US20090277304A1 - Process for production of fe based amorphous alloy - Google Patents

Process for production of fe based amorphous alloy Download PDF

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US20090277304A1
US20090277304A1 US12/296,907 US29690707A US2009277304A1 US 20090277304 A1 US20090277304 A1 US 20090277304A1 US 29690707 A US29690707 A US 29690707A US 2009277304 A1 US2009277304 A1 US 2009277304A1
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mass
content
amorphous alloy
concentration
iron
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Yuji Ogawa
Takeshi Imai
Shigekatsu Ozaki
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Nippon Steel Corp
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    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D7/00Modifying the physical properties of iron or steel by deformation
    • C21D7/02Modifying the physical properties of iron or steel by deformation by cold working
    • C21D7/04Modifying the physical properties of iron or steel by deformation by cold working of the surface
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C45/00Amorphous alloys
    • C22C45/02Amorphous alloys with iron as the major constituent
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21CPROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/56Manufacture of steel by other methods
    • C21C5/562Manufacture of steel by other methods starting from scrap
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21CPROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04Removing impurities by adding a treating agent
    • C21C7/076Use of slags or fluxes as treating agents
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/003Making ferrous alloys making amorphous alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147Alloys characterised by their composition
    • H01F1/153Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15308Amorphous metallic alloys, e.g. glassy metals based on Fe/Ni
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C2200/00Crystalline structure
    • C22C2200/02Amorphous
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Definitions

  • the present invention relates to a process for production of an Fe-based amorphous alloy at a low cost.
  • Amorphous alloy ribbons whose base component system is Fe—B—Si have excellent properties as electromagnetic materials. When used as an iron core material in an electric power transformer, such an amorphous alloy ribbon can lower core loss to about 1 ⁇ 3 that when using conventional grain-oriented Si-steel sheet. However, the implementation of the mass production of Fe—B—Si amorphous alloy ribbons has been slow.
  • a method for inexpensive production of amorphous alloy is described in Japanese Patent Publication (A) No. S58-77509 which provides a process for smelting reduction of boron oxide or boric acid and iron oxide using a carbon-based solid reducing agent such as coke.
  • a carbon reducing agent such as coke.
  • this method has a problem in that when it is attempted to directly produce the amorphous alloy to optimum B and Si contents for obtaining a steel with good electromagnetic properties, the C content comes to exceed the optimum range.
  • Japanese Patent Publication (A) No. S59-38353 describes a method of once producing a matrix alloy with high B and Si contents so that a C content in the optimum range can be obtained and thereafter diluting the B and Si with a separately produced molten steel.
  • this method shortens the service life of the melting furnace refractory and increases raw material consumption per unit product because B reduction yield is lowered.
  • Japanese Patent Publication (A) No. S62-287040 further describes a method for overcoming these problems by adjusting the composition of the matrix alloy to a somewhat low B content and high Si content.
  • Other general methods for producing Fe—B as a B raw material can include methods that perform refining by the aluminum thermite reaction or the electric furnace method.
  • the electric furnace method consumes significant amount of electric power, likely resulting in high power costs and increasing the cost of amorphous alloy production.
  • the aluminum thermite method is low in production cost, the resulting Fe—B includes Al and Ti, and an amorphous alloy produced using the Fe—B is therefore increased in Ti concentration and Al concentration.
  • increased Ti and Al concentration is known to degrade magnetic properties, Fe—B produced by the aluminum thermite reaction cannot be used to produce amorphous alloys until cheap removal of Ti and Al becomes possible.
  • scrap Si-steel sheet or the like as the starting material containing Fe and Si, such scrap is difficult to use for amorphous alloy because the Al contamination of the scrap similarly increases the Al concentration of the amorphous alloy.
  • Exemplary embodiments of the present invention can be provided with an exemplary process for production of an Fe-based amorphous alloy ribbon at low cost by efficiently removing magnetic-property-degrading Al and Ti when using inexpensive Fe—B or scrap as an amorphous alloy raw material.
  • An exemplary embodiment of the present invention for overcoming such problems can provide a process for production of an Fe-based amorphous alloy comprising, by mass, about 2 to 4% of B, about 1 to 6% of Si, and a balance of Fe and unavoidable materials.
  • a molten alloy obtained by melting a main raw material has a Ti concentration or Al concentration of about 0.005 mass % or greater.
  • an iron oxide source having an iron content of about 55 mass % or greater to reduce both Ti and Al to less than about 0.005 mass % by oxidative removal.
  • a process can be provided for a production of an Fe-based amorphous alloy comprising, by mass, about 2 to 4% of B, about 1 to 6% of Si, and a balance of Fe and unavoidable materials.
  • This exemplary process can determine whether a main raw material has a composition whose Ti concentration or Al concentration is 0.005 mass % or greater. When such result is obtained, it is possible to precharge an iron oxide source having an iron content of about 55 mass % or greater into a melting vessel together with the main raw material.
  • the Fe-based amorphous alloy can further include, by mass, one or both of about 0.001 to 3% of C and/or about 0.008 to 0.15% of P. Further, Fe can be partially replaced by at least one of Co plus Ni of at most about 20% of Fe content and Cr of not greater than about 6% of Fe content.
  • FIG. 1 is a diagram showing time-course changes in molten alloy Ti concentration when iron oxide sources are added to molten alloy of an amorphous alloy raw material;
  • FIG. 2 is a diagram showing time-course changes in molten alloy Al concentration when iron oxide sources are added to molten alloy of an amorphous alloy raw material.
  • a small melting furnace using a small melting furnace, it can be determined that addition of iron oxide to an Fe-based amorphous alloy raw material during melting provide an efficient oxidative removal of Ti and Al.
