WO2021153657A1 - 合金材加熱用酸化防止剤、及び、それを用いた合金材の加熱方法 - Google Patents

合金材加熱用酸化防止剤、及び、それを用いた合金材の加熱方法 Download PDF

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Publication number
WO2021153657A1
WO2021153657A1 PCT/JP2021/002990 JP2021002990W WO2021153657A1 WO 2021153657 A1 WO2021153657 A1 WO 2021153657A1 JP 2021002990 W JP2021002990 W JP 2021002990W WO 2021153657 A1 WO2021153657 A1 WO 2021153657A1
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Prior art keywords
heating
alloy material
antioxidant
alloy
mass
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PCT/JP2021/002990
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English (en)
French (fr)
Japanese (ja)
Inventor
功輔 林
日高　康善
近藤　泰光
亜弥 藤田
聖司 宮本
崇敬 加苅
渉 野原
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Nippon Steel Corp
Takara Standard Co Ltd
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Nippon Steel Corp
Takara Standard Co Ltd
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Priority to CN202180011845.9A priority Critical patent/CN115023509B/zh
Priority to JP2021574096A priority patent/JP7333837B2/ja
Priority to EP21748377.5A priority patent/EP4098756B1/en
Publication of WO2021153657A1 publication Critical patent/WO2021153657A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
    • C21D1/70—Temporary coatings or embedding materials applied before or during heat treatment while heating or quenching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium

Definitions

  • the present invention relates to an antioxidant for heating an alloy material and a method for heating the alloy material using the antioxidant.
  • an alloy material for example, an alloy material containing Cr is known.
  • the alloy material is manufactured by the following process. First, molten steel is manufactured. Cast molten steel to obtain castings (slabs, blooms, ingots). Heat the casting. The heated casting material is hot-worked. The intermediate material obtained by hot working is molded by cold working or the like, if necessary.
  • the alloy material is heated before hot working.
  • the alloy material forms a passivation film on the surface when heated before hot working.
  • the passivation film is mainly a film mainly composed of chromia (Cr 2 O 3 ).
  • the coating film mainly composed of chromium (Cr 2 O 3 ) is also referred to as a Cr 2 O 3 coating film.
  • the Cr 2 O 3 coating suppresses the oxidation of the alloy material.
  • the alloy material may be heated at a high temperature of, for example, 1000 ° C. or higher.
  • a scale mainly composed of Fe is likely to be formed on the surface of the alloy material instead of the Cr 2 O 3 coating. If a scale mainly composed of Fe is generated on the surface of the alloy material, subsequent hot working may cause a flaw due to the scale mainly composed of Fe on the surface of the alloy material. Therefore, it is desired that oxidation of the alloy material is suppressed even when the alloy material is heated at a high temperature before hot working.
  • Patent Document 1 JP-A-2007-314875
  • Patent Document 2 JP-A-2-209420
  • Patent Document 3 JP-A-3-291325
  • Patent Document 4 Japanese Patent Application Laid-Open No. 56-026603
  • Patent Document 5 Japanese Patent Application Laid-Open No. 4-072019
  • Patent Document 6 Japanese Patent Application Laid-Open No. 4-072011
  • Patent Document 6 Japanese Patent Application Laid-Open No. 6-158153 (Patent Document) 7
  • JP-A-7-062429 Patent Document 8
  • JP-A-6-198310 Patent Document 9
  • Patent Documents 1 to 9 disclose a technique for suppressing oxidation of an alloy material by using an antioxidant.
  • Patent Documents 1 to 3 assume heating for a short time of about 20 minutes to 4 hours.
  • Patent Document 4 does not cover the time of heating before hot working.
  • Patent Documents 5 to 8 cover processed alloy materials.
  • Patent Document 1 assumes a heat treatment with a processing time of about 20 minutes.
  • the antioxidant composition of Patent Document 1 contains a plurality of glass frits having different softening points.
  • the antioxidant composition maintains an appropriate viscosity according to different temperature ranges, and the antioxidant composition is retained on the steel surface.
  • Patent Document 1 describes that the formation of scale is suppressed during heat treatment.
  • Patent Document 2 assumes heat treatment with a treatment time of about 1 hour.
  • High-temperature antioxidant in Patent Document 2 has a softening point contains a glass component is 1000 ° C. or less, and a viscosity at a temperature of 1200 ° C. as a whole is made of the glass composition is 10 3 poise or more. It is described in Patent Document 2 that this makes it possible to maintain the glass composition on the steel surface during heat treatment at a high temperature and suppress the formation of scale.
  • Patent Document 3 assumes heat treatment with a processing time of about 4 hours.
  • the method for preventing high-temperature oxidation of a metal material in Patent Document 3 is an oxidation for heating a steel material, which comprises 50 to 95% by weight of a glass component and 5 to 50% by weight of an aggregate prior to heating when the metal material is heated and rolled.
  • the inhibitor is applied to a thickness of 50 to 500 ⁇ m.
  • Patent Document 3 describes that surface oxidation can be prevented even when heated to 900 to 1300 ° C. in an oxidizing atmosphere.
  • Patent Document 4 an antioxidant is applied to the surface of a steel piece, and a part or all of the surface is covered with a steel plate and heated. It is described in Patent Document 4 that this suppresses intergranular oxidation.
  • Patent Documents 5 to 8 propose a technique for suppressing scale of an alloy processed material in the annealing treatment after hot rolling and / or cold rolling. In Patent Documents 5 to 8, it is considered that heat treatment with a processing time of about 1 hour is assumed. In Patent Documents 5 to 8, the processed steel material is subject to heat treatment.
  • a material made of an iron-based alloy containing 12 wt% or more of chromium is heated to a predetermined temperature and fed to a subsequent rolling mill to perform a predetermined rolling.
  • a method for producing a stainless steel pipe is characterized in that an antioxidant is applied to the outer surface of the material before heating and the antioxidant is removed before the start of rolling by a rolling mill. It is described in Patent Document 9 that this prevents the formation of scale as a high-temperature oxide.
  • a batch type heating furnace may be used.
  • the alloy materials are heated in a state of being stacked one above the other.
  • the alloy materials are extracted one by one from the heating furnace by a transport means such as a crane. Specifically, the ceiling of the heating furnace is opened. Then, among the plurality of alloy materials laminated in the heating furnace, the alloy material arranged at the highest level is gripped by a transport means such as a crane, and the gripped alloy material is pulled up from the heating furnace and extracted from the heating furnace. ..
  • the extracted alloy material is placed on a transport path connected to a hot working apparatus such as a rolling apparatus.
  • the alloy materials stacked one above the other may adhere to each other due to the antioxidant on the surface. If the alloy materials adhere to each other, it may be difficult to extract the alloy materials by themselves from the heating furnace.
  • blocking is a process in which alloying materials adhere to each other so that it is difficult to extract them from a heating furnace by themselves. When blocking occurs, the work of extracting the alloy material from the heating furnace becomes extremely complicated, and the workability is significantly reduced. Therefore, the antioxidant is required to have excellent blocking resistance.
  • Patent Documents 1 to 9 do not describe the adhesion between alloying materials. That is, in Patent Documents 1 to 9, blocking has not even been examined.
