WO2020093783A1 - 一种抗氧化耐热合金及制备方法 - Google Patents

一种抗氧化耐热合金及制备方法 Download PDF

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WO2020093783A1
WO2020093783A1 PCT/CN2019/105531 CN2019105531W WO2020093783A1 WO 2020093783 A1 WO2020093783 A1 WO 2020093783A1 CN 2019105531 W CN2019105531 W CN 2019105531W WO 2020093783 A1 WO2020093783 A1 WO 2020093783A1
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alloy
oxidation
resistant
molten steel
content
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PCT/CN2019/105531
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English (en)
French (fr)
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骆合力
王兴雷
李尚平
古朝雄
王建涛
魏丽娟
尹法杰
王振华
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青岛新力通工业有限责任公司
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Priority to KR1020207029897A priority Critical patent/KR102556685B1/ko
Priority to BR112021008637-4A priority patent/BR112021008637A2/pt
Priority to US17/291,151 priority patent/US20220018005A1/en
Priority to UAA202102812A priority patent/UA128118C2/uk
Priority to JP2021517101A priority patent/JP7084551B2/ja
Priority to SG11202012154WA priority patent/SG11202012154WA/en
Priority to CA3115366A priority patent/CA3115366C/en
Application filed by 青岛新力通工业有限责任公司 filed Critical 青岛新力通工业有限责任公司
Priority to MX2021005478A priority patent/MX2021005478A/es
Priority to RU2020142945A priority patent/RU2760223C1/ru
Priority to ES19207077T priority patent/ES2891575T3/es
Priority to DK19207077.9T priority patent/DK3650560T3/da
Priority to EP19207077.9A priority patent/EP3650560B1/en
Priority to RS20211142A priority patent/RS62395B1/sr
Publication of WO2020093783A1 publication Critical patent/WO2020093783A1/zh
Priority to ZA2021/02705A priority patent/ZA202102705B/en
Priority to IL283000A priority patent/IL283000A/en

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    • 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/053—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 30% but less than 40%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
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    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/023—Alloys based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
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    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • 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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • 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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising
    • C23C8/12—Oxidising using elemental oxygen or ozone
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising
    • C23C8/12—Oxidising using elemental oxygen or ozone
    • C23C8/14—Oxidising of ferrous surfaces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/80—After-treatment

Definitions

  • This application relates to the technical field of alloys, in particular to an oxidation-resistant heat-resistant alloy and a preparation method.
  • the oxide film formed at high temperatures is mainly Cr 2 O 3 , Cr 2 O 3 is very stable below 1000 ° C and has good protection, but it is unstable above 1000 ° C, it is easy to vaporize, form pores, and lose the protection of the alloy matrix.
  • Al 2 O 3 can be stable in a high temperature environment above 1000 ° C. Therefore, to make the alloy have excellent oxidation resistance above 1000 ° C, a dense Al 2 O 3 film must be formed, and the oxide film formed on the surface of the alloy The larger the Al 2 O 3 area, the less likely the oxide film will flake off and the better the oxidation resistance of the alloy.
  • Adding a certain amount of aluminum to heat-resistant steel can form an Al 2 O 3 film, which obviously improves the high-temperature oxidation resistance of the alloy.
  • the ethylene cracking tube in the petrochemical field has begun to use aluminum-containing heat-resistant alloys to replace traditional heat-resistant steel, of which the performance is the most The best and most representative is the HTE alloy (ZL102187003B) developed by the German Schmidt-Clemens company.
  • the ethylene cracking furnace tube prepared from the alloy has good anti-oxidation and anti-coking performance, and the furnace tube life and coking cycle are compared with Traditional heat-resistant steel has been greatly improved.
  • the alloy's high-temperature mechanical properties, oxidation resistance and oxide film stability have room for further improvement.
  • the addition of active elements such as aluminum and titanium can easily form oxide and nitride inclusions with oxygen and nitrogen in the alloy, affecting the mechanical properties of the alloy, and consuming the main elements such as aluminum and titanium, affecting the aluminum oxide film Therefore, in order to achieve high-quality preparation of aluminum alloys and ensure excellent service performance, the oxygen and nitrogen contents must be strictly controlled.
  • sulfur has a great influence on the adhesion of the oxide film and the alloy substrate. In order to ensure the stability of the oxide film Ground adhesion to the surface of the alloy substrate plays a protective role, and the sulfur content in the alloy must be strictly controlled.
  • the existing aluminum alloy-containing preparation process has too wide a control range for the harmful element nitrogen, and does not control the harmful elements such as oxygen and sulfur, which seriously affects the performance and quality stability of the alloy furnace tube .
  • this application aims to provide an oxidation-resistant heat-resistant alloy and a preparation method, which can at least solve one of the following technical problems:
  • the present application provides an oxidation-resistant heat-resistant alloy.
  • the alloy contains: Al, 2.5% -6%, Ni, 30% -50%, W, 2% -8% in terms of mass percentage. Hf, 0.01% -0.4%.
  • the alloy contains: Al, 2.5% -6%, Cr, 24% -30%, C, 0.3% -0.55%, Ni, 30% -50%, W, 2% -8%, Ti, 0.01% -0.2%, Zr, 0.01% -0.2%, Hf, 0.01% -0.4%, Y, 0.01% -0.2%, V, 0.01% -0.2%; wherein, both Ti and V include one of them.
  • the alloy contains: N ⁇ 0.05%, O ⁇ 0.003%, S ⁇ 0.003%, Si ⁇ 0.5%, and the balance is Fe and inevitable impurities.
  • the alloy includes: Al, 3.3% -5.5%, Ni, 34% -46%.
  • the alloy includes: W, 3% -6%.
  • the alloy includes: Y, 0.01% -0.06%.
  • the oxide film formed on the surface of the alloy is an Al 2 O 3 film.
  • the present application also provides a method for preparing an oxidation-resistant heat-resistant alloy, including the following steps:
  • Step 1 Melt carbon and inactive elements to obtain molten steel after complete melting
  • Step 2 The molten steel is heated and refined
  • Step 3 Add mixed rare earth
  • Step 4 Add slag
  • Step 5 The pouring tank is filled with inert gas, and active elements such as aluminum, hafnium, titanium, zirconium, and yttrium are placed in the pouring tank, the temperature is increased, the molten steel is poured into the pouring tank, and the molten steel is introduced into the tundish to be cast.
  • active elements such as aluminum, hafnium, titanium, zirconium, and yttrium
  • the refining temperature in step 2 is above 1640 ° C.
  • step 1 part of the carbon is first added in step 1, and the remaining carbon is added after the molten steel temperature in step 2 is raised above 1640 ° C.
  • the amount of mixed rare earth added is 0.05% -0.25% of the molten steel mass.
  • the slag contains CaO.
  • the inert gas is argon
  • the pressure of argon is 0.15-0.3MPa
  • the flow rate is 1-5L / min.
  • step 5 casting is also included, and the speed from tapping to completion of casting is 60-100 kg / min.
  • This application adjusts the process steps and process parameters so that the N content in the alloy prepared by the preparation method of this application is less than 0.05%, the O content is less than 0.003%, the S content is less than 0.003%, and the Si content is less than 0.5% .
  • FIG. 1 is the cyclic oxidation weight gain curve of alloy No. 8 and alloy No. 8 of the comparative example at 1100 ° C;
  • FIG. 3 is the oxidative peeling curve of alloy No. 9 and alloy No. 9 of the comparative example at 1150 ° C;
  • FIG. 4 is the cyclic oxidation peeling curve of alloy No. 9 and alloy No. 9 of the comparative example at 1200 ° C;
  • FIG. 5 is a microscopic scanning photo of the oxide film on the surface of the alloy No. 3 of the present application after being oxidized at 1200 ° C for 100 hours;
  • Fig. 6 is a micro-scan photo of the oxide film on the surface of the comparative material No. 9 alloy after cyclic oxidation at 1200 °C for 100h;
  • Fig. 8 is a scanning photograph of the cross-section of the oxide film of the alloy No. 9 after being oxidized at 1200 ° C for 100 hours.
