WO2021179844A1 - 一种钛铝合金熔炼用耐火材料及其制备方法 - Google Patents

一种钛铝合金熔炼用耐火材料及其制备方法 Download PDF

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WO2021179844A1
WO2021179844A1 PCT/CN2021/074587 CN2021074587W WO2021179844A1 WO 2021179844 A1 WO2021179844 A1 WO 2021179844A1 CN 2021074587 W CN2021074587 W CN 2021074587W WO 2021179844 A1 WO2021179844 A1 WO 2021179844A1
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titanium
aluminum alloy
smelting
containing calcium
fine powder
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French (fr)
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付绿平
顾华志
黄奥
张美杰
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武汉科技大学
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Publication of WO2021179844A1 publication Critical patent/WO2021179844A1/zh

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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/3218—Aluminium (oxy)hydroxides, e.g. boehmite, gibbsite, alumina sol
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/442—Carbonates
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
    • C04B2235/9676—Resistance against chemicals, e.g. against molten glass or molten salts against molten metals such as steel or aluminium

Definitions

  • the invention belongs to the technical field of titanium aluminum alloy smelting. Specifically, it relates to a refractory material for smelting titanium aluminum alloy and a preparation method thereof.
  • Titanium aluminum alloy has low density, high specific strength, high specific rigidity, good heat resistance, excellent high temperature creep resistance and good oxidation resistance. It is the material of choice for supersonic aircraft and next-generation advanced aero-engines. Titanium-aluminum alloy melts have high chemical activity at high temperatures and easily react with refractory materials to contaminate alloy melts. Therefore, the development of refractory materials for smelting titanium-aluminum alloys with excellent performance has become one of the important topics of concern in this field.
  • refractory materials for smelting titanium alloys are alumina, calcium oxide, zirconium oxide, yttrium oxide and perovskite materials.
  • CaO refractory materials and crucible preparation methods for titanium alloy smelting (CN 101830715A) patented technology, using 82 to 92% calcium oxide powder, 5 to 15% zirconia powder and 1 ⁇ 5% titanium oxide micropowder is used as raw material to prepare CaO refractories and crucibles for titanium alloy smelting; Li et al. (Li C H, HeJ, ZhangZ, et al.
  • zirconia crucibles are prepared using zirconium powder of different particle sizes as raw materials; Chang et al.
  • yttrium oxide materials such as "a method for preparing a crucible for smelting titanium and titanium alloys" (CN 101381242A)
  • the patented technology uses yttrium oxide and an appropriate amount of additives as the main raw materials to prepare titanium by isostatic pressing or casting.
  • titanium alloy smelting yttrium oxide crucible such as "Electro-fusion yttrium trioxide ceramic crucible for titanium alloy fusion casting and its preparation method" (CN106116578B) patented technology, using yttrium oxide and zirconium slices as the main raw materials, using electric fusion method
  • perovskite materials such as "BaZrO3 refractory material for titanium alloy smelting and preparation method of its crucible” (CN102503489A) and "A BaZrO3 refractory material doped with Y2O3" (CN 105777162A) patented technology
  • using barium carbonate and Zirconia was used as a raw material to prepare BaZrO3 refractories for titanium alloy smelting.
  • the chemical stability of perovskite materials still has defects, which will pollute the titanium aluminum alloy after smelting, resulting in high oxygen content.
  • the present invention aims to overcome the defects of the prior art, and aims to provide a method for preparing refractory materials for smelting titanium aluminum alloy with low cost and simple process; the refractory materials for smelting titanium aluminum alloy prepared by the method have good high-temperature chemical stability , Good thermal shock resistance, strong resistance to titanium aluminum alloy melt, and low pollution to titanium aluminum alloy.
  • the technical solution adopted by the present invention is: 60-75wt% of titanium-containing calcium hexaaluminate particles are used as aggregates, and 25-40wt% of titanium-containing calcium hexaaluminate fine powders are used as matrix materials; Mix the matrix material uniformly, then add the mixed matrix material to the aggregate, mix evenly, and then add a binding agent that accounts for 0.5-2wt% of the total of the aggregate and the matrix material, and mix and crush , Press molding under the condition of 100-200MPa, and keep the temperature at 110-200°C for 20-36 hours to obtain the refractory material for smelting titanium aluminum alloy.
  • the preparation method of the titanium-containing calcium hexaaluminate particles and the titanium-containing calcium hexaaluminate fine powder is as follows: 60 to 80 wt% of alumina powder, 5 to 20 wt% of calcium carbonate powder, and 10 to 20 wt% of oxidation Titanium micropowder and 1-10wt% manganous oxide micropowder are used as raw materials, and the raw materials are uniformly mixed in a planetary ball mill to obtain a mixture; then the mixture is press-formed under a condition of 100 to 200 MPa to obtain a green body; Finally, the green body is dried at 110-200°C for 12-36 hours, and kept at 1500-1800°C for 1-8 hours to prepare titanium-containing calcium hexaaluminate material.
  • the titanium-containing calcium hexaaluminate material is crushed to a particle size of 0.088-10mm to obtain titanium-containing calcium hexaaluminate particles; the titanium-containing calcium hexaaluminate material is crushed to a particle size of less than 0.088mm to obtain Calcium titanium hexaaluminate fine powder.
  • the Ca((Al0.84Ti0.16)2)6O19 phase content of the titanium-containing calcium hexaaluminate particles and the titanium-containing calcium hexaaluminate fine powder is greater than 90 wt%.