  • the alloy material contains a large amount of alloying elements. Therefore, segregation is likely to occur in alloy materials. If heating is carried out at a high temperature for a long time, the diffusion of alloying elements proceeds and segregation is reduced. Therefore, the alloy material may be heated at a high temperature for a long time. Specifically, before hot working, heat equalization may be carried out at a temperature of 1000 to 1350 ° C. for 15 hours to 50 hours, particularly 25 hours or more.
  • Patent Documents 1 to 9 do not mainly aim at high-temperature long-term heating (equalizing heat) for the purpose of reducing segregation of alloy materials. Therefore, when the antioxidants disclosed in Patent Documents 1 to 9 are applied to the above-mentioned high-temperature long-term heating (equalizing heat) of the alloy material, scale formation may not be sufficiently suppressed.
  • An object of the present invention is an antioxidant for heating an alloy material, which has excellent blocking resistance and also has excellent oxidation resistance even when heated at a high temperature for a long time, and can suppress blocking, and further, has a high temperature length. It is an object of the present invention to provide a method for heating an alloy material, which can suppress oxidation of the alloy material even when it is heated for a long time.
  • the present-disclosed antioxidant for heating alloy materials is When converted to oxide, in mass%, SiO 2 : 40.0 to 80.0%, Al 2 O 3 : 0 to 30.0%, MgO: 0-5.0%, A total of 10.00 to 50.00% of one or more selected from the group consisting of Na 2 O: 10.0% or less, K 2 O: 20.00% or less, and Ca O: 25.0% or less. ,as well as, B 2 O 3 : Contains 0 to less than 0.5%, The balance is composed of impurities and satisfies the formula (1).
  • the method for heating the alloy material of the present disclosure is as follows. The process of applying the above-mentioned antioxidant for heating alloy materials to the surface of alloy materials, and A step of heating the alloy material coated with the antioxidant for heating the alloy material is provided.
  • the antioxidant for heating alloy materials of the present disclosure has excellent blocking resistance, and further has excellent oxidation resistance even when heated at a high temperature for a long time. Further, the method for heating the alloy material of the present disclosure can suppress blocking, and further, it is possible to suppress oxidation of the alloy material even when it is heated at a high temperature for a long time.
  • FIG. 1 is a plan view of the plate-shaped test piece of test number 1-1 in the example.
  • FIG. 2 is a plan view of the plate-shaped test piece of test number 1-2 in the example.
  • FIG. 3 is a plan view of the plate-shaped test piece of test number 1-3 in the example.
  • FIG. 4 is a cross-sectional observation view taken with a scanning electron microscope (SEM) of test number 1-1 in the example.
  • FIG. 5 is a cross-sectional observation view by SEM of test number 1-2 in the example.
  • FIG. 6 is a cross-sectional observation view of Test No. 1-3 in the examples by SEM.
  • FIG. 7 is a diagram obtained by analyzing a cross section of the plate-shaped test piece of Test No.
  • FIG. 8 is a diagram obtained by analyzing the cross section of the plate-shaped test piece of test number 1-2 in the example by EPMA.
  • FIG. 9 is a diagram obtained by analyzing the cross section of the plate-shaped test piece of test number 1-3 in the example by EPMA.
  • FIG. 10 is a graph of the amount of dust generated (mg / m 3 ) when the antioxidants for heating alloy materials of Test No. 1-1 and Test No. 1-2 in the Examples were used.
  • FIG. 11 is a schematic view of an apparatus for evaluating blocking resistance.
  • the present inventors have conducted various investigations and studies on an antioxidant for heating an alloy material, which has excellent blocking resistance and also has excellent oxidation resistance even when heated at a high temperature for a long time.
  • the process of heating at a temperature of 1000 to 1350 ° C. for 15 to 50 hours is referred to as "high temperature long-time heating”.
  • the present inventors may not obtain sufficient oxidation resistance when heated at a high temperature for a long time even if the antioxidants disclosed in the above-mentioned Patent Documents 1 to 9 are used. The cause was investigated.
  • the alloy material when the alloy material is heated at a high temperature for a long time, a scale mainly composed of Fe is likely to be generated instead of the Cr 2 O 3 coating.
  • the total amount of oxygen supplied to the surface of the alloy material during heating becomes larger than that in the short-time heating.
  • the amount of Cr supplied from the inside of the alloy material to the surface of the alloy material is insufficient with respect to the amount of Cr required for maintaining and forming the Cr 2 O 3 film.
  • Fe is preferentially oxidized over Cr on the surface of the alloy material to form FeO.
  • Cr 2 O 3 is consumed and the Cr 2 O 3 coating is broken.
  • Oxidation of the alloy material is further accelerated at the portion where the Cr 2 O 3 coating is broken.
  • scales mainly composed of FeO and FeCr 2 O 4 are generated on the surface of the alloy material.
  • the formation of scales mainly composed of FeO and FeCr 2 O 4 is called abnormal oxidation. When abnormal oxidation occurs, the yield may decrease. Therefore, it is preferable that the occurrence of abnormal oxidation can be suppressed by heating at a high temperature for a long time.
  • the present inventors have investigated an antioxidant capable of suppressing abnormal oxidation.
  • the present inventors performed high-temperature long-term heating on an alloy material coated with a conventional antioxidant on the surface.
  • the antioxidant flows downward or drips from the surface of the alloy material during high-temperature and long-term heating.
  • the alloy material to be heated is not composed only of a plane parallel to the horizontal plane, but has a three-dimensional shape having an upper surface, a lower surface, a side surface, and the like.
  • the antioxidant softens during long-term heating and drips from the surface of the alloy material.
  • the antioxidant applied to the side surface or the lower surface of the alloy material in the furnace tends to drip downward during long-term heating.
  • the hanging drop portions alloy material heating antioxidants Cr 2 O 3 becomes the coating is easily broken, abnormal oxidation is likely to occur.
  • the present inventors have studied an antioxidant material that does not easily drip from the surface of the alloy material during high-temperature long-term heating, that is, an antioxidant material that easily remains on the alloy material surface even during high-temperature long-term heating. did.
  • the present inventors considered to increase the softening point of the alloy antioxidant in order to leave the alloy antioxidant on the surface of the alloy material.
  • the softening point of the antioxidant for heating the alloy material is 800 ° C. or higher, the antioxidant for heating the alloy material is an alloy even if heating is performed at a high temperature for a long time.
  • the present inventors have investigated the composition of an antioxidant for heating an alloy material, which can have a softening point of 800 ° C. or higher, and obtained an antioxidant for heating an alloy material, which has a softening point of 800 ° C. or higher.
  • Glass frit is commonly used as an antioxidant for heating alloy materials.
  • the glass frit means flake-like, granular, or powder-like glass obtained by crushing glass to an appropriate size.
  • B 2 O 3 is usually used as the glass frit.
  • B 2 O 3 dissolves the Cr 2 O 3 film by reacting with Cr 2 O 3 coating. Therefore, in the alloy material heating antioxidants of this embodiment, better to reduce as much as possible the content of B 2 O 3 is preferred.
  • Na 2 O is also usually used as a glass frit of an antioxidant for heating an alloy material.
  • Na 2 O is also B 2 O 3, react with Cr 2 O 3 coating to dissolve Cr 2 O 3 coating. Therefore, it is preferable that the content of Na 2 O in the antioxidant for heating the alloy material of the present embodiment is reduced as much as possible.