  • the content refers to the mass percentage content.
  • the functions of the elements in the iron-nickel-based high-temperature oxidation-resistant heat-resistant alloy of the present application are described in detail as follows:
  • Ni can stabilize the austenite structure, expand the austenite phase area, make the alloy have high strength and plastic matching, and ensure that the alloy has good high temperature strength and creep resistance, but the Ni content is too high, affecting nitrogen
  • the solubility in the matrix exacerbates the precipitation tendency of nitrides in the alloy and affects the creep strength of the alloy.
  • too high content of Ni can easily form Ni 3 Al phase with Al in the alloy, affecting the toughness and machining performance of the alloy If the Ni content is greater than 60%, even if the Al content is controlled below 4%, Ni 3 Al phase will be formed, which affects the toughness and workability of the alloy.
  • the cost of the Ni element is high, and the excessive content will affect the preparation cost of the alloy . Therefore, the content of Ni in the material of the present application is controlled to be 30% -50%, preferably 34% -46%.
  • Al is an essential element for the formation of a high-stability Al 2 O 3 film on the surface of the alloy of this application during high-temperature oxidation, but the Al element content is too high, it is easy to form an intermetallic compound Ni 3 Al phase with Ni, which can improve the alloy ’s Strength, but harmful to toughness and processing performance.
  • Ni 3 Al phase dissolves and disappears, so it has no benefit to the high temperature strength and service life of the alloy.
  • the presence of Ni 3 Al will increase the strength of the alloy, but the increase in strength at room temperature or low and medium temperatures will not help the service of the alloy, and the reduction in toughness at room temperature and the reduction in machining performance will seriously affect the forming and processing of parts Cost, therefore, for the present application, it is necessary to control the joint adjustment of the Ni content and the Al content to avoid the formation of the Ni 3 Al phase.
  • the Al content in this application is controlled It is 2.5% -6%, preferably 3.3% -5.5%.
  • the addition of Cr in this application can reduce the critical value of the amount of Al that forms the Al 2 O 3 film.
  • the addition of Cr reduces the amount of Al that forms the Al 2 O 3 film on the surface of the alloy, thereby promoting the Al 2 O 3 protective layer.
  • Cr is also a carbide forming element, which forms carbides to improve the high temperature strength of the alloy, but Cr is a strong ferrite forming element, and excessive addition will weaken the stability of the austenite phase, which is not conducive to the high temperature of the alloy Strength, so the content of Cr in this application should be controlled at 24% -30%.
  • C is a carbide-forming element.
  • the carbide phase is formed in the alloy of the present application, which plays a role of dispersion strengthening.
  • the carbon content is low, the number of carbide phases is small, which affects the strengthening effect.
  • the carbon content is too high and the number of carbides is too much. , which is detrimental to the toughness of the alloy. Therefore, the content of C in the materials of this application is controlled at 0.3% -0.55%.
  • W dissolves in the alloy matrix for solid solution strengthening, and forms carbides for dispersion strengthening, which can effectively improve the high temperature strength of the alloy, but too high W content will affect the toughness of the alloy, so the W content control in this application 2% -8%, preferably 3% -6%.
  • Ti, V can change the grain boundary carbide morphology, refine the carbide and make it evenly distributed, thereby improving the high-temperature creep strength of the alloy.
  • the content is too high, which has an adverse effect on the carbide morphology and is easy to form Ni 3 (Al, Ti) phase affects the toughness of the alloy. Therefore, the content of Ti in this application should be controlled at 0.01% -0.2%, and the content of V should be controlled at 0.01% -0.2%
  • Zr segregates at the grain boundary and plays a role in strengthening the grain boundary, but too much content is easy to form a low melting point phase of Ni 5 Zr, which affects the high temperature performance of the alloy, so the content of Zr in the material of this application should be controlled at 0.01% -0.2% .
  • Hf, Y Appropriate amounts of Hf and Y elements can be added to this application, which can affect the morphology and chemical composition of the oxide and the degree of internal oxidation, improve the adhesion of the oxide film, and greatly improve the high temperature oxidation resistance of the alloy. ,Better results. Because the rare earth element Y is very active, Y is easily burned or oxidized when the alloy is not vacuum-smelted, and it is difficult to effectively control the content in the project and cannot guarantee service stability. The Hf is relatively stable, and the content is easy to control during smelting. In addition, Hf can significantly increase the adhesion of the oxide film under a high temperature environment above 1000 °C, but the Hf and Y content is too high.
  • the materials of the present application are combined with Hf and Y, the content of Hf is controlled at 0.01% -0.4%, and the content of Y is controlled at 0.01% -0.2%.
  • Si is easily brought into the alloy through raw materials such as ferrochromium. Si will promote the precipitation of harmful ⁇ phases, thereby reducing the longevity of the alloy. Therefore, the content of Si should be strictly controlled.
  • the raw materials are used to control the Si in the alloy.
  • the Si content is controlled to be less than 0.5%.
  • the alloy components of this application contain active elements such as Al, Hf, Y, Zr, Ti, if the O and N content is high, it is easy to form inclusions such as oxides and nitrides, which damages the strength and toughness of the alloy. It also consumes favorable elements such as Al and Hf and affects the formation of the aluminum oxide film. Therefore, the lower the O and N content, the better.
  • the O content in the alloy of this application is controlled below 0.003%, and the N content is controlled below 0.05%.
  • S S segregates on the grain boundary, destroying the continuity and stability of the grain boundary, significantly reducing the long-term creep performance and tensile plasticity of the alloy, weakening the adhesion of the surface oxide film, easily causing the oxide film to peel off, and reducing the alloy Antioxidant properties. Therefore, the S content should be controlled as low as possible, and the S content in the alloy of this application should be controlled below 0.003%.
  • the oxidation-resistant heat-resistant alloy contains: Al, 2.5% -6%, Cr, 24% -30%, C, 0.3% -0.55 %, Ni, 30% -50%, W, 2% -8%, Ti, 0.01% -0.2%, Zr, 0.01% -0.2%, Hf, 0.01% -0.4%, Y, 0.01% -0.2%, V, 0.01% -0.2%, N ⁇ 0.05%, O ⁇ 0.003%, S ⁇ 0.003%, Si ⁇ 0.5%, the balance is Fe and inevitable impurities; among them, Ti and V include one of them .
  • the present application adjusts the composition and addition amount of the alloy so that the alloy has excellent oxidation resistance, better high-temperature strength and good weldability.
  • the beneficial effects of the oxidation-resistant heat-resistant alloy of the present application are as follows:
  • composition and mass percentage content of the alloy of the present application may also be Al, 4.5% -5.5%, Ni, 34% -46%, W, 3% -6%, Y, 0.01% -0.06%.
  • the preparation method of the oxidation-resistant heat-resistant alloy of this application differs according to different uses. If it is used for high-temperature parts in the aerospace field, vacuum induction melting and casting must be used, including the following steps:
  • Electrolytic nickel, metallic chromium (or ferrochromium), pure iron, and metallic tungsten are placed in the crucible, and other elements are added from the hopper.
  • Power transmission at low power for 10 minutes to remove hydrogen, then power at high power to complete melting, and start refining, refining temperature 1530 ⁇ 1580 °C, refining time depends on the amount of molten steel, controlled at 10 ⁇ 60 minutes, vacuum during refining The degree should be less than 5Pa.
  • the above-mentioned vacuum induction melting method is used to prepare the alloy of the present application, although active elements such as Al and Y can be accurately controlled, and harmful elements such as O, N, and S can be reduced to a very low level.
  • active elements such as Al and Y can be accurately controlled, and harmful elements such as O, N, and S can be reduced to a very low level.
  • the preparation method is costly, and the preparation parts are also subject to the current vacuum furnace equipment. Therefore, vacuum casting is only suitable for precision casting aerospace castings.
  • the present application also provides a method for preparing an oxidation-resistant heat-resistant alloy under non-vacuum conditions, including the following steps:
  • Step 1 Melt carbon and inactive elements to obtain molten steel after complete melting
  • Step 2 The molten steel is heated to above 1640 ° C for refining
  • Step 3 Add mixed rare earth
  • Step 4 Add slag
  • Step 5 Active elements such as aluminum, hafnium, titanium, zirconium, yttrium, etc. are placed in the pouring tank.
