <0.05; Cr 17-23; Ni 35-63; Mo 2.5-9.5; Ti 0.3-3.0; Al 0-0.7; Si 0-0.5; Nb 0-4.5; Cu 0-3; Mn 0-0.1; S 0-0.003; P: 0-0.02;
    balance Fe.
EP19199984.6A 2019-09-26 2019-09-26 A mould flux and the use thereof Active EP3797898B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19199984.6A EP3797898B1 (en) 2019-09-26 2019-09-26 A mould flux and the use thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19199984.6A EP3797898B1 (en) 2019-09-26 2019-09-26 A mould flux and the use thereof

Publications (2)

Publication Number Publication Date
EP3797898A1 EP3797898A1 (en) 2021-03-31
EP3797898B1 true EP3797898B1 (en) 2022-07-27

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Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1016724A (en) * 1972-09-18 1977-09-06 Smc Corporation Flux for continuous casting of steel
JP2994718B2 (en) * 1990-09-29 1999-12-27 株式会社神戸製鋼所 Flux for continuous casting
EP2035169B1 (en) * 2006-06-22 2017-03-15 Posco Mold flux and continuous casting method using the same
JP5585347B2 (en) * 2010-09-27 2014-09-10 品川リフラクトリーズ株式会社 Mold powder for continuous casting of steel
KR102073318B1 (en) * 2015-11-05 2020-02-03 닛폰세이테츠 가부시키가이샤 Mold flux for continuous casting and continuous casting method
KR102033641B1 (en) * 2018-02-13 2019-10-18 주식회사 포스코 Mold flux and casting method

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Publication number Publication date
EP3797898A1 (en) 2021-03-31

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