  • the present inventors have suppressed the contents of B 2 O 3 and Na 2 O, which easily react with the Cr 2 O 3 film when heated at a high temperature for a long time, and the components of the antioxidant having a softening point of 800 ° C. or higher. It was investigated. As a result, when converted to oxides, in mass%, SiO 2: 40.0 ⁇ 80.0 %, Al 2 O 3: 0 ⁇ 30.0%, MgO: 0 contain ⁇ 5.0%, Further, one or more selected from the group consisting of Na 2 O: 10.0% or less, K 2 O: 20.00% or less, and Ca O: 25.0% or less, totaling 10.00 to 50.
  • the antioxidant for heating the alloy material contains 00% and further contains B 2 O 3 : 0 to less than 0.5%, it does not easily drip from the surface of the alloy material even during high-temperature long-term heating, and the alloy material It has been found that it easily remains on the surface and that the occurrence of abnormal oxidation due to the reaction with Cr 2 O 3 can be suppressed.
  • the alloy material was heated at a high temperature for a long time by using the antioxidant for heating the alloy material having the above composition and softening point, the oxidation of the alloy material could be sufficiently suppressed.
  • the antioxidant for heating an alloy material having the above composition and softening point may not be able to suppress the above-mentioned blocking even if it can suppress the oxidation of the alloy material at high temperature for a long time.
  • the present inventors have investigated the cause in detail. As a result, the following findings were obtained.
  • the antioxidant for heating alloy materials is, for example, flaky, granular, or powdery before heating. By heating, the antioxidant for heating the alloy material melts.
  • a network structure is formed in the molten alloy material heating antioxidant.
  • the network structure is a structure that spreads in a network in the molten alloy material heating antioxidant and can be connected to each other.
  • the molten alloy material heating antioxidant has improved spinnability by connecting the network structures to each other. The spinnability refers to the property of extending into a thread. If the alloy material heating antioxidant has a high spinnability, the alloy material heating antioxidant tends to stretch into a thread.
  • a batch type heating furnace may be used as a heating furnace for heating the alloy material.
  • the alloy material is heated in a laminated state in the batch type heating furnace.
  • the alloy material is stacked with other alloy materials with the antioxidant attached to the surface. Therefore, an antioxidant is interposed between the laminated alloy materials. If the antioxidant has a high spinnability, the alloying materials laminated with each other will adhere to each other via the antioxidant in a high temperature environment. If the alloy materials laminated with each other are excessively adhered to each other, it becomes difficult to extract them from the heating furnace by themselves.
  • blocking is a process in which alloying materials adhere to each other so that it is difficult to extract them from a heating furnace by themselves.
  • the antioxidant for heating the alloy material has a low spinnability, the alloy materials are less likely to adhere to each other. In this case, blocking is suppressed.
  • the present inventors further investigated an antioxidant having a composition that does not easily react with Cr 2 O 3 and having a softening point of 800 ° C. or higher and capable of suppressing blocking from the viewpoint of composition.
  • an antioxidant having a composition that does not easily react with Cr 2 O 3 and having a softening point of 800 ° C. or higher and capable of suppressing blocking from the viewpoint of composition.
  • the components that form the network structure in the film are SiO 2 and Al 2 O 3 . Meanwhile, components of cutting the network structure, MgO, a B 2 O 3, Na 2 O , K 2 O and CaO.
  • the components that form the network structure enhance the spinnability of the antioxidant for heating alloy materials.
  • the component that cuts the network structure lowers the spinnability of the antioxidant for heating the alloy material. Therefore, the present inventors have considered that the spinnability of the antioxidant for heating an alloy material can be lowered by appropriately adjusting the balance between the component forming the network structure and the component cutting the network structure. ..
  • F1 can be used as an index showing the spinnability of the antioxidant for heating alloy materials. If F1 ⁇ 2.50, the component that cuts the network structure is sufficiently contained with respect to the component that forms the network structure. In this case, the spinnability of the antioxidant for heating the alloy material is lowered. As a result, blocking can be suppressed.
  • the antioxidant for heating the alloy material and the method for heating the alloy material of the present embodiment completed based on the above knowledge have the following configurations.
  • An antioxidant for heating alloy materials When converted to oxide, in mass%, SiO 2 : 40.0 to 80.0%, Al 2 O 3 : 0 to 30.0%, MgO: 0-5.0%, A total of 10.00 to 50.00% of one or more selected from the group consisting of Na 2 O: 10.0% or less, K 2 O: 20.00% or less, and Ca O: 25.0% or less. ,as well as, B 2 O 3 : Contains 0 to less than 0.5%, The balance consists of impurities and satisfies equation (1). Antioxidant for heating alloy materials.
  • the antioxidant for heating an alloy material according to the present embodiment is suitable for heating an alloy material that forms a Cr 2 O 3 film at a temperature of 1000 to 1350 ° C. for 15 to 50 hours, and in particular, a high temperature of 1300 ° C. or higher. Moreover, it is suitable for heating for 25 hours or more.
  • the alloy material that forms a Cr 2 O 3 film is acid resistant even if it is heated for a long time at a temperature of 1000 to 1350 ° C. for 15 to 50 hours. Excellent in chemistry.
  • the antioxidant for heating alloy materials of the present embodiment is further excellent in blocking resistance.
  • % for each component means mass% when the total amount of the compounds of the antioxidant for heating the alloy material is 100%.
  • the antioxidant for heating alloy materials of this embodiment contains the following compounds. If the alloy material heating antioxidant is composed of the following compounds, the softening point of the alloy material heating antioxidant can be set to 800 ° C. or higher.
  • the heat-sensitive antioxidant for the alloy material is a flake-like, granular, or powder-like glass frit, and the content of each compound is the content that one grain of the glass frit contains on average.
  • SiO 2 40.0 to 80.0%
  • Silica (SiO 2 ) forms a protective film on the surface of the alloy material together with other components during high-temperature and long-term heating.
  • SiO 2 becomes a matrix of protective coatings.
  • the protective coating suppresses the supply of oxygen to the surface of the alloy material.
  • SiO 2 further has a high softening point of 1600 ° C. or higher. If the alloy material heating antioxidant contains SiO 2 , the softening point of the alloy material heating antioxidant is increased. Therefore, even during high-temperature and long-term heating, the antioxidant for heating the alloy material does not easily drip from the surface of the alloy material and tends to remain on the surface of the alloy material.
  • the SiO 2 content of the antioxidant for heating the alloy material is 40.0% or more, the antioxidant coats the surface of the alloy material even during high-temperature long-term heating and suppresses the supply of oxygen to the surface of the alloy material. can. As a result, oxidation resistance is increased. If the oxidation resistance is improved, soot dust derived from MoO 3 can be suppressed when an alloy material containing Mo is used. That is, the dust resistance is improved. When the SiO 2 content is less than 40.0%, the viscosity of the antioxidant for heating the alloy material becomes low during high-temperature long-term heating, and the material tends to drip. As a result, the above effect cannot be sufficiently obtained.
  • the SiO 2 content exceeds 80.0%, the softening point of the antioxidant for heating the alloy material becomes too high. In this case, the antioxidant for heating the alloy material is less likely to get wet and spread. As a result, it becomes difficult to uniformly cover the entire surface of the alloy material with the antioxidant for heating the alloy material, and the oxidation resistance is lowered. If the oxidation resistance is lowered, the dust resistance is also lowered when an alloy material containing Mo is used.