  • the pouring tank is filled with inert gas.
  • the temperature rises to 1650-1750 ° C the molten steel is poured into the pouring tank.
  • the liquid is introduced into the tundish for centrifugal casting.
  • This application adjusts the process steps and process parameters so that the N content in the alloy prepared by the preparation method of this application is less than 0.05%, the O content is less than 0.003%, the S content is less than 0.003%, and the Si content is less than 0.5% .
  • the use of carbon to react with O in the molten steel to generate CO gas can be deoxidized, on the other hand, using the formed CO for bubble carrying denitrification.
  • the mixed rare earth reacts with free O and S in molten steel to form oxides or sulfides, thereby desulfurizing and further deoxidizing.
  • the active element is not directly melted, but the active element is placed in a pouring tank protected by an inert gas, the molten steel in which the inactive element is melted is poured onto the active element, and the molten steel is used
  • the heat melts the active elements and uses the kinetic energy of the tapping to make the active elements uniform in the spout. The above process can effectively reduce the oxidation of active elements, thereby effectively protecting the alloy elements from being consumed.
  • carbon is added in a stepwise manner in the preparation method of the present application. This is because smelting is carried out in the air, and as the smelting progresses, oxygen will enter continuously
  • For the molten steel firstly add some carbon to the preliminary deoxidation and denitrification in the above preparation method, wait for the molten steel temperature to rise above 1640 °C, then add the remaining carbon, and the free energy of CO under high temperature is lower than NiO, Fe 2 O 3 and Cr 2 O 3 Like oxides, it replaces the oxygen that may exist in the oxide, performs deep deoxidation, and protects the alloy elements from being lost. In addition, if too much carbon is added at one time, it is easy to catch fire and damage, so that the carbon cannot effectively enter the molten steel, thereby affecting the deoxidation and denitrification effects.
  • the pouring temperature differs according to the castings to be cast.
  • the high pouring temperature is to ensure that the molten steel has sufficient fluidity to facilitate the formation of the centrifuge tube.
  • the elements in molten steel are more likely to burn. Therefore, considering the fluidity of molten steel and element burning, the temperature when casting the centrifuge tube is selected to be 1650 ⁇ 1750 °C.
  • the crucible in the above preparation method is made of alumina material with good high-temperature stability.
  • a covering slag containing CaO is added to the surface of the molten steel.
  • CaO is used for further desulfurization to achieve further deoxidation , Nitrogen and Sulfur; on the other hand, it can also effectively remove inclusions and obtain highly clean molten steel.
  • CaO reacts with S for pre-desulfurization.
  • the reaction process is: the surface begins with a desulfurization reaction, and the desulfurization generates CaS, which covers the CaO surface. After coating with CaO powder, the product layer diffuses inward to the desulfurization reaction, and the CaS layer on the surface of CaO gradually thickens, and the diffusion desulfurization reaction gradually slows down until it stops.
  • the addition amount of slag is controlled to 3% of the quality of the molten steel ⁇ 5%, so that the slag can not only play a good role in further deoxidation, nitrogen and sulfur; but also can effectively remove inclusions and obtain highly clean molten steel.
  • the mixed rare earth used in the preparation method of the present application is a mixture of the rare earth elements La and Ce, and the added amount is 0.05% to 0.25% of the mass of the molten steel. This is because the amount of mixed rare earth added is small, the number of chemical reactions participating in desulfurization is small, and the desulfurization effect is not good. .
  • the amount of mixed rare earth added is selected to be 0.05% -0.25% of the quality of the molten steel, which not only ensures a good desulfurization effect, but also does not cause the rare earth elements remaining in the molten steel to form a low melting point phase with Ni, Affect the high temperature mechanical properties of the alloy.
  • the top surface of the pouring tank is filled with flowing argon gas to form a gas curtain to protect the molten steel containing easily oxidized elements and slow down its oxidation.
  • the pressure of argon is selected to be 0.15-0.3MPa, and the flow rate is selected to be 1-5L / min. This is because the argon gas pressure is too low to effectively form an argon gas curtain to isolate the air and avoid molten steel from being oxidized; the argon gas pressure is too large, which is easy to form waste, increase production costs, and is unfavorable to the safety of the operating workers.
  • the centrifugal casting process is as follows: the molten steel in the tundish with qualified components, suitable superheat and suitable weight is quickly cast into a high-speed rotating metal mold barrel, and the molten steel solidifies Become a centrifugal cast tube.
  • the alloy prepared by the preparation method of the present application can be used not only for casting centrifugal casting tubes, but also for casting other castings that need to be served at high temperatures, especially high temperatures and oxidation at 1100-1200 ° C Castings in service in harsh environments.
  • the entire tapping operation process is required to be very fast. Specifically, the speed from tapping to completion of casting is controlled at 60 to 100 kg / min.
  • the chemical composition and content of the alloy in the examples of the present application are shown in Table 1, the process parameters of the preparation method are shown in Table 2, the peeling amount of the alloy after being oxidized at different temperatures for 100h is shown in Table 3, and the oxide film formed after the alloy is oxidized at different temperatures and high temperature cycles The content of alumina is shown in Table 4, and the endurance life of the alloy at 1100 °C / 17MPa is shown in Table 5.
  • Example 1 corresponds to No. 1 alloy
  • Example 2 corresponds to No. 2 alloy
  • No. 8 alloy and No. 9 alloy are prior art comparative materials.
  • No. 8 alloy is the highest weldable high temperature alloy GH3230, which is widely used in high temperature parts of aerospace engine combustion chamber.
  • No. 9 alloy is currently the best material HTE alloy for ethylene cracking furnace tubes in the petrochemical field.
  • the oxidation-resistant heat-resistant alloys of Examples 1-7 were prepared as follows:
  • Step 1 Weigh the raw materials for use
  • Step 2 Put electrolytic nickel, pure iron and part of graphite in the crucible of a non-vacuum intermediate frequency melting furnace with fixed-point casting function, and completely melt to obtain molten steel;
  • Step 3 The molten steel is heated to the refining temperature and the remaining graphite is added;
  • Step 4 Add a certain amount of mixed rare earth
  • Step 5 Add a certain amount of slag containing CaO;
  • Step 6 Fill the top surface of the pouring tank with flowing argon gas, and place active elements such as aluminum metal, sponge hafnium, sponge titanium, sponge zirconium, and metal yttrium into the pouring tank, and wait for the chemical composition of the molten steel in step 2
  • active elements such as aluminum metal, sponge hafnium, sponge titanium, sponge zirconium, and metal yttrium into the pouring tank, and wait for the chemical composition of the molten steel in step 2
  • the temperature is qualified and the temperature of the molten steel rises to the pouring temperature
  • the molten steel is cast into the pouring channel at the opening above the pouring channel, and the molten steel is introduced into the tundish at the opening below the pouring channel to wait for centrifugal casting;
  • Casting centrifuge tube The molten steel in the tundish is quickly cast into a metal mold barrel rotating at high speed to prepare a centrifuge tube for experiment.
  • No. 8 alloy does not form an alumina film at a high temperature of 1150 ° C. Therefore, there is no data for No. 8 alloy in the table.
  • the 1100 ° C oxidation resistance of the alloy material according to the embodiment of the present application is 2.5 to 4 times that of the prior art comparative material No. 8 alloy. Above 1100 ° C, No. 8 alloy does not form a continuous and stable oxide film, and the oxidizability drops sharply.
  • the amount of oxidized peeling of the prior art comparative material No. 9 alloy is 5 to 10 times that of the alloy material of the embodiment of the present application.
  • the prior art comparative material No. 9 The amount of oxidized peeling of the alloy is 27 times that of the alloy material of the embodiment of the present application. It shows that the adhesion force between the alloy oxide film and the substrate of the example of this application is much greater than the adhesion force between the alloy oxide film of No. 9 and the substrate, and the higher the temperature, the more obvious the advantages of the alloy of the application.