  • the binding agent is one of polyvinyl alcohol, phenolic resin and aluminum sol.
  • the Al2O3 content of the alumina micropowder is ⁇ 98wt%, and the particle size D50 of the alumina micropowder is 1-8 ⁇ m.
  • the particle size D50 of the calcium carbonate powder is 1-10 ⁇ m.
  • the TiO2 content of the titanium oxide fine powder is ⁇ 90wt%, and the particle size D50 of the titanium oxide fine powder is 1-10 ⁇ m.
  • the MnO content of the manganous oxide fine powder is ⁇ 90wt%, and the particle size D50 of the manganous oxide fine powder is 1-8 ⁇ m.
  • the present invention has the following positive effects compared with the prior art:
  • titanium-containing calcium hexaaluminate particles are used as aggregate and titanium-containing calcium hexaaluminate fine powder is used as the matrix material.
  • the binder is added, mixed and crushed, machine-pressed and formed by heat treatment at 110-200°C for 20- In 36 hours, a refractory material for smelting of titanium and aluminum alloy was prepared, so the preparation process was simple.
  • the titanium-containing calcium hexaaluminate material used in the invention uses alumina micropowder, calcium carbonate micropowder and titanium oxide micropowder as main raw materials, and has a wide range of raw material sources and low production cost.
  • the titanium-aluminum alloy smelting refractories prepared by the present invention use titanium-containing calcium hexaaluminate particles as aggregates and titanium-containing calcium hexaaluminate fine powder as matrix materials.
  • the phase composition of the aggregate and the matrix material is, The chemical properties and physical properties are the same, the composition is uniform, and the stability is good under high temperature conditions.
  • the Ca((Al0.84 Ti0.16)2)6O19 phase content of the titanium-containing calcium hexaaluminate particles used in the present invention and the titanium-containing calcium hexaaluminate fine powder is greater than 90wt%, and both have calcium hexaaluminate and Calcium titanate has excellent characteristics, high refractoriness, high temperature thermodynamics and good volume stability. Therefore, the prepared refractory material for titanium aluminum alloy smelting has good high temperature chemical stability.
  • the titanium-containing calcium hexaaluminate material used in the present invention has a lower coefficient of thermal expansion and thermal conductivity.
  • the prepared refractory material for smelting of titanium and aluminum alloy can effectively buffer thermal stress and reduce stress concentration when it withstands sudden changes in temperature.
  • the prepared refractories for smelting titanium and aluminum alloys have excellent thermal shock stability.
  • the aggregate and matrix materials used in the present invention have both TiO2 and Al2O3 components. When in contact with the titanium-aluminum alloy melt, it can simultaneously inhibit the interaction of the Ti and Al components in the alloy melt with the refractory material. Therefore, the prepared refractory material for smelting titanium aluminum alloy can better resist the corrosion of titanium aluminum alloy melt.
  • the prepared refractory material for smelting titanium aluminum alloy has excellent high temperature chemical stability and strong resistance to titanium aluminum alloy melt, it is not easy to react with the alloy melt when it comes into contact with the titanium aluminum alloy melt. Alloy pollution is small.
  • the titanium-aluminum alloy smelting refractory prepared by the invention has been tested: the service life is greater than 18 times; the thickness of the reaction interface with the titanium-aluminum alloy is about 10-50 ⁇ m; the oxygen content of the titanium-aluminum alloy after smelting is less than 0.1wt%.
  • the present invention has low cost and simple process, and the prepared refractory material for smelting titanium aluminum alloy has the characteristics of good high-temperature chemical stability, good thermal shock resistance, strong resistance to titanium aluminum alloy melt, and low pollution to titanium aluminum alloy .
  • the preparation method of the titanium-containing calcium hexaaluminate particles and the titanium-containing calcium hexaaluminate fine powder is as follows: 60 to 80 wt% of alumina powder, 5 to 20 wt% of calcium carbonate powder, and 10 to 20 wt% of oxidation Titanium micropowder and 1-10wt% manganous oxide micropowder are used as raw materials, and the raw materials are uniformly mixed in a planetary ball mill to obtain a mixture; then the mixture is press-formed under a condition of 100 to 200 MPa to obtain a green body; Finally, the green body is dried at 110-200°C for 12-36 hours, and kept at 1500-1800°C for 1-8 hours to prepare titanium-containing calcium hexaaluminate material.
  • the titanium-containing calcium hexaaluminate material is crushed to a particle size of 0.088-10mm to obtain titanium-containing calcium hexaaluminate particles; the titanium-containing calcium hexaaluminate material is crushed to a particle size of less than 0.088mm to obtain Calcium titanium hexaaluminate fine powder.
  • the Ca((Al0.84 Ti0.16)2)6O19 phase content of the titanium-containing calcium hexaaluminate particles and the titanium-containing calcium hexaaluminate fine powder is greater than 90wt%.
  • the Al2O3 content of the alumina micropowder is ⁇ 98wt%, and the particle size D50 of the alumina micropowder is 1-8 ⁇ m.
  • the particle size D50 of the calcium carbonate powder is 1-10 ⁇ m.
  • the TiO2 content of the titanium oxide fine powder is ⁇ 90wt%, and the particle size D50 of the titanium oxide fine powder is 1-10 ⁇ m.
  • the MnO content of the manganous oxide fine powder is ⁇ 90wt%, and the particle size D50 of the manganous oxide fine powder is 1-8 ⁇ m.