  • the SiO 2 content exceeds 80.0%, the softening point of the antioxidant for heating the alloy material becomes higher. Therefore, it becomes difficult for the mixed components to melt, and it becomes difficult to manufacture the antioxidant for heating the alloy material itself. Therefore, the SiO 2 content is 40.0 to 80.0%.
  • the preferred lower limit of the SiO 2 content is 45.0%, more preferably 50.0%.
  • the preferred upper limit of the SiO 2 content is 75.0%, more preferably 70.0%.
  • Al 2 O 3 0 to 30.0% Aluminium (Al 2 O 3 ) may not be contained. That is, the Al 2 O 3 content may be 0%.
  • Al 2 O 3 like SiO 2 , forms a protective film on the surface of the alloy material during high-temperature and long-term heating.
  • Al 2 O 3 further increases the softening point of the alloy material heating antioxidant. Therefore, the antioxidant for heating the alloy material does not easily drip and easily remains on the surface of the alloy material during high-temperature and long-term heating. As a result, the oxidation resistance of the alloy material is increased. When the oxidation resistance of the alloy material is increased, the dust resistance is also increased when the alloy material containing Mo is used.
  • the Al 2 O 3 content is 0 to 30.0%.
  • the preferred lower limit of the Al 2 O 3 content is 1.0%, more preferably 5.0%, and even more preferably 10.0%.
  • the preferred upper limit of the Al 2 O 3 content is 28.0%, more preferably 25.0%.
  • MgO 0-5.0% Magnesia (MgO) may not be contained. That is, the MgO content may be 0%.
  • MgO like SiO 2 and Al 2 O 3 , forms a protective film on the surface of the alloy material during high-temperature and long-term heating. MgO further lowers the softening point of the alloy material heating antioxidant. Therefore, the antioxidant for heating the alloy material spreads wet during heating at a high temperature for a long time, and uniformly covers the surface of the alloy material.
  • the MgO content exceeds 5.0%, the Cr 2 O 3 film, which is a protective film, is dissolved by MgO, so that the Cr 2 O 3 film is not sufficiently formed.
  • the MgO content is 0 to 5.0%.
  • the preferred lower limit of the MgO content is 0.1%, more preferably 0.2%.
  • the preferred upper limit of the MgO content is 4.0%, more preferably 3.0%.
  • Na 2 O 10.0% or less, K 2 O: 20.00% or less, and Ca O: 25.0% or less: 10.00 to 50.00% in total.
  • Na 2 O is greater than 0%
  • K 2 O is greater than 0%
  • Ca O is greater than 0%.
  • the total content of one or more selected from the group consisting of Na 2 O: 10.0% or less, K 2 O: 20.00% or less, and Ca O: 25.0% or less is less than 10.00%.
  • the fluidity of the alloy material heating antioxidant at high temperatures decreases.
  • the total content of one or more selected from the group consisting of Na 2 O: 10.0% or less, K 2 O: 20.00% or less, and Ca O: 25.0% or less is 50.00%. If it exceeds, the softening point of the antioxidant for heating the alloy material is excessively lowered. If the softening point of the alloy material heating antioxidant is lowered, the alloy material heating antioxidant drips from the surface of the alloy material during high-temperature long-term heating. Therefore, the total content of one or more selected from the group consisting of Na 2 O: 10.0% or less, K 2 O: 20.00% or less, and Ca O: 25.0% or less is 10.00. It is ⁇ 50.00%.
  • the preferable lower limit of the total content of one or more selected from the group consisting of Na 2 O: 10.0% or less, K 2 O: 20.00% or less, and Ca O: 25.0% or less is 15.00. %, More preferably 20.00%.
  • the preferred upper limit of the total content of one or more selected from the group consisting of Na 2 O: 10.0% or less, K 2 O: 20.00% or less, and Ca O: 25.0% or less is 45.00. %, More preferably 40.00%.
  • Na 2 O 10.0% or less Sodium oxide (Na 2 O) is inevitably contained in the antioxidant for heating alloy materials mainly in SiO 2. Na 2 O enhances the fluidity of the alloy material heating antioxidant at high temperatures. However, Na 2 O reacts with Cr 2 O 3 film is Cr 2 O 3 film is easily torn. In particular, when the Cr content of the alloy material is less than 20.0% by mass, the Cr 2 O 3 coating is easily broken. Further, if the Na 2 O content exceeds 10.0%, the softening point of the antioxidant for heating the alloy material is excessively lowered. Therefore, the Na 2 O content is 10.0% or less, and more specifically, the Na 2 O content is more than 0% to 10.0%.
  • the preferred lower limit of Na 2 O is 0.1%, more preferably 0.2%.
  • the preferable upper limit of the Na 2 O content is 9.0%, more preferably 7.0%, still more preferably 6.0%, still more preferably 5.0%, still more preferably 4.0%, still more preferable. Is 3.0%, more preferably 2.0%.
  • K 2 O 20.00% or less Potassium oxide (K 2 O) is inevitably contained in the antioxidant for heating alloy materials mainly in SiO 2.
  • K 2 O lowers the softening point of the antioxidant for heating alloy materials.
  • the softening point is lowered, the fluidity at high temperature is increased, and it becomes easy to wet and spread on the surface of the alloy material. As a result, it becomes easy to uniformly coat the surface of the alloy material with the antioxidant for heating the alloy material.
  • the content of K 2 O is more than 20.00% softening point of the alloy material heating antioxidants decreases excessively. In this case, during heating at a high temperature for a long time, the antioxidant for heating the alloy material drips from the surface of the alloy material, and abnormal oxidation is likely to occur.
  • the K 2 O content is 20.00% or less, and more specifically, the K 2 O content is more than 0% to 20.00%.
  • a preferable lower limit of the content of K 2 O is 0.01%, more preferably 0.02%.
  • Preferred upper limit of the content of K 2 O is 19.50%, more preferably 19.00%.
  • CaO 25.0% or less Calcium oxide (CaO) is inevitably contained in the antioxidant for heating alloy materials mainly in SiO 2.
  • CaO similarly to the K 2 O, lower the softening point of the alloy material heating antioxidants. When the softening point is lowered, the fluidity at high temperature is increased, and it becomes easy to wet and spread on the surface of the alloy material. As a result, it becomes easy to uniformly coat the surface of the alloy material with the antioxidant for heating the alloy material.
  • the CaO content exceeds 25.0%, the softening point of the antioxidant for heating the alloy material is excessively lowered.
  • the CaO content is 25.0% or less, and more specifically, the CaO content is more than 0% to 25.0%.
  • the preferred lower limit of the CaO content is 0.6%, more preferably 0.8%, still more preferably 10.0%, still more preferably 11.0%, still more preferably 12.0. %.
  • the preferred upper limit of the CaO content is 24.5%, more preferably 24.0%.
  • B 2 O 3 0 to less than 0.5% Boric acid (B 2 O 3 ) is an impurity. That is, the B 2 O 3 content may be 0%.
  • B 2 O 3 is a well-known compound as an antioxidant.
  • B 2 O 3 reacts with Cr 2 O 3 film, in a high temperature for a long time heating, to dissolve the Cr 2 O 3 coating. In this case, abnormal oxidation is likely to occur. Cr 2 O 3 further be dissolved coating, when an alloy material containing Mo, from the dust is likely to occur MoO 3. Therefore, the B 2 O 3 content is less than 0-0.5%.
  • the B 2 O 3 content is preferably as low as possible.