  • Ti and Al are oxidized preferentially relative to B or Si constituting the main components of the amorphous alloy and can therefore be oxidatively removed without significantly reducing B or Si yield.
  • a main raw material mixed with the required B and Si components can be melted in a melting furnace.
  • Ti and Al can be oxidatively removed by adding an iron oxide source containing at least 55 mass % of iron.
  • an amorphous alloy raw material containing B: about 3.2 mass % and Si: about 1.8 mass % was produced in a melting furnace, the temperature of the molten alloy was raised to about 1,500° C., and an iron oxide source was added at the rate of, by mass, about 50 kg per ton of molten alloy.
  • the experiment was conducted using various iron oxide sources.
  • a graph of certain results of the time-course changes in the concentrations of Ti and Al in the molten alloy is provided in FIG. 1 .
  • Ti and Al were reduced to less than about 0.005 mass %, a level at which no effect on magnetic properties is observed.
  • the holding time after iron oxide source refining can depends on the amount of iron oxide source used, and may be preferably about 15 min or longer.
  • an iron oxide source containing at least about 55 mass % of iron can be precharged into a melting furnace together with a main raw material prepared to include the required B and Si contents. Thereafter, melting may be conducted to produce an amorphous alloy raw material.
  • this exemplary embodiment can be preferably adopted because the prior-described exemplary embodiment in which the iron oxide source can be added after producing the molten alloy may generate dust at the time of the addition.
  • Table 1 shows exemplary Ti and Al concentrations of the molten alloy when, in the small-scale experiment discussed earlier, the various iron oxide sources were precharged into the melting furnace at the rate of, by mass, about 50 kg per ton of molten alloy and melted together with the main raw material.
  • the temperature at 10 min after meltdown was about 1,370 to 1,380° C. If Ti and Al had not been removed, their concentrations would have stayed the same as the initial values in FIG. 1 . However, e.g., in every case where an iron oxide source having an iron concentration of at least about 55% was used, the Ti and Al concentrations were less than about 0.005 mass %, demonstrating that Ti and Al were oxidatively removed at the melting stage.
  • Ti and Al are oxidatively removed at the melting stage, refining is completed within the time the material melts and rises to the temperature required for tapping.
  • the Ti concentration was about 0.005 mass % or greater.
  • the Fe-based amorphous alloy and its content ranges are explained below. Unless specifically indicated, all content ranges are expressed in mass %.
  • B can effectively improve amorphous phase forming ability and thermal stability. It may be added in an amount suitable in light of the property requirements. When B content is less than about 2%, amorphous phase cannot be obtained stably, and when it exceeds about 4%, the melting point rises to make amorphous phase formation difficult.
  • Si can also effectively improve amorphous phase forming ability and thermal stability. It may be added in an amount suitable in light of the property requirements. When Si content is less than about 1%, amorphous phase cannot be obtained stably, and when it exceeds about 6%, its effect of improving thermal stability saturates.
  • C can effectively enhances the magnetic flux density of amorphous alloy ribbon and improves amorphous phase forming ability (improves castability). Its content is decided as a suitable amount in light of the property requirements.
  • the wettability between the molten alloy and the cooling substrate can be improved to form a good amorphous alloy ribbon by making the C content 0.001% or greater and preferably 0.003% or greater.
  • C content is preferably made 0.01% or greater, because an effect of improving amorphous phase forming ability is obtained. When C content exceeds 3%, the effect of enhancing magnetic flux density declines.
  • P can effectively improves core loss property and amorphous phase forming ability.
  • P may be included in an amount suitable in light of the property requirements. Although presence of P can improve core loss property and amorphous phase forming ability, and may increase the allowable content of impurity elements, the effects of amorphous phase forming ability improvement and core loss property improvement may not be observed at a P content of less than about 0.008%. In addition, the effect of increasing the allowable content of the impurity elements Mn and S may not be exhibited. With increasing amount of P addition, cracks more readily propagate in the amorphous alloy ribbon, thereby degrading workability. Therefore, to avoid such problem, P content may be preferably about 0.15% or less.
  • the effect of the exemplary embodiment of the present invention is not particularly impaired when for the purpose of improving magnetic flux density, corrosion resistance property, annealing conditions and the like, the Fe of the composition of the exemplary embodiment of the present invention Fe-based amorphous alloy can be partially replaced by at least one of Co plus Ni of at most about 20% of the Fe content and Cr of not greater than about 6% of the Fe content.
  • Co and Ni can effectively improve magnetic flux density, they are expensive, so that from the viewpoint of raw material cost, the replacement of Fe thereby may be preferably held to about 10% or less and also preferably to about 5% or less of the Fe content.
  • the effect of the exemplary embodiment of the present invention is in no way impaired by including in the composition of the invention Fe-based amorphous alloy as constituent elements not only Fe, B, Si, C, P, Ni, Co and Cr and also known constituents such as N, Ti, Zr, V, Nb, Mo, and Cu.
  • Ti and Al can decline to less than about 0.005 mass % insofar as the temperature is equal to or higher than the matrix melting point but that the higher the temperature, the better is the Ti and Al oxidation efficiency, the lower is the final Ti and Al concentration, and the better are the B and Si yields.
  • the higher the temperature the greater is the amount of electric power needed for melting and the greater is the melting furnace refractory cost.
  • the molten alloy temperature may therefore be preferably lowered to the level at which the required amount of Ti and Al oxidative removal can be achieved.
  • Amorphous alloy raw material produced using a 3-ton class high-frequency melting furnace were subjected to Ti and Al oxidative refining.
  • main raw material was used low-cost magnetic steel scrap and Fe—B of the compositions shown in Table 2.
  • Certain amount of Fe—Si was used for Si concentration adjustment.
  • the amounts of the raw materials per unit mass are also shown in Table 2.
  • the main raw materials were melted and the molten alloy was then heated to 1,500° C.