  • a refractory material for smelting titanium aluminum alloy and a preparation method thereof Take 60-64wt% of titanium-containing calcium hexaaluminate particles as aggregate, and 36-40wt% of titanium-containing calcium hexaaluminate fine powder as matrix material; The matrix material is added to the aggregate, mixed uniformly, and then 0.5 to 1.5 wt% of the binder is added, which accounts for the sum of the aggregate and the matrix material, mixed and crushed, and molded under the conditions of 150 to 200 MPa.
  • the refractory material for smelting titanium aluminum alloy is prepared by keeping the temperature at 160°C for 20-28 hours.
  • the binding agent is polyvinyl alcohol.
  • the titanium-aluminum alloy smelting refractory material prepared in this embodiment has been tested: the service life is greater than 18 times; the thickness of the reaction interface with the titanium-aluminum alloy is about 29-48 ⁇ m; the oxygen content of the titanium-aluminum alloy after smelting is less than 0.1wt%.
  • a refractory material for smelting titanium aluminum alloy and a preparation method thereof Take 60-64wt% of titanium-containing calcium hexaaluminate particles as aggregate, and 36-40wt% of titanium-containing calcium hexaaluminate fine powder as matrix material; The matrix material is added to the aggregate and mixed uniformly, and then 1 to 2 wt% of the binder accounting for the sum of the aggregate and the matrix material is added.
  • the refractory material for smelting titanium aluminum alloy is prepared by keeping the temperature for 28-36 hours under the condition of °C.
  • the binding agent is a phenolic resin.
  • the titanium-aluminum alloy smelting refractory prepared in this embodiment has been tested: the service life is greater than 18 times; the thickness of the reaction interface with the titanium-aluminum alloy is about 28-50 ⁇ m; the oxygen content of the titanium-aluminum alloy after smelting is less than 0.1wt%.
  • a refractory material for smelting titanium aluminum alloy and a preparation method thereof Use 63-67wt% of titanium-containing calcium hexaaluminate particles as aggregate, and 33-37wt% of titanium-containing calcium hexaaluminate fine powder as matrix material; The matrix material is added to the aggregate, mixed uniformly, and then 0.5 to 1.5 wt% of the binder is added, which accounts for the sum of the aggregate and the matrix material, mixed and crushed, and molded under the conditions of 150 to 200 MPa.
  • the refractory material for smelting titanium aluminum alloy is prepared by keeping the temperature at 160°C for 20-28 hours.
  • the binding agent is aluminum sol.
  • the titanium-aluminum alloy smelting refractory prepared in this embodiment has been tested: the service life is greater than 19 times; the thickness of the reaction interface with the titanium-aluminum alloy is about 21-41 ⁇ m; the oxygen content of the titanium-aluminum alloy after smelting is less than 0.1wt%.
  • a refractory material for smelting titanium aluminum alloy and a preparation method thereof Use 63-67wt% of titanium-containing calcium hexaaluminate particles as aggregate, and 33-37wt% of titanium-containing calcium hexaaluminate fine powder as matrix material; The matrix material is added to the aggregate and mixed uniformly, and then 1 to 2 wt% of the binder accounting for the sum of the aggregate and the matrix material is added.
  • the refractory material for smelting titanium aluminum alloy is prepared by keeping the temperature for 28-36 hours under the condition of °C.
  • the binding agent is polyvinyl alcohol.
  • the titanium-aluminum alloy smelting refractory prepared in this embodiment has been tested: the service life is greater than 18 times; the thickness of the reaction interface with the titanium-aluminum alloy is about 19-40 ⁇ m; the oxygen content of the titanium-aluminum alloy after smelting is less than 0.1wt%.
  • a refractory material for smelting titanium aluminum alloy and a preparation method thereof Use 67-71wt% of titanium-containing calcium hexaaluminate particles as aggregate, and 29-33wt% of titanium-containing calcium hexaaluminate fine powder as matrix material; The matrix material is added to the aggregate, mixed uniformly, and then 0.5 to 1.5 wt% of the binder is added, which accounts for the sum of the aggregate and the matrix material, mixed and crushed, and molded under the conditions of 150 to 200 MPa.
  • the refractory material for smelting titanium aluminum alloy is prepared by keeping the temperature at 160°C for 20-28 hours.
  • the binding agent is a phenolic resin.
  • the titanium-aluminum alloy smelting refractory prepared in this embodiment has been tested: the service life is greater than 19 times; the thickness of the reaction interface with the titanium-aluminum alloy is about 15-36 ⁇ m; the oxygen content of the titanium-aluminum alloy after smelting is less than 0.1wt%.
  • a refractory material for smelting titanium aluminum alloy and a preparation method thereof Use 67-71wt% of titanium-containing calcium hexaaluminate particles as aggregate, and 29-33wt% of titanium-containing calcium hexaaluminate fine powder as matrix material; The matrix material is added to the aggregate and mixed uniformly, and then 1 to 2 wt% of the binder accounting for the sum of the aggregate and the matrix material is added.
  • the refractory material for smelting titanium aluminum alloy is prepared by keeping the temperature for 28-36 hours under the condition of °C.
  • the binding agent is aluminum sol.
  • the titanium-aluminum alloy smelting refractory prepared in this embodiment has been tested: the service life is greater than 19 times; the thickness of the reaction interface with the titanium-aluminum alloy is about 16-35 ⁇ m; the oxygen content of the titanium-aluminum alloy after smelting is less than 0.1wt%.
