CN109468484B - Method for realizing high-temperature titanium alloy composite reinforcement by adding zirconium nitride - Google Patents

Method for realizing high-temperature titanium alloy composite reinforcement by adding zirconium nitride Download PDF

Info

Publication number
CN109468484B
CN109468484B CN201811595900.XA CN201811595900A CN109468484B CN 109468484 B CN109468484 B CN 109468484B CN 201811595900 A CN201811595900 A CN 201811595900A CN 109468484 B CN109468484 B CN 109468484B
Authority
CN
China
Prior art keywords
titanium alloy
temperature titanium
temperature
alloy
zrn
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811595900.XA
Other languages
Chinese (zh)
Other versions
CN109468484A (en
Inventor
孔凡涛
苏宇
陈玉勇
王晓鹏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Institute of Technology
Original Assignee
Harbin Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harbin Institute of Technology filed Critical Harbin Institute of Technology
Priority to CN201811595900.XA priority Critical patent/CN109468484B/en
Publication of CN109468484A publication Critical patent/CN109468484A/en
Application granted granted Critical
Publication of CN109468484B publication Critical patent/CN109468484B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C22C32/0068—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only nitrides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon

Abstract

The invention discloses a method for realizing high-temperature titanium alloy composite reinforcement by adding zirconium nitride, and relates to a method for realizing high-temperature titanium alloy composite reinforcement by adding zirconium nitride. The invention adds a novel grain refiner ZrN, uses Zr element in ZrN to replace Zr in high-temperature titanium alloy, and the adding amount of the refiner ZrN depends on the Zr content in the high-temperature titanium alloy. After ZrN is added, crystal grains of the high-temperature titanium alloy can be effectively refined, so that fine grain strengthening of the titanium alloy is achieved, meanwhile, a large amount of N elements can be introduced into the high-temperature titanium alloy, and according to a Ti + N (titanium plus nitrogen) reaction formula, N and Ti in a matrix are combined to form a large amount of finely dispersed TiN, so that second phase strengthening is achieved. Therefore, ZrN is added into the alloy, so that the solid solution strengthening of Zr in the alloy is ensured, and the superposition of fine grain strengthening and second phase strengthening can be simultaneously realized. The invention can effectively improve the mechanical property of the high-temperature titanium alloy.