  • the same iron oxide sources as used in the small-scale experiment namely, iron ore (Mount Newman: iron content of 65 mass %), steelmaking dust (dust occurring during decarburization treatment: iron content of 64 mass %), and sintered ore (iron content of 58 mass %), were each added in an amount of 150 kg (50 kg/t) and the melt was tapped 20 min thereafter.
  • C, P, Co, Ni and Cr were added to the main raw material for property improvement.
  • the molten composition after melting was made to contain one or both of C: about 0.001 to 3% and P: about 0.008 to 0.15%, and/or the Fe thereof was partially replaced by one or more among Co plus Ni of not greater than about 20% of the Fe content and Cr of not greater than about 6% of the Fe content.
  • a refining operation was also similarly conducted.
  • the same or similar method was used except that the refining treatment was conducted with addition of iron oxide sources having an iron content of less than 55 mass %, e.g., about 150 kg of steelmaking dust (e.g., dust occurring during hot metal pretreatment: iron content of about 53 mass %) or mixed steelmaking dust and slag.
  • Table 3 shows the compositions of the molten alloys sampled just before iron oxide source addition and Table 4 shows the compositions of the molten alloys just before tapping.
  • the Exemplary Embodiment which used iron oxide sources having iron content of 55 mass % or greater, had their concentrations of both Ti and Al lowered to less than 0.005 mass %, a level at which no effect on magnetic properties is observed. They were also found to be low in B and Si oxidative loss and have yields of 95% or greater relative to the initial mixing proportions.
  • Raw material of the same kind in the same amount as used in Example 1 was charged into a 3-ton class high-frequency melting furnace together with an iron oxide source that, as shown in FIG. 2 , had an iron content of more than 55 mass % before melting, whereafter melting was conducted.
  • an iron oxide source that, as shown in FIG. 2 , had an iron content of more than 55 mass % before melting, whereafter melting was conducted.
  • the temperature was measured and the molten alloy was sampled. After the temperature had risen to 1,500° C., the molten alloy was sampled and then tapped.
  • C, P, Co, Ni and Cr were added to the main raw material for property improvement.
  • the amorphous alloy composition after melting was made to contain one or both of C: 0.001 to 3% and P: 0.008 to 0.15%, and/or the Fe thereof was partially replaced by one or more among Co plus Ni of not greater than 20% of the Fe content and Cr of not greater than 6% of the Fe content.
  • a refining operation was also similarly conducted.
  • the same method was used except that, as shown in Table 4, melting was conducted using iron oxide sources having an iron content of less than 55 mass %.
  • Table 5 shows the compositions of the molten alloys after meltdown and Table 6 shows their compositions just before tapping.
  • the Exemplary Embodiments which used iron oxide sources having iron content of 55 mass % or greater, had their concentrations of both Ti and Al lowered to less than 0.005 mass %, a level at which no effect on magnetic properties is observed, from the stage in which the material melted down, and the Ti and Al concentrations decreased still further at the tapping stage after temperature increase. They were also found to be low in B and Si oxidative loss and have yields of 92% or greater relative to the mixing proportions before tapping.
  • the exemplary embodiments of the present invention provides a process for production of an amorphous alloy at low cost by efficiently removing magnetic-property-degrading Al and Ti when using inexpensive Fe—B or scrap as an amorphous alloy raw material.

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Abstract

According to exemplary embodiments of the present invention, a process for production of an amorphous alloy can be provided at low cost by, e.g., efficiently removing magnetic-property-degrading Al and Ti when using inexpensive Fe—B or scrap as an amorphous alloy raw material. An exemplary embodiment of the process for production of an Fe-based amorphous alloy ribbon can comprise, by mass, e.g., 2 to 4% of B, 1 to 6% of Si, and a balance of Fe and unavoidable materials is provided. For example, it can be determined whether the molten alloy obtained by melting a main raw material has a Ti concentration or Al concentration of 0.005 mass % or greater: When such even occurs, iron oxide source having an iron content of 55 mass % or greater can be added thereto to reduce both Ti and Al to less than 0.005 mass % by oxidative removal. Alternatively, it is possible to determine whether the main raw material has a composition whose Ti concentration or Al concentration is 0.005 mass % or greater, and when it does, an iron oxide source having an iron content of 55 mass % or greater is precharged into a melting vessel together with the main raw material.

Description

    CROSS-REFERENCE TO RELATED APPLICATION(S)
  • This application is a national stage application of PCT Application No. PCT/JP2007/058121 which was filed on Apr. 6, 2007, and published on Oct. 25, 2007 as International Publication No. WO 2007/119806 (the “International Application”). This application claims priority from the International Application pursuant to 35 U.S.C. § 365, and from Japanese Patent Application No. 2006-108422 filed Apr. 11, 2006, under 35 U.S.C. § 119. The disclosures of the above-referenced applications are incorporated herein by reference in their entities.
  • FIELD OF THE INVENTION
  • The present invention relates to a process for production of an Fe-based amorphous alloy at a low cost.
  • BACKGROUND INFORMATION
  • Amorphous alloy ribbons whose base component system is Fe—B—Si have excellent properties as electromagnetic materials. When used as an iron core material in an electric power transformer, such an amorphous alloy ribbon can lower core loss to about ⅓ that when using conventional grain-oriented Si-steel sheet. However, the implementation of the mass production of Fe—B—Si amorphous alloy ribbons has been slow.
  • One of the main reasons for this may be that the cost of the amorphous alloy ribbons is much higher than that of Si-steel sheet. Most of the cost is accounted for by the Fe—B or other main raw material.