  • the preferred upper limit of the B 2 O 3 content is 0.4%, more preferably 0.3%, and even more preferably 0%.
  • the rest of the composition of the compound of the antioxidant for heating alloy materials according to the embodiment of the present invention consists of impurities.
  • the impurities are those mixed from an inorganic material as a raw material, a manufacturing environment, or the like when an antioxidant for heating an alloy material is industrially manufactured, and the oxidation for heating the alloy material of the present embodiment. It means an acceptable one as long as it does not adversely affect the inhibitor.
  • F1 exceeds 2.50, the components forming the network structure are excessively contained in the components of the antioxidant for heating the alloy material with respect to the components that cut the network structure. Therefore, the spinnability of the antioxidant for heating the alloy material is enhanced. As a result, after heating at a high temperature for a long time, the alloy materials adhere to each other and blocking occurs. Therefore, F1 ⁇ 2.50.
  • the preferred upper limit of F1 is 2.45, more preferably 2.40, and even more preferably 2.30.
  • the lower limit of F1 is not particularly limited, but is, for example, 0.62.
  • the softening point of the antioxidant for heating the alloy material is 800 ° C. or higher.
  • the softening point of the alloy material heating antioxidant is 800 ° C. or higher, the alloy material heating antioxidant spreads wet over the entire surface of the alloy material and covers the surface when heating is performed at a high temperature for a long time. As a result, oxidation of the surface of the alloy material is suppressed.
  • the softening point of the alloy material heating antioxidant is less than 800 ° C., the alloy material heating antioxidant drips from the alloy material surface and the alloy material surface is partially exposed when high temperature and long-term heating is performed. do. In the exposed portion, the supply of oxygen to the surface of the alloy material cannot be suppressed.
  • the softening point of the antioxidant for heating the alloy material is 800 ° C. or higher.
  • the preferred lower limit of the softening point of the alloy material heating antioxidant is 820 ° C, more preferably 840 ° C, still more preferably 860 ° C.
  • the upper limit of the softening point of the antioxidant for heating the alloy material is not particularly limited, but is, for example, 1100 ° C.
  • the softening point of the antioxidant for heating the alloy material is determined by the composition of the compound of the antioxidant for heating the alloy material. According to the composition of the compound of the antioxidant for heating the alloy material of the present embodiment, the softening point is 800 ° C. or higher.
  • the softening point of the antioxidant for heating the alloy material is measured using a thermogravimetric-differential thermal simultaneous measuring device (TG-DTA). Specifically, it is as follows. Place 10 mg of the alloy material heating antioxidant in the sample holder of TG-DTA. The antioxidant for heating the alloy material is heated up to 1300 ° C. at a heating rate of 10 ° C./min. The atmosphere during heating is the atmosphere. The differential heat at this time is measured, and the fourth inflection point of the DTA (differential heat) chart is set as the softening point of the antioxidant for heating the alloy material.
  • TG-DTA thermogravimetric-differential thermal simultaneous measuring device
  • the above-mentioned antioxidant for heating alloy materials has excellent blocking resistance, and further has excellent oxidation resistance even when heated at a high temperature for a long time.
  • the present inventors have further found that the above-mentioned antioxidant for heating an alloy material exhibits excellent dust resistance when applied to an alloy material containing Mo.
  • the antioxidant for heating the alloy material of the present embodiment When the antioxidant for heating the alloy material of the present embodiment is used, the Cr 2 O 3 coating is difficult to dissolve. Therefore, Mo inside the alloy material is less likely to undergo an oxidation reaction, and MoO 3 is less likely to be generated. As a result, it is possible to suppress the generation of white soot dust derived from MoO 3 during high-temperature long-time heating and hot working.
  • the antioxidant for heating alloy materials is glass frit.
  • the glass frit is glass in which the powder of each of the above components is melted, solidified, and then crushed.
  • the alloy material heating antioxidant is, for example, flaky, granular, or powdery.
  • the preferable particle size is 25 ⁇ m or less.
  • the particle size referred to here is the volume average particle size (median diameter) D50.
  • the volume average particle diameter D50 is determined by the following method.
  • the volume particle size distribution of the glass frit is obtained by a particle size distribution measuring device. Using the obtained volume particle size distribution, the particle size at which the cumulative volume becomes 50% from the small particle size side in the cumulative volume distribution is defined as the volume average particle size D50.
  • the particle size is 25 ⁇ m or less, the antioxidant for heating the alloy material is easily dispersed in the solution (water) at room temperature, and a slurry is easily generated.
  • the alloy material heating antioxidant of the present embodiment is produced by the following method.
  • the above components constituting the antioxidant for heating the alloy material are mixed.
  • the mixed components are melted and rapidly cooled in water or air to vitrify.
  • the melting temperature is, for example, 1400 to 1600 ° C. After melting, quench and crush.
  • the particle size of the antioxidant for heating the alloy material of the present embodiment is, for example, 1 ⁇ m to 25 ⁇ m. Thereby, the softening point of the antioxidant for heating the alloy material of the present embodiment can be adjusted.
  • the antioxidant for heating the alloy material of the present embodiment is produced by the above steps.
  • the antioxidant for heating the alloy material of the present embodiment can be used for producing the alloy material.
  • the antioxidant for heating an alloy material of the present embodiment is, for example, heating an alloy material having a Cr content of 12 to 50% by mass at a temperature of 1000 to 1350 ° C. for 15 to 50 hours (high temperature and long time heating). Can be applied when implementing.
  • the antioxidant for heating alloy materials of the present embodiment is particularly suitable for heating at 1300 ° C. or higher for 25 hours or longer. It has excellent oxidation resistance even when it is heated for a short time of less than 15 hours at a temperature of 1000 to 1350 ° C. This point will be described below.
  • the alloy material for which the antioxidant for heating the alloy material of the present embodiment is used is an alloy material of Fe group or Ni group containing Cr.
  • the Fe-based alloy material is an alloy material having an Fe content of 50% by mass or more.
  • the Ni-based alloy material is an alloy material having a Ni content of 50% by mass or more.
  • the Cr content in the alloy material may be 12 to 50% by mass.
  • the Cr content in the alloy material may be 20 to 40% by mass.
  • the alloy material containing Cr is, for example, Si: 0 to 5%, Mn: 0 to 20%, Cr: 12 to 50%, Mo: 0 to 15%, W: 0 to 10%, Cu: 0 to 5%.
  • the antioxidant for heating alloy materials of this embodiment is particularly suitable for alloy materials of casting materials.
  • the alloy material is, for example, a stainless steel material, for example, a martensite-based stainless steel material, a ferrite-based stainless steel material, an austenitic stainless steel material, a precipitation hardening stainless steel material, and a two-phase stainless steel material.
  • the antioxidant for heating an alloy material of the present embodiment is particularly suitable for an alloy material of a casting material.
  • the antioxidant for heating an alloy material of the present embodiment is not limited to the cast material, and may be applied to a processed material obtained by hot-working the cast material. In short, the antioxidant for heating alloy materials of the present embodiment can be widely applied to alloy materials (casting materials, processed materials).
  • the antioxidant for heating the alloy material of the present embodiment has excellent dust resistance when the alloy material having a Mo content of more than 0% is used.
  • the Cr 2 O 3 coating is easily dissolved when heated at a high temperature for a long time.