  • a refractory material for smelting titanium aluminum alloy and a preparation method thereof Use 71 ⁇ 75wt% of titanium-containing calcium hexaaluminate particles as aggregate, and 25-29wt% of titanium-containing calcium hexaaluminate fine powder as matrix material; The matrix material is added to the aggregate, mixed uniformly, and then 0.5 to 1.5 wt% of the binder is added, which accounts for the sum of the aggregate and the matrix material, mixed and crushed, and molded under the conditions of 150 to 200 MPa.
  • the refractory material for smelting titanium aluminum alloy is prepared by keeping the temperature at 160°C for 20-28 hours.
  • the binding agent is polyvinyl alcohol.
  • the titanium aluminum alloy smelting refractory material prepared in this embodiment has been tested: the service life is greater than 20 times; the thickness of the reaction interface with the titanium aluminum alloy is about 10 to 32 ⁇ m; the oxygen content of the titanium aluminum alloy after smelting is less than 0.1 wt%.
  • a refractory material for smelting titanium aluminum alloy and a preparation method thereof Use 71 ⁇ 75wt% of titanium-containing calcium hexaaluminate particles as aggregate, and 25-29wt% of titanium-containing calcium hexaaluminate fine powder as matrix material; The matrix material is added to the aggregate and mixed uniformly, and then 1 to 2 wt% of the binder accounting for the sum of the aggregate and the matrix material is added.
  • the refractory material for smelting titanium aluminum alloy is prepared by keeping the temperature for 28-36 hours under the condition of °C.
  • the binding agent is a phenolic resin.
  • the titanium-aluminum alloy smelting refractory prepared in this embodiment has been tested: the service life is greater than 20 times; the thickness of the reaction interface with the titanium-aluminum alloy is about 10 to 31 ⁇ m; the oxygen content of the titanium-aluminum alloy after smelting is less than 0.1 wt%.
  • titanium-containing calcium hexaaluminate particles are used as aggregate and titanium-containing calcium hexaaluminate fine powder is used as matrix material.
  • the binder is added, mixed and crushed, machine-compressed, and heat-treated at 110-200°C. In 20-36 hours, a refractory material for smelting titanium aluminum alloy is prepared, so the process is simple.
  • the titanium-containing calcium hexaaluminate material used in this embodiment uses alumina micropowder, calcium carbonate micropowder and titanium oxide micropowder as main raw materials, and has a wide range of raw materials and low production costs.
  • the titanium-aluminum alloy smelting refractories prepared in this embodiment use titanium-containing calcium hexaaluminate particles as aggregates and titanium-containing calcium hexaaluminate fine powders as matrix materials.
  • the phases of the aggregate and the matrix material are The composition, chemical properties and physical properties are the same, the composition is uniform, and the stability is good under high temperature conditions.
  • the titanium-containing calcium hexaaluminate particles and the Ca((Al0.84 Ti0.16)2)6O19 phase content of the titanium-containing calcium hexaaluminate fine powder used in this embodiment are greater than 90wt%, and both have hexaaluminate Calcium and calcium titanate have excellent characteristics, high refractoriness, high temperature thermodynamics and good volume stability. Therefore, the prepared refractory material for smelting titanium aluminum alloy has good high temperature chemical stability.
  • the titanium-containing calcium hexaaluminate material used in this embodiment has a low coefficient of thermal expansion and thermal conductivity.
  • the prepared refractory material for smelting titanium and aluminum alloy can effectively buffer thermal stress and reduce stress concentration when subjected to sudden temperature changes. Therefore, the prepared refractories for smelting titanium and aluminum alloys have excellent thermal shock stability.
  • the aggregate and matrix materials used in this embodiment have both TiO2 and Al2O3 components. When in contact with the titanium-aluminum alloy melt, it can simultaneously suppress the Ti component and Al component in the alloy melt from the refractory material. Interaction, therefore, the prepared refractory material for smelting titanium aluminum alloy can better resist the corrosion of titanium aluminum alloy melt.
  • the prepared refractory material for smelting titanium aluminum alloy has excellent high temperature chemical stability and strong resistance to titanium aluminum alloy melt, it is not easy to react with the alloy melt when it comes into contact with the titanium aluminum alloy melt. Alloy pollution is small.
  • the titanium-aluminum alloy smelting refractory prepared in this embodiment has been tested: the service life is greater than 18 times; the thickness of the reaction interface with the titanium-aluminum alloy is about 10-50 ⁇ m; the oxygen content of the titanium-aluminum alloy after smelting is less than 0.1wt%.
  • this embodiment has low cost and simple process, and the prepared refractory material for smelting titanium aluminum alloy has good high temperature chemical stability, good thermal shock resistance, strong resistance to titanium aluminum alloy melt, and low pollution to titanium aluminum alloy specialty.