  • A method for inexpensive production of amorphous alloy is described in Japanese Patent Publication (A) No. S58-77509 which provides a process for smelting reduction of boron oxide or boric acid and iron oxide using a carbon-based solid reducing agent such as coke. However, owing to the use of a carbon reducing agent, this method has a problem in that when it is attempted to directly produce the amorphous alloy to optimum B and Si contents for obtaining a steel with good electromagnetic properties, the C content comes to exceed the optimum range.
  • For overcoming this problem, Japanese Patent Publication (A) No. S59-38353 describes a method of once producing a matrix alloy with high B and Si contents so that a C content in the optimum range can be obtained and thereafter diluting the B and Si with a separately produced molten steel. However, since the product is obtained via the matrix alloy with a high B content, this method shortens the service life of the melting furnace refractory and increases raw material consumption per unit product because B reduction yield is lowered. Japanese Patent Publication (A) No. S62-287040 further describes a method for overcoming these problems by adjusting the composition of the matrix alloy to a somewhat low B content and high Si content.
  • However, the above-described methods all reduce B, Si and Fe oxides with carbon. Such methods can thus be flawed in the point of requiring great reductive energy and also in the point that they increase refractory cost tremendously because the reductive energy is obtained by using a hot air blast to burn the carbon, thus producing a high temperature that forms a molten slag made of B, Si and Fe oxides that readily causes fusion damage of the refractory.
  • Other general methods for producing Fe—B as a B raw material can include methods that perform refining by the aluminum thermite reaction or the electric furnace method. However, the electric furnace method consumes significant amount of electric power, likely resulting in high power costs and increasing the cost of amorphous alloy production. Although the aluminum thermite method is low in production cost, the resulting Fe—B includes Al and Ti, and an amorphous alloy produced using the Fe—B is therefore increased in Ti concentration and Al concentration. As increased Ti and Al concentration is known to degrade magnetic properties, Fe—B produced by the aluminum thermite reaction cannot be used to produce amorphous alloys until cheap removal of Ti and Al becomes possible.
  • Although it is also possible to lower production cost by using scrap Si-steel sheet or the like as the starting material containing Fe and Si, such scrap is difficult to use for amorphous alloy because the Al contamination of the scrap similarly increases the Al concentration of the amorphous alloy.
  • Accordingly, there may be a need to address and/or overcome at least some of the deficiencies described herein above.
  • SUMMARY OF EXEMPLARY EMBODIMENTS OF THE INVENTION
  • In view of the previously-described problems, [0013] Exemplary embodiments of the present invention can be provided with an exemplary process for production of an Fe-based amorphous alloy ribbon at low cost by efficiently removing magnetic-property-degrading Al and Ti when using inexpensive Fe—B or scrap as an amorphous alloy raw material.
  • An exemplary embodiment of the present invention for overcoming such problems can provide a process for production of an Fe-based amorphous alloy comprising, by mass, about 2 to 4% of B, about 1 to 6% of Si, and a balance of Fe and unavoidable materials. Using such exemplary process, it is possible to determine whether a molten alloy obtained by melting a main raw material has a Ti concentration or Al concentration of about 0.005 mass % or greater. When it does, it is possible to add thereto an iron oxide source having an iron content of about 55 mass % or greater to reduce both Ti and Al to less than about 0.005 mass % by oxidative removal.
  • According to another exemplary embodiment of the present invention, a process can be provided for a production of an Fe-based amorphous alloy comprising, by mass, about 2 to 4% of B, about 1 to 6% of Si, and a balance of Fe and unavoidable materials. This exemplary process can determine whether a main raw material has a composition whose Ti concentration or Al concentration is 0.005 mass % or greater. When such result is obtained, it is possible to precharge an iron oxide source having an iron content of about 55 mass % or greater into a melting vessel together with the main raw material.
  • According to yet another exemplary embodiment of the present invention, the Fe-based amorphous alloy can further include, by mass, one or both of about 0.001 to 3% of C and/or about 0.008 to 0.15% of P. Further, Fe can be partially replaced by at least one of Co plus Ni of at most about 20% of Fe content and Cr of not greater than about 6% of Fe content.
  • These and other objects, features and advantages of the present invention will become apparent upon reading the following detailed description of embodiments of the invention, when taken in conjunction with the appended claims.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • Further objects, features and advantages of the invention will become apparent from the following detailed description taken in conjunction with the accompanying figure showing illustrative embodiment(s), result(s) and/or feature(s) of the exemplary embodiment(s) of the present invention, in which:
  • FIG. 1 is a diagram showing time-course changes in molten alloy Ti concentration when iron oxide sources are added to molten alloy of an amorphous alloy raw material; and
  • FIG. 2 is a diagram showing time-course changes in molten alloy Al concentration when iron oxide sources are added to molten alloy of an amorphous alloy raw material.
  • Throughout the figures, the same reference numerals and characters, unless otherwise stated, are used to denote like features, elements, components or portions of the illustrated embodiments. Moreover, while the present invention will now be described in detail with reference to the figures, it is done so in connection with the illustrative embodiments.
  • DETAILED DESCRIPTION OF THE INVENTION
  • According to an exemplary embodiment of the present invention, using a small melting furnace, it can be determined that addition of iron oxide to an Fe-based amorphous alloy raw material during melting provide an efficient oxidative removal of Ti and Al. Ti and Al are oxidized preferentially relative to B or Si constituting the main components of the amorphous alloy and can therefore be oxidatively removed without significantly reducing B or Si yield.
  • In one exemplary embodiment of the present invention, a main raw material mixed with the required B and Si components can be melted in a melting furnace. When a molten alloy has been formed, Ti and Al can be oxidatively removed by adding an iron oxide source containing at least 55 mass % of iron.