  • MoO 3 is formed when the Cr 2 O 3 coating of the alloy material containing Mo is dissolved.
  • dust derived from MoO 3 is generated.
  • the antioxidant for heating the alloy material of the present embodiment is used, the Cr 2 O 3 coating can be maintained for a longer period of time, so that the formation of MoO 3 can be suppressed.
  • the method for heating the alloy material of the present embodiment includes a step of applying an antioxidant for heating the alloy material to the surface of the alloy material and a step of heating the alloy material coated with the antioxidant for heating the alloy material. ..
  • an antioxidant for heating the alloy material is prepared.
  • the prepared antioxidant for heating the alloy material is made into a slurry.
  • the slurry is produced, for example, by mixing water with an antioxidant for heating an alloy material.
  • the slurry is applied to the surface (upper surface, lower surface, and side surface) of the alloy material before heating.
  • the preferable content of water is 70 to 100 parts by mass with respect to 100 parts by mass of the antioxidant for heating the alloy material. If the water content is too low or too high, it is difficult to apply the antioxidant for heating alloy materials. By adjusting the water content, the viscosity of the slurry can be adjusted to such an extent that it can be applied almost uniformly to the surface of the alloy material at room temperature.
  • the slurry may further contain a suspending agent and a dispersant.
  • an antioxidant for heating the alloy material, etc. is dispersed almost uniformly in the solution (water).
  • the suspending agent contains, for example, frog-eye clay and bentonite and / or sepiolite. If the antioxidant for heating the alloy material of the present embodiment is applied to the surface of the alloy material together with the sardine clay and bentonite and / or sepiolite, the antioxidant for heating the alloy material does not easily drip on the surface of the alloy material. Moreover, when the alloy material is dried and solidified, the antioxidant for heating the alloy material is not easily peeled off from the surface of the alloy material.
  • Frog-eye clay contains kalionic clay and a plurality of quartz particles. More specifically, the frog-eye clay contains kaolinite, halosite, and quartz.
  • Frog-eye clay improves the drooling resistance of the liquid alloy material heating antioxidant.
  • the slurry containing frog-eye clay does not easily drip after being applied to the surface of the alloy material at room temperature. Therefore, if frog-eye clay is contained, the antioxidant for heating the alloy material tends to cover the entire surface of the alloy material at room temperature.
  • the preferable content of frog-grain clay in the slurry is 4 parts by mass or more with respect to 100 parts by mass of the antioxidant for heating the alloy material.
  • the antioxidant for heating the alloy material at room temperature does not easily drip.
  • the content of the frog-grained clay is more preferably 5 parts by mass or more, still more preferably 6 parts by mass or more. If the slurry contains an excessive amount of frog-grained clay, it becomes difficult for the antioxidant for heating the alloy material in the slurry to be uniformly dispersed on the surface of the alloy material, and the oxidation resistance is lowered. Therefore, the upper limit of the preferable content of frog-eye clay is 30 parts by mass.
  • the sagging of the antioxidant for heating the alloy material at room temperature can be suppressed to some extent.
  • Bentonite is a clay whose main component is montmorillonite. Bentonite may further contain silicate minerals such as quartz and opal, silicate minerals such as feldspar and zeolite, carbonate minerals such as dolomite, sulfate minerals, and sulfide minerals such as pyrite.
  • Sepiolite is a hydrous magnesium silicate, for example, represented by the chemical formula Mg 8 Si 12 O 30 (OH ) 4 (OH 2) 4 ⁇ 8H 2 O.
  • Both bentonite and sepiolite suppress the peeling of the antioxidant for heating alloy materials.
  • the liquid slurry is applied to the surface of the alloy material. Then, by heating or drying, the moisture of the slurry applied to the alloy material evaporates, and the antioxidant for heating the alloy material solidifies.
  • the slurry contains bentonite and / or sepiolite
  • the bentonite and sepiolite prevent the solidified alloy material heating antioxidant from peeling off from the surface of the alloy material. Slurries containing bentonite and / or sepiolite are difficult to peel off even when subjected to external force.
  • the slurry may contain one or more of bentonite and sepiolite.
  • the lower limit of the content of bentonite and / or sepiolite in the slurry is 4 parts by mass or more with respect to 100 parts by mass of the antioxidant for heating the alloy material.
  • the content of bentonite and / or sepiolite is 4 parts by mass or more, the peeling resistance of the antioxidant for heating the alloy material is further improved.
  • the lower limit of the total value of the bentonite content and the sepiolite content is preferably 5 parts by mass or more.
  • the upper limit of the preferable content of bentonite and / or sepiolite is less than 9 parts by mass with respect to 100 parts by mass of the antioxidant for heating the alloy material.
  • the content of bentonite and / or sepiolite exceeds 9 parts by mass, it becomes difficult for the antioxidant for heating the alloy material to be dispersed in the liquid slurry. That is, it becomes difficult for the antioxidant for heating the alloy material to form a slurry.
  • the upper limit of the total value of the bentonite content and the sepiolite content is preferably less than 8 parts by mass.
  • the suspending agent may contain clays other than the above-mentioned frog-eye clay, bentonite and sepiolite. Clays contain, for example, iron oxide (Fe 2 O 3 ).
  • the slurry does not have to contain a dispersant.
  • the slurry preferably contains a dispersant from the viewpoint of enhancing the dispersibility of the entire alloy material heating antioxidant and enhancing the workability. If the slurry contains a dispersant, the amount of water that disperses the antioxidant for heating the alloy material can be further reduced, and as a result, the adhesiveness is enhanced.
  • Dispersants include, for example, sodium tripolyphosphate, sodium hexametaphosphate, sodium ultrapolyphosphate, sodium acid hexametaphosphate, sodium borate, sodium carbonate, inorganic salts such as polymethaphosphate, sodium citrate, sodium tartrate, polyacrylic acid, polyacrylic.
  • the content of the dispersant is preferably less than 4.5 parts by mass in total with respect to 100 parts by mass of the antioxidant for heating the alloy material.
  • the slurried alloy material heating antioxidant is applied to the surface of the alloy material before heating. That is, the slurried alloy material heating antioxidant is applied to the surface of the alloy material at room temperature.
  • the method of applying the slurried alloy material heating antioxidant is not particularly limited.
  • An operator may use a brush to apply a slurry of an alloy material heating antioxidant to the surface of the alloy material.
  • an antioxidant for heating the alloy material which has been made into a slurry by spraying or the like, may be applied to the surface of the alloy material.
  • a bathtub in which the slurried alloy material heating antioxidant is stored may be prepared, and the alloy material may be immersed in the bathtub (so-called “ditch pickling”).
  • an antioxidant for heating the alloy material is applied to the surface of the alloy material. After applying the alloy material heating antioxidant to the surface of the alloy material, the alloy material heating antioxidant may be dried.
  • the alloy material coated with the antioxidant for heating the alloy material is heated (heating step).
  • the alloy material coated with the antioxidant for heating the alloy material is heated, for example, at a temperature of 1000 to 1350 ° C. for 15 to 50 hours.
  • the antioxidant for heating alloy materials of the present embodiment contains the above-mentioned compound.
  • the above-mentioned compounds do not easily react with the Cr 2 O 3 coating on the surface of the alloy material. Therefore, it suppresses the Cr 2 O 3 coating from breaking during high-temperature and long-term heating. Further, when it is used for an alloy material containing Mo, soot dust derived from MoO 3 can be suppressed.