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Abstract

一种钛铝合金熔炼用耐火材料及其制备方法。以60～75wt％的含钛六铝酸钙颗粒为骨料，以25～40wt％的含钛六铝酸钙细粉为基质料；先将混匀后的基质料加入骨料中，混匀，外加占骨料与基质料之和0.5～2wt％的结合剂，混碾，在100～200MPa条件下压制成型，然后在110～200℃条件下干燥，制得钛铝合金熔炼用耐火材料。所述含钛六铝酸钙颗粒粒径为0.088～10mm，所述含钛六铝酸钙细粉粒径小于0.088mm；所述含钛六铝酸钙颗粒和所述含钛六铝酸钙细粉的Ca((Al 0.84Ti 0.16) 2) 6O 19物相含量大于90wt％。制备方法成本低和工艺简单，制品具有高温化学稳定性好、抗热震性能好、抗钛铝合金熔体能力强和对钛铝合金污染小的特点。

Description

一种钛铝合金熔炼用耐火材料及其制备方法 技术领域
本发明属于钛铝合金熔炼技术领域。具体涉及一种钛铝合金熔炼用耐火材料及其制备方法。
背景技术
钛铝合金密度低、比强度高、比刚度高、耐热性好、抗高温蠕变性能优异和抗氧化能力良好，是超高音速飞行器和下一代先进航空发动机的首选材料。钛铝合金熔体高温下化学活性高，易与耐火材料发生反应而污染合金熔体，因此，开发性能优异的钛铝合金熔炼用耐火材料已成为目前本领域所关注的重要课题之一。
目前常用的钛合金熔炼用耐火材料有氧化铝、氧化钙、氧化锆、氧化钇和钙钛矿材料。
关于氧化铝材料，Fan等(Fan J,Guo J,Wang S,et al.Microstructureevolution and interfacial reaction of TiAl–Si alloy solidified in aluminacrucible[J].Materials Science and Technology,2015,31(14):1727-1734.)和Liu等(LiuD,Li X,SuY,et al.Microstructure evolution in directionally solidified Ti–(50,52)at％Al alloys[J].Intermetallics,2011,19(2):175-181.)采用氧化铝材料对钛合金进行了熔炼，然而，氧化铝材料的化学稳定性不佳，与钛铝合金的反应行为与合金的成分密切相关，适用的合金种类有一定限制。
关于氧化钙材料，如“用于钛合金熔炼的CaO耐火材料及坩埚的制备方法”(CN 101830715A)专利技术，以82～92％的氧化钙微粉、5～15％的氧化锆微粉和1～5％的氧化钛微粉为原料，制备了用于钛合金熔炼的CaO耐火材料及坩埚；Li等(Li C H,HeJ,ZhangZ,et al.Preparation of TiFe based alloys melted by CaO crucible andits hydrogen storage properties[J].Journal of Alloys and Compounds,2015,618:679-684.)采用冷等静压成型制备了CaO含量为97wt％的氧化钙材料；然而，氧化钙材料抗水化性较差，容易导致合金中增氧，对钛合金产生污染。
关于氧化锆材料，如“一种精密铸造用氧化锆坩埚及其热处理方法”(CN109516802A)专利技术，以不同粒径的锆粉为原料，制备了氧化锆坩埚；Chang等(ChangYW,Lin C C.Compositional dependence of phase formation mechanisms at theinterface between titanium and calcia-stabilized zirconiaat 1550℃[J].Journalof the American Ceramic Society,2010,93(11):3893-3901.)以95mol％氧化锆和5mol％氧化钙为原料，制备了 钛铝合金熔炼用氧化钙材料；然而，氧化锆材料化学稳定性不佳，会与钛反应产生固溶体，从而对合金造成污染。
关于氧化钇材料，如“一种钛和钛合金熔炼用坩埚的制备方法”(CN 101381242A)专利技术，以氧化钇和适量的添加剂为主要原料，采用等静压法或浇注法成型制备了钛和钛合金熔炼用氧化钇坩埚；如“钛合金熔融铸造用电熔三氧化二钇陶瓷坩埚及其制备方法”(CN106116578B)专利技术，以氧化钇和锆片为主要原料，采用电熔法制备了钛合金熔融铸造用电熔三氧化二钇陶瓷坩埚；然而，氧化钇材料抗热震性能差，使用寿命短。
关于钙钛矿材料，如“用于钛合金熔炼的BaZrO3耐火材料及其坩埚的制备方法”(CN102503489A)和“一种掺杂Y2O3的BaZrO3耐火材料”(CN 105777162A)专利技术，以碳酸钡和氧化锆为原料，制备了钛合金熔炼用BaZrO3耐火材料，然而，钙钛矿材料化学稳定性仍存在缺陷，熔炼后对钛铝合金产生污染，导致氧含量偏高。