  • In a small-scale experiment, an amorphous alloy raw material containing B: about 3.2 mass % and Si: about 1.8 mass % was produced in a melting furnace, the temperature of the molten alloy was raised to about 1,500° C., and an iron oxide source was added at the rate of, by mass, about 50 kg per ton of molten alloy. The experiment was conducted using various iron oxide sources. A graph of certain results of the time-course changes in the concentrations of Ti and Al in the molten alloy is provided in FIG. 1. In the case of all iron oxide sources having an iron content of at least 55%, Ti and Al were reduced to less than about 0.005 mass %, a level at which no effect on magnetic properties is observed.
  • However, the speed of Ti and Al oxidative removal decreased in proportion as the iron oxide source was lower in iron content and higher in content of gangue constituents other than iron oxide. On the other hand, when steelmaking dust of an iron concentration of less than about 55% was used as the iron oxide source, the Ti and Al oxidative removal speed was slow and Ti was not reduced to less than about 0.005 mass %. A production cost analysis was carried out taking into account the amount of added iron oxide source required, refining time, slag treatment expense owing to increase in generated slag volume from gangue and the like, and other factors. The results showed that the effect can be small unless the iron concentration is about 55% or greater.
  • The holding time after iron oxide source refining can depends on the amount of iron oxide source used, and may be preferably about 15 min or longer.
  • In another exemplary embodiment of the present invention, an iron oxide source containing at least about 55 mass % of iron can be precharged into a melting furnace together with a main raw material prepared to include the required B and Si contents. Thereafter, melting may be conducted to produce an amorphous alloy raw material. When the dust collection capability of the melting furnace is low, this exemplary embodiment can be preferably adopted because the prior-described exemplary embodiment in which the iron oxide source can be added after producing the molten alloy may generate dust at the time of the addition.
  • Table 1 shows exemplary Ti and Al concentrations of the molten alloy when, in the small-scale experiment discussed earlier, the various iron oxide sources were precharged into the melting furnace at the rate of, by mass, about 50 kg per ton of molten alloy and melted together with the main raw material. The temperature at 10 min after meltdown was about 1,370 to 1,380° C. If Ti and Al had not been removed, their concentrations would have stayed the same as the initial values in FIG. 1. However, e.g., in every case where an iron oxide source having an iron concentration of at least about 55% was used, the Ti and Al concentrations were less than about 0.005 mass %, demonstrating that Ti and Al were oxidatively removed at the melting stage. Since Ti and Al are oxidatively removed at the melting stage, refining is completed within the time the material melts and rises to the temperature required for tapping. In contrast, when an iron oxide source having an iron concentration of less than about 55% was used, the Ti concentration was about 0.005 mass % or greater.
  • With respect to exemplary embodiments of the present invention, the Fe-based amorphous alloy and its content ranges are explained below. Unless specifically indicated, all content ranges are expressed in mass %.
  • B can effectively improve amorphous phase forming ability and thermal stability. It may be added in an amount suitable in light of the property requirements. When B content is less than about 2%, amorphous phase cannot be obtained stably, and when it exceeds about 4%, the melting point rises to make amorphous phase formation difficult.
  • Si can also effectively improve amorphous phase forming ability and thermal stability. It may be added in an amount suitable in light of the property requirements. When Si content is less than about 1%, amorphous phase cannot be obtained stably, and when it exceeds about 6%, its effect of improving thermal stability saturates.
  • C can effectively enhances the magnetic flux density of amorphous alloy ribbon and improves amorphous phase forming ability (improves castability). Its content is decided as a suitable amount in light of the property requirements. The wettability between the molten alloy and the cooling substrate can be improved to form a good amorphous alloy ribbon by making the C content 0.001% or greater and preferably 0.003% or greater. In addition, C content is preferably made 0.01% or greater, because an effect of improving amorphous phase forming ability is obtained. When C content exceeds 3%, the effect of enhancing magnetic flux density declines.
  • P can effectively improves core loss property and amorphous phase forming ability. P may be included in an amount suitable in light of the property requirements. Although presence of P can improve core loss property and amorphous phase forming ability, and may increase the allowable content of impurity elements, the effects of amorphous phase forming ability improvement and core loss property improvement may not be observed at a P content of less than about 0.008%. In addition, the effect of increasing the allowable content of the impurity elements Mn and S may not be exhibited. With increasing amount of P addition, cracks more readily propagate in the amorphous alloy ribbon, thereby degrading workability. Therefore, to avoid such problem, P content may be preferably about 0.15% or less.
  • Moreover, the effect of the exemplary embodiment of the present invention is not particularly impaired when for the purpose of improving magnetic flux density, corrosion resistance property, annealing conditions and the like, the Fe of the composition of the exemplary embodiment of the present invention Fe-based amorphous alloy can be partially replaced by at least one of Co plus Ni of at most about 20% of the Fe content and Cr of not greater than about 6% of the Fe content. Although Co and Ni can effectively improve magnetic flux density, they are expensive, so that from the viewpoint of raw material cost, the replacement of Fe thereby may be preferably held to about 10% or less and also preferably to about 5% or less of the Fe content.
  • Moreover, the effect of the exemplary embodiment of the present invention is in no way impaired by including in the composition of the invention Fe-based amorphous alloy as constituent elements not only Fe, B, Si, C, P, Ni, Co and Cr and also known constituents such as N, Ti, Zr, V, Nb, Mo, and Cu.