  • the antioxidant for heating the alloy material of the present embodiment has a softening point of 800 ° C. or higher. Therefore, even during high-temperature and long-term heating, the antioxidant for heating the alloy material does not easily drip from the surface of the alloy material and remains on the surface of the alloy material.
  • the alloy heating antioxidant of the present embodiment further satisfies the formula (1). Therefore, the spinnability of the antioxidant for heating alloy materials is low. As a result, adhesion between alloy materials can be suppressed, and blocking can be suppressed.
  • the effect of the antioxidant for heating the alloy material of the present embodiment will be described more specifically by way of examples.
  • the conditions in the following examples are one condition example adopted for confirming the feasibility and effect of the antioxidant for heating the alloy material of the present embodiment. Therefore, the antioxidant for heating the alloy material of the present embodiment is not limited to this one condition example.
  • the antioxidants for heating alloy materials shown in Table 1 were prepared. Test numbers 1-1 and 1-4 had the compositions shown in Table 1, and the balance was impurities.
  • the composition of the antioxidant for heating the alloy material was obtained by producing the antioxidant for heating the alloy material, drying it, and performing high frequency inductively coupled plasma (ICP) analysis. Specifically, the contents of Si, Al, Mg, Na, K, Ca and B obtained by ICP are set to SiO 2 , Al 2 O 3 , MgO, Na 2 O, K 2 O, CaO and CaO, respectively. The content of each component was determined by converting it into the content of B 2 O 3.
  • the product name Acnas softening point: 700 ° C.
  • Tokan Material Technology Co., Ltd. was used.
  • the composition of the compound of the product name Acnas was unknown.
  • the softening point of the antioxidant for heating the alloy material of each test number was measured using a thermogravimetric-differential thermal simultaneous measuring device (TG-DTA). Specifically, it was as follows. A 10 mg alloy heating antioxidant was placed in the TG-DTA sample holder. The antioxidant for heating the alloy material was heated to 1300 ° C. at a heating rate of 10 ° C./min. The atmosphere during heating was the atmosphere. The latent heat at this time was measured, and the fourth inflection point on the DTA (differential thermal) chart was set as the softening point of the antioxidant for heating the alloy material. The results are shown in Table 1.
  • a plate-shaped test piece simulating an alloy material was prepared.
  • As the plate-shaped test piece a two-phase stainless steel material corresponding to A240 UNS S39274 specified by ASTM was used.
  • the size of the plate-shaped test piece was 13 mm in thickness, 40 mm in length, and 100 mm in width.
  • the slurry was produced by mixing 6 parts by mass of frog clay, 5 parts by mass of bentonite, and 70 to 100 parts by mass of water with 100 parts by mass of an antioxidant for heating an alloy material.
  • the obtained slurry was applied to a 40 mm ⁇ 100 mm surface, which is the upper surface of the plate-shaped test piece, using a brush and then dried.
  • the plate-shaped test piece after applying the antioxidant for heating the alloy material was heated at 1300 ° C. for 25 hours.
  • the atmosphere simulated LNG combustion. Specifically, the atmosphere gas was adjusted so that the composition of the atmosphere gas was 2 to 3% O 2 , 8 to 10% CO 2 , 15 to 20% H 2 O, and the balance was N 2.
  • FIG. 1 is a plan view of the plate-shaped test piece of test number 1-1.
  • FIG. 2 is a plan view of the plate-shaped test piece of test number 1-2.
  • FIG. 3 is a plan view of the plate-shaped test piece of test number 1-3.
  • FIG. 4 is a cross-sectional observation view of Test No. 1-1 by SEM.
  • FIG. 5 is a cross-sectional observation view of test number 1-2 by SEM.
  • FIG. 6 is a cross-sectional observation view of test numbers 1-3 by SEM.
  • FIG. 4 when abnormal oxidation was not observed, it was determined that abnormal oxidation did not occur.
  • FIG. 4 when a clearly abnormally oxidized region is observed in a cross section perpendicular to a surface of 40 mm ⁇ 100 mm (for example, scales as shown by reference numeral 3 in FIG. 5 and reference numeral 4 in FIG. 6 are generated, and the mother When the material was observed to be thinned), it was judged that abnormal oxidation had occurred.
  • FIG. 7 is a diagram showing the element mapping analysis results of Test No. 1-1.
  • FIG. 8 is a diagram showing the results of element mapping analysis of test number 1-2.
  • FIG. 9 is a diagram showing the element mapping analysis results of test numbers 1-3.
  • Test results With reference to Table 1, in Test No. 1-1, the softening point of the antioxidant for heating the alloy material was 800 ° C. or higher because the composition of the compound was appropriate. Therefore, with reference to FIGS. 1 and 7, a Cr 2 O 3 coating 2 having a uniform thickness was formed on the surface of the plate-shaped test piece, and normal oxidation was observed. With reference to FIG. 4, in Test No. 1-1, there was no further thinning of the base metal 10. That is, the oxidation resistance of the alloy material was improved by using the antioxidant for heating the alloy material of Test No. 1-1.
  • the softening point of the antioxidant for heating the alloy material was 800 ° C. or higher because the composition of the compound was appropriate.
  • a Cr 2 O 3 coating having a uniform thickness was formed on the surface of the plate-shaped test piece, and normal oxidation was observed.
  • there was no further thinning of the base metal that is, the oxidation resistance of the alloy material was improved by using the antioxidant for heating the alloy material of Test No. 1-4.
  • the softening point of the antioxidant for heating the alloy material was less than 800 ° C. Since the softening point was less than 800 ° C., it is considered that the composition of the compound was not appropriate in Test No. 1-2. Therefore, with reference to FIG. 2, abnormal oxidation 1 was generated.
  • a recess having a depth of about 1.5 mm was further formed in the base material 20.
  • a scale 3 mainly composed of Fe was further formed with reference to FIG. The oxidation resistance of the alloy material was not improved by using the antioxidant for heating the alloy material of Test No. 1-2.
  • test numbers 1-3 no antioxidant for heating alloy materials was used. Therefore, referring to FIG. 3, the entire surface of the plate-shaped test piece was violently oxidized. In Test No. 1-3, with reference to FIG. 6, the entire surface of the base metal 30 was thinned by about 0.8 mm to form the scale 4. In Test No. 1-3, a scale 4 mainly composed of Fe and Cr was further formed with reference to FIG.
  • the antioxidants for heating alloy materials shown in Table 2 were prepared. Test numbers 2-2 to 2-4 had the compositions shown in Table 2. In Test No. 2-2, the total amount of each component shown in Table 2 was 100% by mass. In Test Nos. 2-3 and 2-4, the total amount of each component shown in Table 2 was less than 100% by mass, and the balance was impurities.
  • the composition of the antioxidant for heating the alloy material was obtained by producing the antioxidant for heating the alloy material, drying it, and performing ICP analysis. Specifically, the contents of Si, Al, Mg, Na, K, Ca and B obtained by ICP are set to SiO 2 , Al 2 O 3 , MgO, Na 2 O, K 2 O, CaO and CaO, respectively. The content of each component was determined by converting it into the content of B 2 O 3.
  • a plate-shaped test piece simulating an alloy material was prepared.
  • the plate-shaped test piece was a stainless steel material containing 87% Fe and 13% Cr in mass%.