发明内容
本发明旨在克服现有技术缺陷，目的在于提供一种成本低和工艺简单的钛铝合金熔炼用耐火材料的制备方法；用该方法制备的钛铝合金熔炼用耐火材料的高温化学稳定性好、抗热震性能好、抗钛铝合金熔体能力强和对钛铝合金污染小。
为实现上述任务，本发明所采用的技术方案是：以60～75wt％的含钛六铝酸钙颗粒为骨料，以25～40wt％的含钛六铝酸钙细粉为基质料；先将所述基质料混匀，再将混匀后的基质料加入所述骨料中，混合均匀，然后外加占所述骨料与所述基质料之和0.5～2wt％的结合剂，混碾，在100～200MPa条件下压制成型，在110～200℃条件下保温20～36小时，制得钛铝合金熔炼用耐火材料。
所述含钛六铝酸钙颗粒和所述含钛六铝酸钙细粉的制备方法是：以60～80wt％的氧化铝微粉、5～20wt％的碳酸钙微粉、10～20wt％的氧化钛微粉和1～10wt％的氧化亚锰微粉为原料，将所述原料在行星球磨机中混合均匀，得到混合料；然后将所述混合料在100～200MPa条件下机压成型，得到生坯；最后将所述生坯在110～200℃条件下干燥12～36小时，在1500～1800℃条件下保温1～8小时，制得含钛六铝酸钙材料。
将所述含钛六铝酸钙材料破碎至粒径为0.088～10mm，即得含钛六铝酸钙颗粒；将所述含钛六铝酸钙材料破碎至粒径小于0.088mm，即得含钛六铝酸钙细粉。所述含钛六铝酸钙颗粒和所述含钛六铝酸钙细粉的Ca((Al0.84Ti0.16)2)6O19物相含量大于90wt％。
所述结合剂为聚乙烯醇、酚醛树脂和铝溶胶中的一种。
所述氧化铝微粉的Al2O3含量≥98wt％，氧化铝微粉的粒径D50为1～8μm。
所述碳酸钙微粉的粒径D50为1～10μm。
所述氧化钛微粉的TiO2含量≥90wt％，氧化钛微粉的粒径D50为1～10μm。
所述氧化亚锰微粉的MnO含量≥90wt％，氧化亚锰微粉的粒径D50为1～8μm。
由于采用上述技术方案，本发明与现有技术相比具有如下积极效果：
1、本发明以含钛六铝酸钙颗粒为骨料和以含钛六铝酸钙细粉为基质料，混合后加入结合剂，混碾，机压成型，经110～200℃热处理20～36小时，制得钛铝合金熔炼用耐火材料，故制备工艺简单。本发明采用的含钛六铝酸钙材料是以氧化铝微粉、碳酸钙微粉和氧化钛微粉为主要原料，原料来源广泛，生产成本低。
2、本发明所制备的钛铝合金熔炼用耐火材料分别以含钛六铝酸钙颗粒为骨料和以含钛六铝酸钙细粉为基质料，骨料和基质料的物相组成、化学性质及物理性能均相同，组成均匀，高温条件下稳定性好。本发明采用的含钛六铝酸钙颗粒和所述含钛六铝酸钙细粉的Ca((Al0.84 Ti0.16)2)6O19物相含量大于90wt％，兼具六铝酸钙和钛酸钙的优良特性，耐火度高、高温热力学和体积稳定性好，因此，所制备的钛铝合金熔炼用耐火材料具有良好的高温化学稳定性。
3、本发明采用的含钛六铝酸钙材料具有较低的热膨胀系数与导热系数，所制备的钛铝合金熔炼用耐火材料在承受温度剧变时，能有效缓冲热应力，减少应力集中，因此，所制备的钛铝合金熔炼用耐火材料热震稳定性能优异。
4、本发明采用的骨料和基质料中兼具TiO2和Al2O3组分，在与钛铝合金熔体接触时，可以同时抑制合金熔体中Ti组分和Al组分与耐火材料的相互作用，因此，所制备的钛铝合金熔炼用耐火材料能够较好地抵御钛铝合金熔体的侵蚀。
5、由于所制备的钛铝合金熔炼用耐火材料高温化学稳定性优异和抗钛铝合金熔体能力强，在与钛铝合金熔体接触时，不易与合金熔体反应，因此，对钛铝合金污染小。
本发明制备的钛铝合金熔炼用耐火材料经检测：使用寿命大于18次；与钛铝合金反应界面厚度约为10～50μm；熔炼后钛铝合金的氧含量小于0.1wt％。
因此，本发明成本低和工艺简单，所制备的钛铝合金熔炼用耐火材料具有高温化学稳定性好、抗热震性能好、抗钛铝合金熔体能力强和对钛铝合金污染小的特点。
具体实施方式
下面结合具体实施方式对本发明作进一步的描述，并非对保护范围的限制。
为避免重复，先将本具体实施方式所涉及的原料统一描述如下，实施例中不再赘述：
所述含钛六铝酸钙颗粒和所述含钛六铝酸钙细粉的制备方法是：以60～80wt％的氧化铝微粉、5～20wt％的碳酸钙微粉、10～20wt％的氧化钛微粉和1～10wt％的氧化 亚锰微粉为原料，将所述原料在行星球磨机中混合均匀，得到混合料；然后将所述混合料在100～200MPa条件下机压成型，得到生坯；最后将所述生坯在110～200℃条件下干燥12～36小时，在1500～1800℃条件下保温1～8小时，制得含钛六铝酸钙材料。
将所述含钛六铝酸钙材料破碎至粒径为0.088～10mm，即得含钛六铝酸钙颗粒；将所述含钛六铝酸钙材料破碎至粒径小于0.088mm，即得含钛六铝酸钙细粉。所述含钛六铝酸钙颗粒和所述含钛六铝酸钙细粉的Ca((Al0.84 Ti0.16)2)6O19物相含量大于90wt％。
所述氧化铝微粉的Al2O3含量≥98wt％，氧化铝微粉的粒径D50为1～8μm。
所述碳酸钙微粉的粒径D50为1～10μm。