  • TABLE 1
    Iron Ti concentration (mass %) Al concentration (mass %)
    Iron oxide concentration Mix After Mix After
    source used (mass %) concentration melting concentration melting
    Sintered ore
    58 0.037 0.003 0.022 0.002
    Iron ore 65 0.039 0.002 0.023 0.001
    Steelmaking 64 0.032 0.002 0.021 0.001
    dust
    FeO reagent 77 0.035 0.001 0.019 <0.001
    Steelmaking 53 0.033 0.006 0.022 0.004
    dust
    Mixed 49 0.034 0.008 0.021 0.006
    steelmaking dust
    & slag
    Mixed 44 0.036 0.012 0.022 0.008
    steelmaking dust
    & slag
  • Ti and Al can decline to less than about 0.005 mass % insofar as the temperature is equal to or higher than the matrix melting point but that the higher the temperature, the better is the Ti and Al oxidation efficiency, the lower is the final Ti and Al concentration, and the better are the B and Si yields. However, the higher the temperature, the greater is the amount of electric power needed for melting and the greater is the melting furnace refractory cost. The molten alloy temperature may therefore be preferably lowered to the level at which the required amount of Ti and Al oxidative removal can be achieved.
  • EXAMPLES
  • The exemplary embodiments of the present invention can be explained based on the following examples.
  • First Set of Examples
  • Amorphous alloy raw material produced using a 3-ton class high-frequency melting furnace were subjected to Ti and Al oxidative refining. As main raw material was used low-cost magnetic steel scrap and Fe—B of the compositions shown in Table 2. Certain amount of Fe—Si was used for Si concentration adjustment. The amounts of the raw materials per unit mass are also shown in Table 2.
  • TABLE 2
    (Mass %)
    Amount per
    Si B Ti Al unit mass (kg/t)
    Magnetic 1.59 0.002 0.002 0.037 825.0
    steel scrap
    Fe—B 0.49 19.89 0.20 0.058 168.4
    Fe—Si 74.9 6.6
    Mixing 1.89 3.35 0.035 0.040 1000.0
    proportion
  • The main raw materials were melted and the molten alloy was then heated to 1,500° C. In the Invention Examples, as shown in Table 3, the same iron oxide sources as used in the small-scale experiment, namely, iron ore (Mount Newman: iron content of 65 mass %), steelmaking dust (dust occurring during decarburization treatment: iron content of 64 mass %), and sintered ore (iron content of 58 mass %), were each added in an amount of 150 kg (50 kg/t) and the melt was tapped 20 min thereafter. In certain Examples, C, P, Co, Ni and Cr were added to the main raw material for property improvement. Specifically, the molten composition after melting was made to contain one or both of C: about 0.001 to 3% and P: about 0.008 to 0.15%, and/or the Fe thereof was partially replaced by one or more among Co plus Ni of not greater than about 20% of the Fe content and Cr of not greater than about 6% of the Fe content. A refining operation was also similarly conducted. In the Comparative Examples, the same or similar method was used except that the refining treatment was conducted with addition of iron oxide sources having an iron content of less than 55 mass %, e.g., about 150 kg of steelmaking dust (e.g., dust occurring during hot metal pretreatment: iron content of about 53 mass %) or mixed steelmaking dust and slag.
  • Table 3 shows the compositions of the molten alloys sampled just before iron oxide source addition and Table 4 shows the compositions of the molten alloys just before tapping. The Exemplary Embodiment, which used iron oxide sources having iron content of 55 mass % or greater, had their concentrations of both Ti and Al lowered to less than 0.005 mass %, a level at which no effect on magnetic properties is observed. They were also found to be low in B and Si oxidative loss and have yields of 95% or greater relative to the initial mixing proportions. Moreover, in cases where the composition contained one or both of C: 0.001 to 3% and P: 0.008 to 0.15%, and the case where the Fe thereof was partially replaced by at least one of Co plus Ni of at most 20% of the Fe content and Cr of not greater than 6% of the Fe content, these effects were not impaired. In contrast, in the Comparative Embodiment, which used iron oxide sources having iron content of less than 55 mass %, the B and Si yields were on the same level but Ti concentration or Al concentration was 0.005 mass % or greater.
  • TABLE 3
    Iron
    Iron oxide source concentration Composition before iron oxide source addition (Mass %)
    Example used (mass %) Si B Ti Al C P Co Ni Cr
    Exemplary Embodiment 1 Iron ore 65 1.87 3.31 0.034 0.039
    Exemplary Embodiment 2 Steelmaking dust 64 1.89 3.31 0.035 0.038
    Exemplary Embodiment 3 Sintered ore 58 1.88 3.32 0.034 0.039
    Exemplary Embodiment 4 Iron ore 65 1.89 3.34 0.034 0.040 2.92 0.007 0.0005 0.002 0.002