  • the size of the plate-shaped test piece was 10 mm in thickness, 20 mm in length, and 20 mm in width.
  • the mass (g) of the plate-shaped test piece before applying the slurry was measured and used as the mass (g) before the test.
  • the slurry was produced by mixing 6 parts by mass of frog clay, 5 parts by mass of bentonite, and 70 to 100 parts by mass of water with 100 parts by mass of an antioxidant for heating an alloy material.
  • the obtained slurry was applied to the entire surface (upper surface, lower surface, and four side surfaces) of the plate-shaped test piece using a brush, and then dried.
  • the plate-shaped test piece was heated at 1200 ° C. for 2 hours, simulating the heating process.
  • the atmosphere simulated LNG combustion. Specifically, the atmosphere gas was adjusted so that the composition of the atmosphere gas was 2 to 3% O 2 , 8 to 10% CO 2 , 15 to 20% H 2 O, and the balance was N 2.
  • the scale adhering to the plate-shaped test piece by heating was removed by immersing it in an alkaline aqueous solution and then further immersing it in a citric acid aqueous solution.
  • the mass (g) of the plate-shaped test piece after removing the scale was measured and used as the mass (g) after the test.
  • the difference between the mass (g) of the plate-shaped test piece before heating and the mass (g) of the plate-shaped test piece after heating is the surface area (1200 mm 2) of the surface area (upper surface and four side surfaces) of the plate-shaped test piece.
  • the value divided by) was taken as the oxidative weight loss. Those having an oxidation weight loss of 0.200 g / mm 2 or less were judged to have excellent oxidation resistance.
  • Test results In Test No. 2-2, the softening point of the antioxidant for heating the alloy material was 800 ° C. or higher because the composition of the compound was appropriate. As a result, the antioxidant for heating the alloy material of Test No. 2-2 had an oxidation weight loss of 0.200 g / mm 2 or less and was excellent in oxidation resistance.
  • Test numbers 3-1 to 3-5 had the compositions shown in Table 3. In Test No. 3-3, the total amount of each component shown in Table 3 was 100% by mass. In test numbers 3-1, 3-2, 3-4 and 3-5, the total amount of each component shown in Table 3 was less than 100% by mass, and the balance was impurities.
  • the composition of the antioxidant for heating the alloy material was obtained by producing the antioxidant for heating the alloy material, drying it, and performing ICP analysis. Specifically, the contents of Si, Al, Mg, Na, K, Ca and B obtained by ICP are set to SiO 2 , Al 2 O 3 , MgO, Na 2 O, K 2 O, CaO and CaO, respectively. The content of each component was determined by converting it into the content of B 2 O 3.
  • the test number 3-1 is the same as the test number 1-1.
  • Test number 3-2 is the same as test number 1-4.
  • Test number 3-3 is the same as test number 2-2.
  • a plate-shaped test piece simulating an alloy material was prepared.
  • a two-phase stainless steel material corresponding to A240 UNS S39274 specified by ASTM was used as the plate-shaped test piece.
  • the size of the plate-shaped test piece was 4 mm in thickness, 25 mm in length, and 80 mm in width.
  • the slurry was produced by mixing 6 parts by mass of frog clay, 5 parts by mass of bentonite, and 70 to 100 parts by mass of water with 100 parts by mass of an antioxidant for heating an alloy material.
  • the obtained slurry was applied to the 25 mm ⁇ 20 mm surface at the end of the 25 mm ⁇ 80 mm surface on the upper surface of the plate-shaped test piece using a brush, and then dried.
  • the two plate-shaped test pieces were stacked so that the slurry-coated surfaces were in full contact with each other.
  • the plate-shaped test piece after applying the antioxidant for heating the alloy material was heated at 1300 ° C. for 2 hours.
  • the atmosphere was an atmospheric atmosphere.
  • FIG. 11 is a schematic view of an apparatus for evaluating blocking resistance. Whether or not the two plate-shaped test pieces were adhered was evaluated using the apparatus shown in FIG. Specifically, with reference to FIG. 11, the metal rod 100 was previously fixed to the end of one of the two plate-shaped test pieces A by welding. The plate-shaped test piece A to which the metal rod 100 was welded and the other plate-shaped test piece B were stacked so that the slurry-coated surfaces were in full contact with each other. The plate-shaped test piece B was fixed in the tube furnace 110 via the fixture 120.
  • the adhesive force F (kg) when the metal rod 100 was pulled in the horizontal direction and the two plate-shaped test pieces were peeled off in the horizontal direction with respect to a surface of 25 mm ⁇ 80 mm was measured.
  • a digital hanging TDTB-25 manufactured by TRUSCO NAKAYAMA Co., Ltd. was used for the measurement of the adhesive strength.
  • the test piece heating temperature at the time of measurement was 1300 ° C.
  • the measurement environment was an atmospheric atmosphere
  • the tensile speed was 10 to 20 cm / sec.
  • the results are shown in the column of "adhesive strength (kg)" in Table 3.
  • the antioxidant for heating alloy materials of Test No. 3-4 did not satisfy the formula (1) although the content of each component was appropriate. Therefore, the adhesive strength when peeling off the two plate-shaped test pieces was 2.84 kg. The antioxidant for heating alloy materials of Test No. 3-4 was not excellent in blocking resistance.
  • a slurry of the antioxidant for heating the alloy material of Test No. 1-1 in Table 1 was applied to the steel material.
  • the slurry of the antioxidant for heating the alloy material was produced by mixing 6 parts by mass of frog clay, 5 parts by mass of bentonite, and 70 to 100 parts by mass of water with 100 parts by mass of the antioxidant for heating the alloy material. ..
  • the obtained slurry was applied to the surface (upper surface, lower surface, and four side surfaces) of the steel material, dried, and subjected to soaking heat treatment.
  • the soaking heat treatment was carried out at 1270 ° C. for 50 hours.
  • the exhaust gas was recovered from the chimney of the soaking furnace every hour. The amount of recovered exhaust gas was measured with an exhaust gas measuring device.
  • the weight was measured using the white solid matter in the recovered exhaust gas as soot.
  • the weight of soot dust (white solid matter) per volume of exhaust gas was calculated as the amount of soot dust generated (mg / m 3). Soaking in a total of 50 times per hour, were tested above and a dust generation amount obtained dust generation amount of test numbers 1-1 the maximum value of (mg / m 3) (mg / m 3) ..
  • the dust-proof evaluation test was carried out on the alloy material heating antioxidant of Test No. 1-2 in Table 1 in the same manner as the alloy material heating antioxidant of Test No. 1-1 in Table 1. As for the heating antioxidant of Test No. 1-2, the slurry produced in the same ratio as that of Test No.
  • the antioxidant for heating the alloy material of Test No. 1-1 had a significantly smaller amount of dust generated than the antioxidant for heating the alloy material of Test No. 1-2, and was excellent in dust resistance.
  • Base material 1 Abnormal oxidation 2 Cr 2 O 3 coating 3 Fe-based scale 4 Fe and Cr-based scale 10 Base material 20 Base material 30 Base material

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PCT/JP2021/002990 2020-01-31 2021-01-28 合金材加熱用酸化防止剤、及び、それを用いた合金材の加熱方法 Ceased WO2021153657A1 (ja)

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WO2025211451A1 (ja) * 2024-04-05 2025-10-09 日本製鉄株式会社 塗布剤、及び、それを用いた鋼材の製造方法

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