  • FIGS. 7 and 8 Further observation of the section of the oxide film formed after cyclic oxidation at 1200 ° C / 100h (see FIGS. 7 and 8) shows that the oxide film formed by the alloy of the present application is continuously dense and tightly bonded to the substrate, and the bonding interface is neat and the thickness of the oxide film is about It is 6 ⁇ m; the oxide film of alloy 9 of the prior art is discontinuous and loose in structure, the remaining oxide film is not tightly bonded to the substrate, and the bonding interface is uneven, with obvious flaking, and the thickness of the remaining oxide layer is about 3 ⁇ m. Comparing the situation of the two oxide films, the protective effect of the oxide film formed by the material of the present application on the alloy substrate is significantly better than that of the prior art comparative material No. 9 alloy.
  • the complete oxidation resistance temperature of the alloy of the examples of the present application reached 1200 ° C, while the complete oxidation resistance temperature of the alloy 9 of the prior art is only 1050 °C.
  • the temperature of the alloy's complete anti-oxidation grade is 150 °C higher than that of existing alloys.
  • the temperature is higher than 1000 °C, especially above 1100 °C, due to the stability of the oxide film and the poor adhesion to the substrate Due to other reasons, the oxidation resistance of the alloy is drastically reduced. For example, the No.
  • alloy No. 9 alloy with excellent oxidation resistance in the prior art, the test temperature is increased from 1150 °C to 1200 °C, the proportion of alumina in the oxide film is reduced from 70% to 25%, and the amount of oxide film peeling is increased by 5 times.
  • alloy No. 9 still belongs to the complete oxidation resistance level. At 1100 ° C, it has been reduced to the oxidation resistance level, and by 1200 ° C, it has been reduced to the secondary oxidation resistance level.
  • Those skilled in the art are well aware that it is very difficult to improve the oxidation resistance of alloys above 1100 ° C.
  • the oxidation-resistant heat-resistant alloy of this application has the advantages of higher use temperature, better high-temperature oxidation resistance, denser oxide film formation, larger area of aluminum oxide film, and better mechanical properties at high temperature.
  • the oxidation-resistant heat-resistant alloy can be used for long-term stable service below 1200 °C, and can form more than 90% alumina film in the oxidizing atmosphere of 1000 ⁇ 1200 °C.
  • below 1200 °C is a complete anti-oxidation grade, which is better than the current
  • solderable high-temperature materials are solderable high-temperature materials.
  • the alloy of this application has excellent overall performance. In addition to being used to cast ethylene cracking furnace tubes, it can also be used to cast other castings that need to be served at high temperatures, especially in harsh environments that require high temperatures and oxidizing temperatures of 1100-1200 ° C. Castings under service.

Abstract

本申请涉及一种抗氧化耐热合金及制备方法，属于合金技术领域，解决了现有合金中氧、硫、氮含量高，合金表面的氧化膜中Al 2O 3膜的比例低，铝含量高时，合金的韧性差的问题。本申请的抗氧化耐热合金，按质量百分含量计，包含：Al、2.5％-6％，Cr、24％-30％，C、0.3％-0.55％，Ni、30％-50％，W、2％-8％，Ti、0.01％-0.2％，Zr、0.01％-0.2％，Hf、0.01％-0.4％，Y、0.01％-0.2％，V、0.01％-0.2％，N<0.05％，O<0.003％，S<0.003％，Si<0.5％，余量为Fe及不可避免的杂质；其中，Ti和V二者包含其中之一。抗氧化耐热合金的制备方法包括：非活泼元素物料熔炼→精炼→加混合稀土→加熔渣→活泼元素合金化。本申请的抗氧化耐热合金的完全抗氧化级温度达到1200℃，实现了合金可在1200℃以下长期稳定服役。