所述氧化钛微粉的TiO2含量≥90wt％，氧化钛微粉的粒径D50为1～10μm。
所述氧化亚锰微粉的MnO含量≥90wt％，氧化亚锰微粉的粒径D50为1～8μm。
实施例1
一种钛铝合金熔炼用耐火材料及其制备方法。以60～64wt％的含钛六铝酸钙颗粒为骨料，以36～40wt％的含钛六铝酸钙细粉为基质料；先将所述基质料混匀，再将混匀后的基质料加入所述骨料中，混合均匀，然后外加占所述骨料与所述基质料之和0.5～1.5wt％的结合剂，混碾，在150～200MPa条件下压制成型，在110～160℃条件下保温20～28小时，制得钛铝合金熔炼用耐火材料。
所述结合剂为聚乙烯醇。
本实施例制备的钛铝合金熔炼用耐火材料经检测：使用寿命大于18次；与钛铝合金反应界面厚度约为29～48μm；熔炼后钛铝合金的氧含量小于0.1wt％。
实施例2
一种钛铝合金熔炼用耐火材料及其制备方法。以60～64wt％的含钛六铝酸钙颗粒为骨料，以36～40wt％的含钛六铝酸钙细粉为基质料；先将所述基质料混匀，再将混匀后的基质料加入所述骨料中，混合均匀，然后外加占所述骨料与所述基质料之和1～2wt％的结合剂，混碾，在100～150MPa条件下压制成型，在150～200℃条件下保温28～36小时，制得钛铝合金熔炼用耐火材料。
所述结合剂为酚醛树脂。
本实施例制备的钛铝合金熔炼用耐火材料经检测：使用寿命大于18次；与钛铝合金反应界面厚度约为28～50μm；熔炼后钛铝合金的氧含量小于0.1wt％。
实施例3
一种钛铝合金熔炼用耐火材料及其制备方法。以63～67wt％的含钛六铝酸钙颗粒为骨料，以33～37wt％的含钛六铝酸钙细粉为基质料；先将所述基质料混匀，再将混 匀后的基质料加入所述骨料中，混合均匀，然后外加占所述骨料与所述基质料之和0.5～1.5wt％的结合剂，混碾，在150～200MPa条件下压制成型，在110～160℃条件下保温20～28小时，制得钛铝合金熔炼用耐火材料。
所述结合剂为铝溶胶。
本实施例制备的钛铝合金熔炼用耐火材料经检测：使用寿命大于19次；与钛铝合金反应界面厚度约为21～41μm；熔炼后钛铝合金的氧含量小于0.1wt％。
实施例4
一种钛铝合金熔炼用耐火材料及其制备方法。以63～67wt％的含钛六铝酸钙颗粒为骨料，以33～37wt％的含钛六铝酸钙细粉为基质料；先将所述基质料混匀，再将混匀后的基质料加入所述骨料中，混合均匀，然后外加占所述骨料与所述基质料之和1～2wt％的结合剂，混碾，在100～150MPa条件下压制成型，在150～200℃条件下保温28～36小时，制得钛铝合金熔炼用耐火材料。
所述结合剂为聚乙烯醇。
本实施例制备的钛铝合金熔炼用耐火材料经检测：使用寿命大于18次；与钛铝合金反应界面厚度约为19～40μm；熔炼后钛铝合金的氧含量小于0.1wt％。
实施例5
一种钛铝合金熔炼用耐火材料及其制备方法。以67～71wt％的含钛六铝酸钙颗粒为骨料，以29～33wt％的含钛六铝酸钙细粉为基质料；先将所述基质料混匀，再将混匀后的基质料加入所述骨料中，混合均匀，然后外加占所述骨料与所述基质料之和0.5～1.5wt％的结合剂，混碾，在150～200MPa条件下压制成型，在110～160℃条件下保温20～28小时，制得钛铝合金熔炼用耐火材料。
所述结合剂为酚醛树脂。
本实施例制备的钛铝合金熔炼用耐火材料经检测：使用寿命大于19次；与钛铝合金反应界面厚度约为15～36μm；熔炼后钛铝合金的氧含量小于0.1wt％。
实施例6
一种钛铝合金熔炼用耐火材料及其制备方法。以67～71wt％的含钛六铝酸钙颗粒为骨料，以29～33wt％的含钛六铝酸钙细粉为基质料；先将所述基质料混匀，再将混匀后的基质料加入所述骨料中，混合均匀，然后外加占所述骨料与所述基质料之和1～2wt％的结合剂，混碾，在100～150MPa条件下压制成型，在150～200℃条件下保温28～36小时，制得钛铝合金熔炼用耐火材料。
所述结合剂为铝溶胶。
本实施例制备的钛铝合金熔炼用耐火材料经检测：使用寿命大于19次；与钛铝合金反应界面厚度约为16～35μm；熔炼后钛铝合金的氧含量小于0.1wt％。
实施例7
一种钛铝合金熔炼用耐火材料及其制备方法。以71～75wt％的含钛六铝酸钙颗粒为骨料，以25～29wt％的含钛六铝酸钙细粉为基质料；先将所述基质料混匀，再将混匀后的基质料加入所述骨料中，混合均匀，然后外加占所述骨料与所述基质料之和0.5～1.5wt％的结合剂，混碾，在150～200MPa条件下压制成型，在110～160℃条件下保温20～28小时，制得钛铝合金熔炼用耐火材料。
所述结合剂为聚乙烯醇。
本实施例制备的钛铝合金熔炼用耐火材料经检测：使用寿命大于20次；与钛铝合金反应界面厚度约为10～32μm；熔炼后钛铝合金的氧含量小于0.1wt％。
实施例8
一种钛铝合金熔炼用耐火材料及其制备方法。以71～75wt％的含钛六铝酸钙颗粒为骨料，以25～29wt％的含钛六铝酸钙细粉为基质料；先将所述基质料混匀，再将混匀后的基质料加入所述骨料中，混合均匀，然后外加占所述骨料与所述基质料之和1～2wt％的结合剂，混碾，在100～150MPa条件下压制成型，在150～200℃条件下保温28～36小时，制得钛铝合金熔炼用耐火材料。