    Exemplary Embodiment 5 Iron ore 65 1.88 3.31 0.035 0.040 0.0009 0.142 0.0006 0.001 0.001
    Exemplary Embodiment 6 Iron ore 65 1.89 3.33 0.034 0.039 0.0011 0.010 0.0005 0.001 0.001
    Exemplary Embodiment 7 Iron ore 65 1.89 3.33 0.036 0.040 0.0008 0.007 17.4 0.001 0.001
    Exemplary Embodiment 8 Iron ore 65 1.87 3.30 0.034 0.039 0.0009 0.007 0.0005 16.9 0.001
    Exemplary Embodiment 9 Iron ore 65 1.89 3.33 0.036 0.038 0.0009 0.006 0.0005 0.001 4.93
    Exemplary Embodiment 10 Iron ore 65 1.90 3.36 0.032 0.039 0.0008 0.006 2.11 1.97 0.001
    Exemplary Embodiment 11 Iron ore 65 1.88 3.33 0.034 0.039 0.0009 0.007 4.84 0.001 4.56
    Exemplary Embodiment 12 Iron ore 65 1.89 3.33 0.034 0.039 0.0007 0.007 0.0005 4.95 3.81
    Exemplary Embodiment 13 Iron ore 65 1.89 3.34 0.034 0.038 0.0007 0.006 1.68 1.77 2.68
    Comparative Embodiment 1 Steelmaking dust 53 1.87 3.31 0.033 0.037
    Comparative Embodiment 2 Mixed steelmaking 49 1.86 3.33 0.036 0.036
    dust & slag
    Comparative Embodiment 3 Mixed steelmaking 44 1.88 3.30 0.032 0.039
    dust & slag
  • TABLE 4
    Composition before tapping (Mass %) Yield (%)
    Example Si B Ti Al C P Co Ni Cr Si B
    Exemplary Embodiment 1 1.80 3.19 0.003 0.002 95.3 95.2
    Exemplary Embodiment 2 1.81 3.21 0.003 0.002 95.8 95.8
    Exemplary Embodiment 3 1.81 3.20 0.004 0.003 95.8 95.5
    Exemplary Embodiment 4 1.80 3.19 0.003 0.002 2.91 0.007 0.0005 0.002 0.002 95.3 95.2
    Exemplary Embodiment 5 1.81 3.21 0.003 0.002 0.0009 0.141 0.0006 0.001 0.001 95.8 95.8
    Exemplary Embodiment 6 1.80 3.19 0.003 0.002 0.0011 0.010 0.0005 0.001 0.001 95.3 95.2
    Exemplary Embodiment 7 1.80 3.20 0.002 0.001 0.0008 0.010 17.4 0.001 0.001 95.3 95.5
    Exemplary Embodiment 8 1.81 3.20 0.003 0.002 0.0009 0.010 0.0005 16.9 0.001 95.8 95.5
    Exemplary Embodiment 9 1.81 3.19 0.004 0.002 0.0009 0.010 0.0005 0.001 4.92 95.8 95.2
    Exemplary Embodiment 10 1.80 3.21 0.003 0.002 0.0008 0.010 2.11 1.97 0.001 95.3 95.8
    Exemplary Embodiment 11 1.81 3.20 0.002 0.001 0.0009 0.010 4.83 0.001 4.56 95.8 95.5
    Exemplary Embodiment 12 1.80 3.19 0.003 0.002 0.0007 0.010 0.0005 4.94 3.81 95.3 95.2
    Exemplary Embodiment 13 1.80 3.19 0.003 0.002 0.0007 0.010 1.68 1.77 2.67 95.3 95.2
    Comparative Embodiment 1 1.80 3.20 0.006 0.004 95.3 95.5
    Comparative Embodiment 2 1.79 3.21 0.008 0.005 94.8 95.8
    Comparative Embodiment 3 1.82 3.18 0.010 0.006 96.4 94.9
  • Second Set of Examples
  • Raw material of the same kind in the same amount as used in Example 1 was charged into a 3-ton class high-frequency melting furnace together with an iron oxide source that, as shown in FIG. 2, had an iron content of more than 55 mass % before melting, whereafter melting was conducted. When approximately 10 min had passed following raw material meltdown, the temperature was measured and the molten alloy was sampled. After the temperature had risen to 1,500° C., the molten alloy was sampled and then tapped. In some Exemplary Embodiments, C, P, Co, Ni and Cr were added to the main raw material for property improvement. Specifically, the amorphous alloy composition after melting was made to contain one or both of C: 0.001 to 3% and P: 0.008 to 0.15%, and/or the Fe thereof was partially replaced by one or more among Co plus Ni of not greater than 20% of the Fe content and Cr of not greater than 6% of the Fe content. A refining operation was also similarly conducted. In the Comparative Embodiments, the same method was used except that, as shown in Table 4, melting was conducted using iron oxide sources having an iron content of less than 55 mass %.
  • Table 5 shows the compositions of the molten alloys after meltdown and Table 6 shows their compositions just before tapping. The Exemplary Embodiments, which used iron oxide sources having iron content of 55 mass % or greater, had their concentrations of both Ti and Al lowered to less than 0.005 mass %, a level at which no effect on magnetic properties is observed, from the stage in which the material melted down, and the Ti and Al concentrations decreased still further at the tapping stage after temperature increase. They were also found to be low in B and Si oxidative loss and have yields of 92% or greater relative to the mixing proportions before tapping. Moreover, in case where the composition contained one or both of C: 0.001 to 3% and P: 0.008 to 0.15%, and the case where the Fe thereof was partially replaced by one or more among Co plus Ni of not greater than 20% of the Fe content and Cr of not greater than 6% of the Fe content, these effects were not impaired. In contrast, in the Comparative Embodiments, which used iron oxide sources having iron content of less than 55 mass %, the B and Si yields were on the same level but Ti concentration or Al concentration was 0.005 mass % or greater.