Description

一种抗氧化耐热合金及制备方法 技术领域
本申请涉及合金技术领域，尤其涉及一种抗氧化耐热合金及制备方法。
背景技术
随着航空、石化等领域的发展，对在1000～1200℃具有优异高温抗氧化性能的材料需求迫切，如航空发动机燃烧室和尾喷管用高温部件、乙烯裂解炉管等，此外，为了实现部件的连接，还要求材料具有良好的焊接性。这些部件的现役材料大多为变形高温合金和耐热钢，焊接性良好，但合金的高温抗氧化主要通过添加高含量的Cr来实现，其高温下形成的氧化膜主要为Cr 2O 3，Cr 2O 3在1000℃以下很稳定，具有良好的保护作用，但在1000℃以上不稳定，容易气化，形成孔洞，对合金基体失去保护作用。Al 2O 3可在1000℃以上的高温环境下保持稳定，因此，要使得合金在1000℃以上具有优异的抗氧化性能，须形成致密的Al 2O 3膜，且合金表面形成的氧化膜中Al 2O 3面积越大，氧化膜越不容易剥落，合金的抗氧化性越好。
在耐热钢中添加一定量的铝，可以形成Al 2O 3膜，明显改善合金高温抗氧化性能，石化领域乙烯裂解管已开始采用含铝耐热合金替代传统的耐热钢，其中性能最优、最具代表性的就是德国Schmidt-Clemens公司开发的HTE合金(ZL102187003B)，由该合金制备的乙烯裂解炉管具有良好的抗氧化和抗结焦性能，炉管寿命和清焦周期都较之传统的耐热钢有较大提高。但是，该合金的高温力学性能、抗氧化性和氧化膜稳定性还有进一步提升空间。
另外，铝含量高时，可以生成充分厚度的Al 2O 3层，从而防止生成的Al 2O 3层在高温使用时剥离，但铝含量太高，合金的韧性差。因此，高温使用时，合金良好的抗氧化性和良好的韧性无法兼得。
与耐热钢不同，铝、钛等活泼元素的加入，容易和合金中的氧和氮 形成氧化物和氮化物夹杂，影响合金的力学性能，并消耗铝、钛等主元素，影响氧化铝膜的形成，因此，含铝合金要实现高质量的制备并保证优良的服役性能，必须严格控制氧、氮含量，此外，硫对氧化膜和合金基体的黏着力影响巨大，为了保证氧化膜能稳定地黏着于合金基体表面起到保护作用，须严格控制合金中的硫含量。但受制于制备工艺，现有含铝合金的制备过程中对有害元素氮的控制范围过宽，且未对氧、硫等有害元素进行控制，严重影响了该合金炉管的性能和质量稳定性。
对于合金领域来说，要提高合金在1050℃以下的综合性能相对容易，而要提高合金服役温度在1050℃以上的性能，尤其是接近1200℃时的综合性能，是本领域的一大难题，正因为提高合金在高温服役温度下的性能如此困难，所以，在1050℃以上，哪怕将合金的使用温度仅提高50℃，其困难程度将是指数级别的，所需要付出的劳动也将是常人难以想象的，区区50℃的提高，其成果不容小觑，可以得到业内人士的认可和普遍尊重。
发明内容
鉴于上述的分析，本申请旨在提供一种抗氧化耐热合金及制备方法，至少可以解决以下技术问题之一：
(1)服役温度为1100℃以上时，合金良好的抗氧化性能和力学性能无法兼得；
(2)未对氧、硫、氮等有害元素进行有效控制，导致该合金的综合性能差、且质量不稳定；
(3)合金在1100℃以上的高温环境下表面形成的氧化膜中Al 2O 3膜的比例低，并且Al 2O 3膜易剥落，导致合金抗氧化性差。
本申请的目的主要是通过以下技术方案实现的：
一方面，本申请提供了一种抗氧化耐热合金，按质量百分含量计，该合金包含：Al、2.5％-6％，Ni、30％-50％，W、2％-8％，Hf、0.01％-0.4％。
在上述方案的基础上，本申请还做了如下改进：
进一步，该合金包含：Al、2.5％-6％，Cr、24％-30％，C、0.3％-0.55％，Ni、30％-50％，W、2％-8％，Ti、0.01％-0.2％，Zr、0.01％-0.2％，Hf、 0.01％-0.4％，Y、0.01％-0.2％，V、0.01％-0.2％；其中，Ti和V二者包含其中之一。
进一步，所述合金含有：N<0.05％，O<0.003％，S<0.003％，Si<0.5％，余量为Fe及不可避免的杂质。
进一步，所述合金包含：Al、3.3％-5.5％，Ni、34％-46％。
进一步，所述合金包含：W、3％-6％。
进一步，所述合金包含：Y、0.01％-0.06％。
进一步，在1000～1200℃的氧化气氛中，合金表面形成的氧化膜中90％以上的面积是Al 2O 3膜。
另一方面，本申请还提供了一种抗氧化耐热合金的制备方法，包括如下步骤：
步骤1：将碳和非活泼元素熔融，完全熔化后得到钢液；
步骤2：钢液升温，精炼；
步骤3：加入混合稀土；
步骤4：加入熔渣；
步骤5：浇流槽内充惰性气体，铝、铪、钛、锆、钇等活泼元素置于浇流槽中，升温，将钢液浇注到浇流槽中，钢液引入中间包待浇铸。
进一步，步骤2中精炼温度为1640℃以上。
进一步，步骤1中先加入部分碳，待步骤2中钢液升温至1640℃以上再加入其余碳。
进一步，混合稀土的加入量为钢液质量的0.05％-0.25％。
进一步，所述熔渣含有CaO。
进一步，所述惰性气体为氩气，氩气的压力为0.15-0.3MPa，流量为1-5L/min。
进一步，所述步骤5之后还包括浇铸，从出钢到完成浇铸的速度为60～100kg/分钟。
本申请有益效果如下：
(1)通过添加适量的Al元素以保证能形成Al 2O 3膜，并兼顾焊接性和力学性能；通过添加适量的C元素以保证析出碳化物强化合金；通过添加适量的Cr元素促进在低铝含量下能形成Al 2O 3膜，并形成碳化物强 化合金；通过添加适量Zr元素强化晶界，提高力学性能；通过添加适量Ti或V元素细化碳化物，提高合金的蠕变性能。
(2)通过联合调整Ni含量和Al含量，减少Ni 3Al相的形成，使得Al含量高于4％时，合金仍具有良好的韧性。
(3)通过加入Hf，并通过Hf和Y二者联合作用，在Y含量低于0.06％时，仍能够改善氧化物的形貌和化学组成以及内氧化程度，使得合金表面形成的氧化膜连续且致密，提高氧化膜和基体的黏结力，进而大幅度提高合金的高温抗氧化性能。
(4)通过加入W，并通过控制W含量，提高合金的高温强度，延长使用寿命。
(5)因为要提高合金在1050℃以上的性能，尤其是接近1200℃时的性能是非常困难的，温度每提高20℃或50℃，这种困难的增加会是指数级别的，绝不是经过有限次的实验，或者根据常规选择就能得到或实现的。实际上，本申请是经过大量实验来调整合金的成分及含量，使得合金可在1100～1200℃的高温环境下形成稳的定Al 2O 3膜，该合金具有优异的抗氧化性能、良好的高温强度和良好的焊接性能，其综合性能优于现有含铝耐热合金材料。
(6)本申请提供的制备方法中，通过分批加入碳，实现多次、深度脱氧和脱氮，从而有效降低合金中N和O的含量，进而提高合金性能。
(7)通过多次加入混合稀土而不是一次性加入，来减少稀土的氧化和烧损，保证稀土能够有效加入；通过控制混合稀土的加入量使得既能保证良好的脱硫效果，又不会使残留在钢液中的稀土元素与Ni形成低熔点相，影响合金的高温力学性能。
(8)通过选择覆盖溶渣的种类以及控制覆盖溶渣的加入量来吸附和捕获上浮的氧化物、氮化物、硫化物和夹杂物，从而获得洁净度高的钢液。
(9)通过控制精炼温度在1640℃以上使得碳与钢液中氧化物夹杂置换反应生成CO的化学反应更易进行，净化效果更好。
(10)本申请通过调整工艺步骤和工艺参数使得使用本申请的制备方法制备的合金中N含量低于0.05％、O含量低于0.003％、S含量低于 0.003％、Si含量低于0.5％。
本申请中，上述各技术方案之间还可以相互组合，以实现更多的优选组合方案。本申请的其他特征和优点将在随后的说明书中阐述，并且，部分优点可从说明书中变得显而易见，或者通过实施本申请而了解。本申请的目的和其他优点可通过说明书、权利要求书中所特别指出的内容中来实现和获得。
附图说明
附图仅用于示出具体实施例的目的，而并不认为是对本申请的限制，在整个附图中，相同的参考符号表示相同的部件。
图1为本申请实施例合金和对比材料8号合金在1100℃循环氧化增重曲线；
图2为本申请实施例合金和对比材料9号合金在1100℃循环氧化剥落曲线；