所述结合剂为酚醛树脂。
本实施例制备的钛铝合金熔炼用耐火材料经检测：使用寿命大于20次；与钛铝合金反应界面厚度约为10～31μm；熔炼后钛铝合金的氧含量小于0.1wt％。
本具体实施方式与现有技术相比具有如下积极效果：
1、本具体实施方式以含钛六铝酸钙颗粒为骨料和以含钛六铝酸钙细粉为基质料，混合后加入结合剂，混碾，机压成型，经110～200℃热处理20～36小时，制得钛铝合金熔炼用耐火材料，故工艺简单。本具体实施方式采用的含钛六铝酸钙材料是以氧化铝微粉、碳酸钙微粉和氧化钛微粉为主要原料，原料来源广泛，生产成本低。
2、本具体实施方式所制备的钛铝合金熔炼用耐火材料分别以含钛六铝酸钙颗粒为骨料和以含钛六铝酸钙细粉为基质料，骨料和基质料的物相组成、化学性质及物理性能均相同，组成均匀，高温条件下稳定性好。本具体实施方式采用的含钛六铝酸钙颗粒和所述含钛六铝酸钙细粉的Ca((Al0.84 Ti0.16)2)6O19物相含量大于90wt％，兼具六铝酸钙和钛酸钙的优良特性，耐火度高、高温热力学和体积稳定性好，因此，所制备的钛铝合金熔炼用耐火材料具有良好的高温化学稳定性。
3、本具体实施方式采用的含钛六铝酸钙材料具有较低的热膨胀系数与导热系数，所制备的钛铝合金熔炼用耐火材料在承受温度剧变时，可以有效缓冲热应力，减少应力集中，因此，所制备的钛铝合金熔炼用耐火材料热震稳定性能优异。
4、本具体实施方式采用的骨料和基质料中兼具TiO2和Al2O3组分，在与钛铝合金熔体接触时，可以同时抑制合金熔体中Ti组分和Al组分与耐火材料的相互作用，因此，所制备的钛铝合金熔炼用耐火材料能够较好地抵御钛铝合金熔体的侵蚀。
5、由于所制备的钛铝合金熔炼用耐火材料高温化学稳定性优异和抗钛铝合金熔体能力强，在与钛铝合金熔体接触时，不易与合金熔体反应，因此，对钛铝合金污染小。
本具体实施方式制备的钛铝合金熔炼用耐火材料经检测：使用寿命大于18次；与钛铝合金反应界面厚度约为10～50μm；熔炼后钛铝合金的氧含量小于0.1wt％。
因此，本具体实施方式成本低和工艺简单，所制备的钛铝合金熔炼用耐火材料具有高温化学稳定性好、抗热震性能好、抗钛铝合金熔体能力强和对钛铝合金污染小的特点。

Claims (7)

  1. 一种钛铝合金熔炼用耐火材料的制备方法，其特征在于以60～75wt％的含钛六铝酸钙颗粒为骨料，以25～40wt％的含钛六铝酸钙细粉为基质料；先将所述基质料混匀，再将混匀后的基质料加入所述骨料中，混合均匀，然后外加占所述骨料与所述基质料之和0.5～2wt％的结合剂，混碾，在100～200MPa条件下压制成型，在110～200℃条件下保温20～36小时，制得钛铝合金熔炼用耐火材料；
    所述含钛六铝酸钙颗粒和所述含钛六铝酸钙细粉的制备方法是：以60～80wt％的氧化铝微粉、5～20wt％的碳酸钙微粉、10～20wt％的氧化钛微粉和1～10wt％的氧化亚锰微粉为原料，将所述原料在行星球磨机中混合均匀，得到混合料；然后将所述混合料在100～200MPa条件下机压成型，得到生坯；最后将所述生坯在110～200℃条件下干燥12～36小时，在1500～1800℃条件下保温1～8小时，制得含钛六铝酸钙材料；
    将所述含钛六铝酸钙材料破碎至粒径为0.088～10mm，即得含钛六铝酸钙颗粒；将所述含钛六铝酸钙材料破碎至粒径小于0.088mm，即得含钛六铝酸钙细粉；所述含钛六铝酸钙颗粒和所述含钛六铝酸钙细粉的Ca((Al 0.84 Ti 0.16)2)6 O 19物相含量大于90wt％。
  2. 根据权利要求1所述的钛铝合金熔炼用耐火材料的制备方法，其特征在于所述结合剂为聚乙烯醇、酚醛树脂和铝溶胶中的一种。
  3. 根据权利要求1所述的钛铝合金熔炼用耐火材料的制备方法，其特征在于所述氧化铝微粉的Al 2 O 3含量≥98wt％，氧化铝微粉的粒径D 50为1～8μm。
  4. 根据权利要求1所述的钛铝合金熔炼用耐火材料的制备方法，其特征在于所述碳酸钙微粉的粒径D 50为1～10μm。
  5. 根据权利要求1所述的钛铝合金熔炼用耐火材料的制备方法，其特征在于所述氧化钛微粉的TiO 2含量≥90wt％，氧化钛微粉的粒径D 50为1～10μm。
  6. 根据权利要求1所述的钛铝合金熔炼用耐火材料的制备方法，其特征在于所述氧化亚锰微粉的MnO含量≥90wt％，氧化亚锰微粉的粒径D 50为1～8μm。
  7. 一种钛铝合金熔炼用耐火材料，其特征在于所述的钛铝合金熔炼用耐火材料是根据权利要求1～6项中任一项所述的钛铝合金熔炼用耐火材料的制备方法所制备的钛铝合金熔炼用耐火材料。
PCT/CN2021/074587 2020-03-13 2021-02-01 一种钛铝合金熔炼用耐火材料及其制备方法 WO2021179844A1 (zh)

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