  • TABLE 5
    Iron
    concentration Composition after meltdown (Mass %)
    Example Iron oxide source used (mass %) Si B Ti Al C P Co Ni Cr
    Exemplary Iron ore 65 1.87 3.31 0.003 0.002
    Embodiment 1
    Exemplary Steelmaking dust 64 1.89 3.31 0.003 0.002
    Embodiment 2
    Exemplary Sintered ore 58 1.88 3.32 0.004 0.003
    Embodiment 3
    Exemplary Iron ore 65 1.89 3.34 0.003 0.002 1.99 0.007 0.0005 0.002 0.002
    Embodiment 4
    Exemplary Iron ore 65 1.88 3.31 0.003 0.001 0.0009 0.144 0.0006 0.001 0.001
    Embodiment 5
    Exemplary Iron ore 65 1.89 3.33 0.004 0.002 0.0012 0.010 0.0005 0.001 0.001
    Embodiment 6
    Exemplary Iron ore 65 1.89 3.33 0.002 0.002 0.0008 0.007 15.8 0.001 0.001
    Embodiment 7
    Exemplary Iron ore 65 1.87 3.30 0.003 0.002 0.0009 0.006 0.0005 16.2 0.001
    Embodiment 8
    Exemplary Iron ore 65 1.89 3.33 0.002 0.001 0.0008 0.007 0.0005 0.001 4.88
    Embodiment 9
    Exemplary Iron ore 65 1.90 3.36 0.003 0.002 0.0008 0.006 2.38 1.56 0.001
    Embodiment 10
    Exemplary Iron ore 65 1.88 3.33 0.004 0.002 0.0009 0.007 4.64 0.001 3.24
    Embodiment 11
    Exemplary Iron ore 65 1.89 3.33 0.003 0.002 0.0008 0.007 0.0005 4.95 4.22
    Embodiment 12
    Exemplary Iron ore 65 1.89 3.34 0.003 0.002 0.0007 0.007 1.22 1.58 2.34
    Embodiment 13
    Comparative Steelmaking dust 53 1.87 3.31 0.033 0.037
    Embodiment 1
    Comparative Mixed steelmaking dust 49 1.86 3.33 0.008 0.006
    Embodiment 2 & slag
    Comparative Mixed steelmaking dust 44 1.88 3.30 0.011 0.008
    Embodiment 3 & slag
  • TABLE 6
    Meltdown
    temp Composition before tapping (Mass %) Yield (%)
    Example (° C.) Si B Ti Al C P Co Ni Cr Si B
    Exemplary 1376 1.75 3.10 0.002 0.001 92.7 92.5
    Embodiment 1
    Exemplary 1370 1.74 3.11 0.002 0.001 92.1 92.8
    Embodiment 2
    Exemplary 1380 1.76 3.09 0.003 0.002 93.2 92.2
    Embodiment 3
    Exemplary 1380 1.75 3.09 0.003 0.002 1.98 0.007 0.0005 0.002 0.002 92.7 92.2
    Embodiment 4
    Exemplary 1375 1.75 3.10 0.002 0.001 0.0009 0.144 0.0006 0.001 0.001 92.7 92.5
    Embodiment 5
    Exemplary 1372 1.76 3.10 0.003 0.002 0.0012 0.010 0.0005 0.001 0.001 93.2 92.5
    Embodiment 6
    Exemplary 1380 1.77 3.10 0.002 0.001 0.0008 0.007 15.8 0.001 0.001 93.7 92.5
    Embodiment 7
    Exemplary 1382 1.75 3.09 0.003 0.002 0.0009 0.005 0.0005 16.2 0.001 92.7 92.2
    Embodiment 8
    Exemplary 1380 1.76 3.11 0.002 0.001 0.0008 0.006 0.0005 0.001 4.86 93.2 92.8
    Embodiment 9
    Exemplary 1371 1.75 3.09 0.003 0.002 0.0008 0.006 2.38 1.56 0.001 92.7 92.2
    Embodiment 10
    Exemplary 1379 1.75 3.10 0.003 0.001 0.0009 0.007 4.64 0.001 3.24 92.7 92.5
    Embodiment 11
    Exemplary 1371 1.76 3.09 0.002 0.001 0.0008 0.007 0.0005 4.95 4.21 93.2 92.2
    Embodiment 12
    Exemplary 1375 1.76 3.09 0.003 0.002 0.0007 0.007 1.22 1.58 2.33 93.2 92.2
    Embodiment 13
    Comparative 1375 1.75 3.11 0.006 0.004 92.7 92.8
    Embodiment 1
    Comparative 1374 1.75 3.09 0.008 0.005 92.7 92.2
    Embodiment 2
    Comparative 1376 1.74 3.09 0.010 0.006 92.1 92.2
    Embodiment 3
  • INDUSTRIAL APPLICABILITY
  • The exemplary embodiments of the present invention provides a process for production of an amorphous alloy at low cost by efficiently removing magnetic-property-degrading Al and Ti when using inexpensive Fe—B or scrap as an amorphous alloy raw material.
  • The foregoing merely illustrates the exemplary principles of the present invention. Various modifications and alterations to the described embodiments will be apparent to those skilled in the art in view of the teachings herein. It will thus be appreciated that those skilled in the art will be able to devise numerous modification to the exemplary embodiments of the present invention which, although not explicitly shown or described herein, embody the principles of the invention and are thus within the spirit and scope of the invention. All publications, applications and patents cited above are incorporated herein by reference in their entireties.

Claims (7)

1-4. (canceled)
5. A process for producing an Fe-based amorphous alloy which comprises, by mass, about 2 to 4% of B, about 1 to 6% of Si, and a balance of Fe and unavoidable materials, the process comprising:
determining whether an iron melt obtained by melting a main raw material has a Ti concentration or an Al concentration of at least about 0.005 mass %; and
when such determination yields a positive result, adding an iron oxide source having an iron content of at least about 55 mass % to the molten alloy to reduce Ti and Al to less than about 0.005 mass % using an oxidative removal procedure.
6. The process according to claim 5, wherein the Fe-based amorphous alloy further comprises, by mass, at least one of about 0.001 to 3% of C or about 0.008 to 0.15% of P.
7. The process according to claim 5, wherein, by mass, Fe is partially replaced by at least one of Co plus Ni of at most about 20% of Fe content and Cr of at most about 6% of Fe content.
8. A process for producing an Fe-based amorphous alloy which comprises, by mass, about 2 to 4% of B, about 1 to 6% of Si, and a balance of Fe and unavoidable materials, the process comprising:
determining whether a main raw material has a composition which includes a Ti concentration or an Al concentration of at least about 0.005 mass %; and
when such determination yields a positive result, precharging an iron oxide source having an iron content of at least about 55 mass % into a melting vessel with the main raw material.
9. The process according to claim 8, wherein the Fe-based amorphous alloy Fe-based amorphous alloy further comprises, by mass, at least one of about 0.001 to 3% of C or about 0.008 to 0.15% of P.
10. The process according to claim 8, wherein, by mass, Fe is partially replaced by at least one of Co plus Ni of at most about 20% of Fe content and Cr of at most about 6% of Fe content.
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