图3为本申请实施例合金和对比材料9号合金在1150℃循环氧化剥落曲线；
图4为本申请实施例合金和对比材料9号合金在1200℃循环氧化剥落曲线；
图5为本申请实施例3号合金经1200℃循环氧化100h后表面氧化膜微观扫描照片；
图6为对比材料9号合金经1200℃循环氧化100h后表面氧化膜微观扫描照片；
图7为本申请实施例3号合金经1200℃循环氧化100h后氧化膜剖面扫描照片；
图8为对比材料9号合金经1200℃循环氧化100h后氧化膜剖面扫描照片。
具体实施方式
下面结合附图来具体描述本申请的优选实施例，其中，附图构成本申请一部分，并与本申请的实施例一起用于阐释本申请的原理，并非用 于限定本申请的范围。
本申请中如无特别说明，含量均指质量百分含量。本申请的铁镍基高温抗氧化耐热合金中各元素所起的作用详细叙述如下：
Ni:Ni可以稳定奥氏体组织，扩大奥氏体相区，使合金具有高的强度和塑性匹配，并且保证合金具有较好的高温强度和蠕变抗力，但是，Ni含量过高，影响氮在基体中的溶解度，加剧合金中氮化物的析出倾向，影响合金的蠕变强度，此外，过高含量的Ni还易与合金中的Al形成Ni 3Al相，影响合金的韧性和机加工性能，如果Ni含量大于60％，即使Al含量控制在4％以下，也会形成Ni 3Al相，影响合金的韧性和加工性能，而且，Ni元素成本较高，含量过高会影响合金的制备成本。所以本申请材料中Ni的含量控制为30％-50％，优选为34％-46％。
Al：Al是本申请合金在高温氧化时表面形成高稳定性Al 2O 3膜的必须元素，但Al元素含量过高，易与Ni形成金属间化合物Ni 3Al相，该相可提高合金的强度，但对韧性和加工性能有害。温度高于1000℃时，Ni 3Al相回溶消失，因而对合金的高温强度和服役寿命无益处。在中低温下，Ni 3Al的存在会提高合金的强度，但室温或中低温强度的提高对合金的服役没有帮助，而室温韧性的降低和机加工性能的降低会严重影响部件的成型和加工成本，因而，对于本申请而言，要通过Ni含量和Al含量的联合调整控制，避免形成Ni 3Al相。基于本申请中Ni含量不高，所以Al含量高于4％时，仍未形成Ni 3Al相，同时为了在更高温度下形成稳定的Al 2O 3膜，所以本申请中Al的含量控制为2.5％-6％，优选为3.3％-5.5％。
Cr：本申请中加入Cr可以降低形成Al 2O 3膜的Al量临界值，Cr的添加使得该合金表面形成Al 2O 3膜层的Al量降低，从而促进了Al 2O 3保护层的形成；此外，Cr还是碳化物形成元素，形成碳化物提高合金的高温强度，但是，Cr是强铁素体形成元素，加入量过多将削弱奥氏体相的稳定性，不利于合金的高温强度，所以本申请中Cr的含量应控制在24％-30％。
C：C是碳化物形成元素，在本申请合金中形成碳化物相，起到弥散强化的作用，碳含量低，碳化物相数量少，影响强化效果，碳含量过高，碳化物数量过多，对合金的韧性不利。所以本申请材料中C的含量控制 在0.3％-0.55％。
W：W固溶于合金基体起固溶强化作用，并形成碳化物起到弥散强化作用，可以有效提高合金的高温强度，但W含量过高会影响合金的韧性，所以本申请中W含量控制在2％-8％，优选为3％-6％。
Ti、V：Ti、V可以改变晶界碳化物形态，细化碳化物，使其均匀弥散分布，从而提高合金的高温蠕变强度，含量过高，对碳化物形态有不利影响，且容易形成Ni 3(Al,Ti)相，影响合金韧性。所以本申请中Ti的含量应控制在0.01％-0.2％，V的含量应控制在0.01％-0.2％
Zr：Zr偏析于晶界，起到晶界强化作用，但含量过多易形成Ni 5Zr低熔点相，影响合金的高温性能，所以本申请材料中Zr的含量应控制在0.01％-0.2％。
Hf、Y：本申请中加入适量Hf、Y元素，可以影响氧化物的形貌和化学组成以及内氧化程度，提高氧化膜的粘着力，大幅度提高合金的高温抗氧化性能，二者联合作用，效果更好。由于稀土元素Y非常活泼，在非真空熔炼合金时，Y极易烧损或氧化，工程上难以有效控制含量，不能保证服役稳定性。而Hf相对较稳定，冶炼时含量容易控制，加之，Hf可显著提高氧化膜1000℃以上高温环境下的粘着力，但Hf、Y含量过高，一方面，会增加材料成本，另一方面，易与Ni形成低熔点相，影响合金的高温力学性能。所以本申请材料联合加入Hf和Y，Hf的含量控制在0.01％-0.4％、Y含量控制在0.01％-0.2％。
Si：Si容易通过铬铁等原材料带入合金中，Si会促进有害的σ相析出，从而降低合金的持久寿命，因此Si的含量应严格控制，本申请中通过优选原材料来达到控制合金中Si含量的目的，本申请中控制Si含量低于0.5％。
O、N：因本申请的合金成分中含有Al、Hf、Y、Zr、Ti等活泼元素，如果O、N含量较高，易形成氧化物和氮化物等夹杂，既损害合金的强韧性，又消耗Al、Hf等有利元素，影响氧化铝膜的形成，因此，O、N含量应该控制得越低越好，本申请合金中O含量控制在0.003％以下，N含量控制在0.05％以下。
S：S偏聚于晶界，破坏了晶界的连续性和稳定性，显著降低合金的 持久蠕变性能和拉伸塑性，削弱表面氧化膜的粘附性，易导致氧化膜剥落，降低合金的抗氧化性能。因此，S含量应控制得越低越好，本申请合金中S含量控制在0.003％以下。
本申请提供了一种抗氧化耐热合金，按质量百分含量计，所述抗氧化耐热合金含有：Al、2.5％-6％，Cr、24％-30％，C、0.3％-0.55％，Ni、30％-50％，W、2％-8％，Ti、0.01％-0.2％，Zr、0.01％-0.2％，Hf、0.01％-0.4％，Y、0.01％-0.2％，V、0.01％-0.2％，N<0.05％，O<0.003％，S<0.003％，Si<0.5％，，余量为Fe及不可避免的杂质；其中，Ti和V二者包含其中之一。
与现有技术相比，本申请通过调整合金的成分及添加量使得合金具有优异的抗氧化性能、较好的高温强度且焊接性好的合金。
具体来说，本申请的抗氧化耐热合金的有益效果如下：
(1)通过添加适量的Al元素以保证能形成Al 2O 3膜，并兼顾焊接性和力学性能；通过添加适量的C元素以保证析出碳化物强化合金；通过添加适量的Cr元素促进在低铝含量下能形成Al 2O 3膜，并形成碳化物强化合金；通过添加适量Zr元素强化晶界，提高力学性能；通过添加适量Ti或V元素细化碳化物，提高合金的蠕变性能。
(2)通过联合调整Ni含量和Al含量，减少Ni 3Al相的形成，使得Al含量高于4％时，合金仍具有良好的韧性。
(3)通过加入Hf，并通过Hf和Y二者联合作用，在Y含量低于0.06％时，仍能够改善氧化物的形貌和化学组成以及内氧化程度，使得合金表面形成的氧化膜连续且致密，提高氧化膜和基体的黏结力，进而大幅度提高合金的高温抗氧化性能。
(4)通过加入W，并通过控制W含量，提高合金的高温强度，延长使用寿命。
(5)因为要提高合金在1050℃以上的性能，尤其是接近1200℃时的性能是非常困难的，温度每提高20℃或50℃，这种困难的增加会是指数级别的，绝不是经过有限次的实验，或者根据常规选择就能得到或实现的。实际上，本申请是经过大量实验来调整合金的成分及含量，使得合金可在1100～1200℃的高温环境下形成稳的定Al 2O 3膜，该合金具有优 异的抗氧化性能、良好的高温强度和良好的焊接性能，其综合性能优于现有含铝耐热合金材料。
示例性地，本申请合金的成分及质量百分含量还可以为Al、4.5％-5.5％，Ni、34％-46％、W、3％-6％，Y、0.01％-0.06％。
本申请抗氧化耐热合金的制备方法根据用途的不同而有差异，如果用于航空航天领域用的高温部件，必须采用真空感应熔炼和铸造，包括如下步骤：
1.配料。选用电解镍、金属铝、金属铬(或铬铁)、纯铁、金属钨、石墨、海绵铪、海绵钛、海绵锆、金属钇为原料，按比例称取原料待用。
2.加料。电解镍、金属铬(或铬铁)、纯铁、金属钨放于坩埚中，其它元素从料斗中加入。
3.熔炼，熔炼在中频感应真空熔炼炉中进行。
小功率送电10分钟以去氢，然后大功率送电至全熔，并开始精炼，精炼温度1530～1580℃，精炼时间视钢液的多少而定，控制在10～60分钟，精炼期间真空度应小于5Pa。
4.铸造：熔清后，大功率搅拌1～2分钟，控制钢液温度为1450～1580℃时浇注。
采用上述真空感应熔炼的方法制备本申请的合金，虽然可以精确控制Al、Y等活泼元素，并可以将O、N、S等有害元素降到很低的水平。但该制备方法成本高，制备部件也受制于目前的真空炉装备，因此，真空铸造只适于精密铸造航空航天铸件。
如果用于石化领域的乙烯裂解炉管，由于单支炉管的长度达数米，如果冶炼和离心铸造都在真空环境下进行，在装备条件上难以实现，且成本太高，只能在非真空环境下进行冶炼和离心铸造，但由于本申请合金的制备原料中活泼元素含量较高，所以在非真空条件下制备合格的上述合金非常困难。
本申请还提供了一种在非真空条件下制备抗氧化耐热合金的方法，包括如下步骤：
步骤1：将碳和非活泼元素熔融，完全熔化后得到钢液；
步骤2：钢液升温至1640℃以上进行精炼；
步骤3：加入混合稀土；
步骤4：加入熔渣；
步骤5：铝、铪、钛、锆、钇等活泼元素置于浇流槽中，浇流槽内充惰性气体，温度升至1650-1750℃时，将钢液浇注到浇流槽中，钢液引入中间包进行离心浇铸。
与现有技术相比，本申请提供的抗氧化耐热合金的制备方法的有益效果如下：
(1)通过分批加入碳，实现多次、深度脱氧和脱氮，从而有效降低合金中N和O的含量，进而提高合金性能。
(2)通过多次加入混合稀土而不是一次性加入，来减少稀土的氧化和烧损，保证稀土能够有效加入；通过控制混合稀土的加入量使得既能保证良好的脱硫效果，又不会使残留在钢水中的稀土元素与Ni形成低熔点相，影响合金的高温力学性能。
(3)通过选择覆盖溶渣的种类以及控制覆盖溶渣的加入量来吸附和捕获上浮的氧化物、氮化物、硫化物和夹杂物，从而获得洁净度高的钢液。
(4)通过控制精炼温度在1640℃以上使得碳与钢液中氧化物夹杂置换反应生成CO的化学反应更易进行，净化效果更好。。
(5)本申请通过调整工艺步骤和工艺参数使得使用本申请的制备方法制备的合金中N含量低于0.05％、O含量低于0.003％、S含量低于0.003％、Si含量低于0.5％。
具体来说，利用碳和钢液中的O发生反应生成CO气体，一方面可以脱氧，另一方面，利用形成的CO进行气泡携带脱氮。利用混合稀土与钢液中游离的O和S反应生成氧化物或硫化物，从而脱硫和进一步脱氧。
考虑到铝、铪、钛、锆、钇等元素非常活泼，如果直接熔化会与空气中的氧发生化学反应生成氧化物，从而消耗合金元素。因此，上述制备方法中，活泼元素不是直接熔化，而是将活泼元素放置于有惰性气体保护的浇流槽中，将非活泼元素熔化后的钢液浇注到活泼元素上，利用钢液的过热度熔化活泼元素，利用出钢的动能使活泼元素在浇流槽中均 匀化。上述工艺能够有效降低活泼元素的氧化，从而有效保护合金元素不被消耗。
为了尽可能降低钢液中O和N的含量，本申请的制备方法中，碳采用分步加入的方式，这是因为，冶炼是在空气中进行的，随着冶炼的进行，不断有氧进入钢液，上述制备方法中先加入部分碳初步脱氧、脱氮，待钢液升温至1640℃以上再加入其余碳，利用高温下CO的自由能低于NiO、Fe 2O 3以及Cr 2O 3等氧化物，置换可能存在氧化物中的氧，进行深度脱氧，并可保护合金元素不被损耗。另外，如果一次性加入碳太多，容易着火烧损，使得碳不能有效进入钢液中，从而影响脱氧、脱氮效果。
上述制备方法中，浇注温度根据所浇铸的铸件不同而不同。示例性地，浇铸离心管时，高的浇注温度是为了保证钢水有足够的流动性以利于离心管的成型，离心管越细，浇注温度越高，温度越高，钢水的流动性越好，但钢水中的元素越容易烧损，因此，综合考虑钢水的流动性和元素烧损，浇铸离心管时温度选择为1650～1750℃。
为了防止后续高温熔炼脱氧时钢液(合金熔体)和坩埚发生反应，上述制备方法中坩埚采用高温稳定性好的氧化铝材料制备而成。
值得注意的是，为了吸附和捕获上浮的氧化物、氮化物和硫化物，本申请的制备方法中，在钢液表面加入含有CaO的覆盖熔渣，一方面，利用CaO进一步脱硫，达到进一步脱氧、氮、硫的作用；另一方面，还可以有效去除夹杂物，获得高洁净的钢液。
具体来说，CaO与S发生反应进行前期脱硫，反应方程式为：CaO+[S]＝CaS+[O]，反应过程为：开始表面为脱硫反应，脱硫生成CaS，覆盖于CaO表面，在CaS完全包覆CaO粉末后，进行产物层向内扩散到脱硫反应，并使CaO表面的CaS层逐渐增厚，扩散脱硫反应逐渐减慢，直至停止。
考虑到熔渣的加入量过少，不能完全覆盖钢液表面；加入量过多，会造成浪费，增加成本，因此，本申请的制备方法中控制熔渣的加入量为钢液质量的3％～5％，使得熔渣既能起到很好的进一步脱氧、氮、硫的作用；又可以有效去除夹杂物，获得高洁净的钢液。
本申请的制备方法中所使用的混合稀土是稀土元素La和Ce的混合 物，加入量为钢液质量的0.05％-0.25％。这是因为，混合稀土加入量少，参与脱硫的化学反应数量少，脱硫效果不好，但加入量过多，残留在钢水中的稀土元素易与Ni形成低熔点相，影响合金的高温力学性能。该制备方法中，将混合稀土的加入量选择为钢液质量的0.05％-0.25％，既能保证良好的脱硫效果，又不会使残留在钢液中的稀土元素与Ni形成低熔点相，影响合金的高温力学性能。
上述制备方法中，在浇流槽顶面充流动的氩气，形成一个气幕保护含有易氧化元素的钢液，减缓其氧化。具体来说，氩气的压力选择为0.15-0.3MPa，流量选择为1-5L/min。这是因为，氩气压力过小，不能有效形成氩气幕隔绝空气，避免钢水氧化；氩气压力过大，易形成浪费，增加生产成本，而且对操作工人的安全不利。本申请利用上述方法制备得到成分合格的钢液后，离心浇铸过程如下：将成分合格、过热度合适、重量合适的中间包中的钢液迅速浇铸到高速旋转的金属模桶内，钢液凝固成为离心铸管。
具体来说，使用本申请的制备方法制备得到的合金除了可以用于浇铸离心铸管外，还可以用于浇铸其他需要在高温下服役的铸件，尤其是需要在1100～1200℃的高温、氧化性的恶劣环境下服役的铸件。
考虑到合金成分中含有大量的活泼元素，为了防止活泼元素的氧化烧损，所以整个出钢操作过程要求非常快速。具体来说，从出钢到完成浇铸的速度控制在60～100kg/分钟。
本申请实施例合金的化学成分及含量见表1，制备方法的工艺参数见表2，合金经不同温度100h氧化后的剥落量见表3，合金经不同温度高温循环氧化后形成的氧化膜中氧化铝含量见表4，合金在1100℃/17MPa的持久寿命见表5。
实施例1对应1号合金，实施例2对应2号合金，以此类推，为了便于比较，8号合金和9号合金为现有技术对比材料。其中，8号合金为服役温度最高的可焊高温合金GH3230，广泛用于航空航天发动机燃烧室高温部件，9号合金是目前石化领域乙烯裂解炉管最好的材料HTE合金。
实施例1-7的抗氧化耐热合金按下列方法制备：
步骤1：称取原料待用；
步骤2：将电解镍、纯铁和部分石墨放于有定点浇铸功能的非真空中频熔炼炉的坩埚内，完全熔化后得到钢液；
步骤3：钢液升温至精炼温度加入其余石墨；
步骤4：加入一定量的混合稀土；
步骤5：加入一定量的含有CaO的熔渣；
步骤6：在浇流槽的顶面充流动的氩气，将金属铝、海绵铪、海绵钛、海绵锆、金属钇等活泼元素置于浇流槽中，待步骤2中钢液的化学成分合格，并且钢液温度升至浇注温度时，在浇流槽上面的开口处将钢液浇铸到浇流槽中，在浇流槽下面的开口处将钢液引入中间包等待离心浇铸；
(7)浇铸离心管：将中间包中的钢液迅速浇铸到高速旋转的金属模桶内，制备成实验用离心管。
表1实施例1-7的合金制备原料及含量
Figure PCTCN2019105531-appb-000001
表2本申请实施例的工艺参数
Figure PCTCN2019105531-appb-000002
在相同的实验条件下，分别测试本申请实施例合金和现有技术中的两种合金经不同温度氧化100h后的剥落量，实验结果列于表3，经不同温度氧化100h后的氧化膜完整情况列于表4，高温持久性能列于表5，本申请实施例合金的高温拉伸延伸率列于表6。
表3本申请实施例合金与对比材料经不同温度氧化100h后的剥落量(mg/cm 2)
试验温度/℃ 3号合金 9号合金
1000 0.04 0.07
1050 0.035 0.10
1100 0.024 0.26
1150 0.064 0.35
1200 0.077 2.09
表4经不同温度氧化100h后合金表面氧化铝所占面积比例
试验温度/℃ 1100 1150 1200
1号合金 94％ 91％ 90％
2号合金 95％ 93％ 93％
3号合金 96％ 93％ 92％
4号合金 96％ 93％ 92％
5号合金 94％ 92％ 91％
6号合金 95％ 94％ 92％
7号合金 96％ 94％ 93％
9号合金 80％ 70％ 25％
注：8号合金在1150℃的高温下形不成氧化铝膜，所以，表中没有8号合金的数据。
表5各合金在1100℃/17MPa的持久寿命
合金 1 2 3 4 5 6 7 8 9
持久寿命/h 95 98 111 99 120 97 92 40 11、27、53
表6本申请合金在1000℃时拉伸延伸率
合金 1 2 3 4 5 6 7
拉伸延伸率/％ 41 43 46 46 40 49 45
由图1可知，从氧化增重速率上分析，本申请实施例合金材料的1100℃抗氧化性是现有技术对比材料8号合金的2.5～4倍。大于1100℃，8号合金形不成连续稳定的氧化膜，氧化性急剧下降。
由表3、图2、图3和图4可知，在1000～1200℃的温度范围内，随着氧化温度的升高，本申请合金的剥落量增加幅度非常小，表明本申请合金在1200℃以下均具有优异的抗氧化性能；而对比材料9号合金随着温度升高抗氧化性能急剧降低，尤其在1150℃以上抗氧化性降低幅度尤其显著，在氧化100h的情况下，氧化温度由1150℃增加至1200℃，氧化剥落量增加了5倍。经1100℃/100h循环氧化后，现有技术对比材料9号合金的氧化剥落量是本申请实施例合金材料的5～10倍，经1200℃/100h循环氧化后，现有技术对比材料9号合金的氧化剥落量是本申请实施例合金材料的27倍。说明本申请实施例合金氧化膜与基体的黏结力远远大于9号合金氧化膜与基体的黏结力，而且，温度越高，本申请合金的优势越明显。
进一步分析合金氧化后表面形成的氧化膜情况可知(见表4、图5和图6)，本申请合金在1200℃以下的高温环境下氧化100h后，试样表面形成的氧化膜中氧化铝占90％以上，氧化膜连续、致密，而且随温度的升高，氧化铝膜的数量基本不减少，在1200℃时仍然保持在90％以上。氧化铝在高温下的稳定性非常好，致密的氧化铝膜可保护合金基体不受进一步氧化，如果作为乙烯裂解炉管，氧化铝膜可以起到良好的抗渗碳和结焦等作用。而现有技术对比材料9号合金1100℃/100h氧化后形成的氧化膜中氧化铝占80％，试验温度提高至1150℃后，氧化膜中的氧化铝下降为70％，进一步提高试验温度至1200℃，氧化膜中的氧化铝急剧降低至25％，伴随着大量的氧化膜剥落。表明，在1100℃以上，本申请合金与现有技术材料的抗氧化性优势逐渐拉大，温度越高，优势越大。图5和图6中白色区域为剥落区，黑色区域为氧化铝膜，灰白色区域为复合氧化物膜。
进一步观察1200℃/100h循环氧化后形成的氧化膜剖面(见图7和图8)发现，本申请实施例合金形成的氧化膜连续致密，与基体结合紧密，且结合界面整齐，氧化膜厚度约为6μm；现有技术对比材料9号合金的 氧化膜不连续、结构松散，残存的氧化膜与基体结合不紧密，且结合界面参差不齐，有明显剥落，残存氧化层厚度约为3μm。对比两种氧化膜的情况，本申请材料形成的氧化膜对合金基体的保护作用要明显优于现有技术对比材料9号合金。
按照HB5258-2000(钢及高温合金的抗氧化性测定试验方法)评定，本申请实施例合金完全抗氧化级温度达到1200℃，而现有技术对比材料9号合金的完全抗氧化温度仅为1050℃。本申请的合金完全抗氧化级温度比现有合金提高了150℃，对于合金技术领域来说，温度高于1000℃，尤其在1100℃以上时，由于氧化膜稳定性和与基体的黏结力差等原因，导致合金的抗氧化性急剧降低。如现有技术中抗氧化性非常优异的9号合金，试验温度由1150℃提高至1200℃，氧化膜中氧化铝的比例由70％降低至25％，氧化膜剥落量增加了5倍。1050℃时，9号合金还属于完全抗氧化级别，1100℃时已降为抗氧化级别了，而到1200℃时，已降至次抗氧化级别了。本领域技术人员深知，提高合金在1100℃以上的抗氧化性能是非常困难的，温度每提高20℃或50℃，这种困难的增加会是指数级别的，而本申请的合金完全抗氧化级温度达到了1200℃可以说是抗氧化合金领域的一座里程碑，是经过大量实验，反复调整合金成分及含量，并不断优化工艺步骤和工艺参数才得以实现的。
由表5可知，本申请实施例的合金材料在1100℃/17MPa的持久寿命是现有技术对比材料8号合金2.4～3倍。表5中的11、27、53表示，三根9号合金管的持久寿命各不相同，而且不同合金管的寿命相差较大，说明9号合金的质量稳定性差，不同管的性能差异大，也说明9号合金的总体水平较低。而本申请多根同一实施例合金管的持久寿命差值不超过3h，说明本申请实施例合金的质量稳定性好，本申请实施例合金的总体水平高。由此可见，本申请材料的高温力学性能明显优于8号合金和9号合金，并且本申请实施例合金的质量稳定性好于9号合金。
由表6可知，本申请合金在1000℃时的拉伸延伸率为40％～50％，说明在高铝含量的情况下，本申请合金的韧性仍然良好。
综上所述，本申请的抗氧化耐热合金具有使用温度更高、高温抗氧化性更优异、形成的氧化膜更致密、氧化铝膜面积更大、高温力学性能 更好等优点，本申请抗氧化耐热合金可在1200℃以下长期稳定服役，在1000～1200℃的氧化气氛中可形成90％以上的氧化铝膜，按照HB5258-2000，1200℃以下为完全抗氧化级，优于现有可焊高温材料。
本申请的合金综合性能非常优异，除了可以用于浇铸乙烯裂解炉管外，还可以用于浇铸其他需要在高温下服役的铸件，尤其是需要在1100～1200℃的高温、氧化性的恶劣环境下服役的铸件。
以上所述，仅为本申请较佳的具体实施方式，但本申请的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本申请的保护范围之内。

Claims (10)

  1. 一种抗氧化耐热合金，其特征在于，按质量百分含量计，所述抗氧化耐热合金包含：Al、2.5％-6％，Cr、24％-30％，C、0.3％-0.55％，Ni、30％-50％，W、2％-8％，Ti、0.01％-0.2％，Zr、0.01％-0.2％，Hf、0.01％-0.4％，Y、0.01％-0.2％，V、0.01％-0.2％；其中，Ti和V二者包含其中之一。
  2. 根据权利要求1所述的抗氧化耐热合金，其特征在于，所述合金含有：N<0.05％，O<0.003％，S<0.003％，Si<0.5％，余量为Fe及不可避免的杂质。
  3. 根据权利要求1所述的抗氧化耐热合金，其特征在于，所述合金包含：Al、3.3％-5.5％，Ni、34％-46％。
  4. 根据权利要求1所述的抗氧化耐热合金，其特征在于，所述合金包含：W、3％-6％。
  5. 根据权利要求1所述的抗氧化耐热合金，其特征在于，所述合金包含：Y、0.01％-0.06％。
  6. 根据权利要求1所述的抗氧化耐热合金，其特征在于，在1000～1200℃的氧化气氛中，合金表面形成的氧化膜中90％以上的面积是Al 2O 3膜。
  7. 一种抗氧化耐热合金的制备方法，其特征在于，用于制备权利要求1-6任一项所述的合金，包括如下步骤：
    步骤1：将碳和非活泼元素熔融，完全熔化后得到钢液；
    步骤2：钢液升温，精炼；
    步骤3：加入混合稀土；
    步骤4：加入熔渣；
    步骤5：浇流槽内充惰性气体，铝、铪、钛、锆、钇等活泼元素置于浇流槽中，升温，将钢液浇注到浇流槽中，钢液引入中间包待浇铸。
  8. 根据权利要求7所述的抗氧化耐热合金的制备方法，其特征在于，混合稀土的加入量为钢液质量的0.05％-0.25％。
  9. 根据权利要求7所述的抗氧化耐热合金的制备方法，其特征在于，所述熔渣含有CaO。
  10. 根据权利要求7所述的抗氧化耐热合金的制备方法，其特征在 于，所述步骤5之后还包括浇铸，从出钢到完成浇铸的速度为60～100kg/分钟。
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