Description

Method for realizing high-temperature titanium alloy composite reinforcement by adding zirconium nitride
Technical Field
The invention relates to a method for realizing high-temperature titanium alloy composite reinforcement by adding zirconium nitride.
Background
The titanium alloy has the advantages of low density, high specific strength, high specific modulus, no magnetism, corrosion resistance, weldability and the like, and is widely applied to the fields of aerospace, war industry and the like. In recent years, with the increasing speed of aerospace vehicles, more stringent requirements are also put forward on the mechanical properties of high-temperature structural materials used in the aerospace vehicles and power systems thereof. As a structural material applied to key parts in the aerospace field, the room temperature or high temperature strength is an important index for measuring the reliability of the high temperature titanium alloy. Therefore, how to improve the room temperature or high temperature strength of the high temperature titanium alloy has very important significance.
At present, the main strengthening modes of the high-temperature titanium alloy comprise fine-grain strengthening, solid solution strengthening, second phase strengthening and the like. However, at present, certain amount of Al, Sn, Zr, Si and other elements are added into the high-temperature titanium alloy for solid solution strengthening, and Ti in the high-temperature titanium alloy is utilized3The Al phase and the silicide phase perform second phase strengthening. For certain high temperature titanium alloy based compositesThe existence of the material and the reinforcement can refine grains and realize the superposition of fine grain reinforcement and second phase reinforcement. However, in the high-temperature titanium alloy, the superposition of the triple strengthening effects of solid solution strengthening, fine grain strengthening and second phase strengthening can be realized only by adding the refiner, and a literature report is not available at present.
Disclosure of Invention
The invention provides a method for realizing composite strengthening of a high-temperature titanium alloy by adding zirconium nitride, aiming at solving the problem of low strength of the existing high-temperature titanium alloy.
The method for realizing the composite strengthening of the high-temperature titanium alloy by adding the zirconium nitride comprises the following steps:
calculating the mass percent of each element according to the nominal chemical composition of the final product zirconium-containing high-temperature titanium alloy, and batching according to each element contained in the zirconium-containing high-temperature titanium alloy to obtain a raw material to be melted; in the material mixing process, Ti element is provided by sponge titanium, Zr element is provided by ZrN, and the rest elements are provided by pure metal or intermediate alloy;
secondly, smelting the raw materials to be smelted to obtain a high-temperature titanium alloy ingot to be heat-treated;
and thirdly, carrying out homogenizing annealing on the high-temperature titanium alloy ingot to be subjected to heat treatment, and then cooling along with the furnace to obtain the zirconium nitride reinforced zirconium-containing high-temperature titanium alloy.
The invention has the beneficial effects that:
the invention relates to CN201210374505.5, a high-temperature titanium alloy and a preparation method thereof, and provides a preparation method of a novel near α high-temperature titanium alloy which is provided by the subject group, wherein the short-time use temperature of the high-temperature titanium alloy is raised to 650-700 ℃ by increasing the Zr content and adding high-melting-point elements such as Nb and W, and the high-temperature titanium alloy has excellent mechanical properties.
According to the invention, the grain refinement is realized only by adding the refiner ZrN into the high-temperature titanium alloy, and meanwhile, the alloy contains TiN synthesized by in-situ reaction and solid-solution Zr element, so that the superposition of various strengthening modes such as fine grain strengthening and TiN second-phase strengthening can be realized while the solid-solution strengthening of the Zr element is ensured, and the strength of the high-temperature titanium alloy is obviously improved. The high-temperature titanium alloy can be produced by using the existing high-temperature titanium alloy smelting equipment and process, does not increase extra preparation cost, and has important commercial value and wide application prospect.
Drawings
FIG. 1 shows the room temperature tensile properties of a TA15 alloy without ZrN added and a TA15 alloy with ZrN;
FIG. 2 shows room temperature tensile properties of Ti60 alloy without ZrN added and Ti60 alloy with ZrN;
FIG. 3 shows the room temperature tensile properties of Ti6242 alloy without ZrN added and Ti6242 alloy with ZrN;
FIG. 4 shows room temperature tensile properties of Ti1100 alloy without ZrN added and Ti1100 alloy with ZrN;
FIG. 5 shows room temperature tensile properties of Ti-6Al-3Sn-10Zr-0.8Mo-1Nb-1W-0.3Si alloy without ZrN added and Ti-6Al-3Sn-10Zr-0.8Mo-1Nb-1W-0.3Si alloy with ZrN added.
Detailed Description
The first embodiment is as follows: the method for realizing the composite strengthening of the high-temperature titanium alloy by adding the zirconium nitride specifically comprises the following steps:
calculating the mass percent of each element according to the nominal chemical composition of the final product zirconium-containing high-temperature titanium alloy, and batching according to each element contained in the zirconium-containing high-temperature titanium alloy to obtain a raw material to be melted; in the material mixing process, Ti element is provided by sponge titanium, Zr element is provided by ZrN, and the rest elements are provided by pure metal or intermediate alloy;
secondly, smelting the raw materials to be smelted to obtain a high-temperature titanium alloy ingot to be heat-treated;
and thirdly, carrying out homogenizing annealing on the high-temperature titanium alloy ingot to be subjected to heat treatment, and then cooling along with the furnace to obtain the zirconium nitride reinforced zirconium-containing high-temperature titanium alloy.
In the embodiment, a novel grain refiner ZrN is added to refine grains so as to realize fine grain strengthening, meanwhile, Zr element in the ZrN replaces Zr in the high-temperature titanium alloy to play a role in solid solution strengthening, and N is combined with Ti in a matrix to form a large amount of finely dispersed TiN to play a role in second phase strengthening. The addition amount of the refiner ZrN depends on the Zr content in the high-temperature titanium alloy, and the method is suitable for all high-temperature titanium alloys containing Zr and can effectively improve the mechanical property of the high-temperature titanium alloy.
The refiner is directly purchased for industrial production of ZrN.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the method is used for composite strengthening of Zr-containing high-temperature titanium alloy, and the addition amount of ZrN is 2.3-11.36 wt.%. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: in the step one, the purity of the sponge titanium is more than or equal to 99 percent, the purity of ZrN is more than or equal to 99 percent, the purity of pure metal is more than or equal to 99 percent, and the purity of the intermediate alloy is more than or equal to 99 percent. The others are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: and in the second step, the smelting is vacuum non-consumable arc smelting, vacuum induction smelting or electron beam cold hearth smelting. The rest is the same as one of the first to third embodiments.
According to the embodiment, the copper plate with the thickness of more than or equal to 30mm is placed at the bottom of the mold, so that sequential solidification of high-temperature titanium alloy ingots can be realized, and the quality of the alloy ingots is improved.
Fifth specific embodiment, the difference between this embodiment and one of the first to fourth specific embodiments is that the smelting process in the second step is to put the prepared raw materials into a vacuum induction smelting furnace, and vacuumize the furnace until the vacuum degree in the furnace is less than or equal to 3.0 × 10-3Pa, pouring after the raw materials are melted and heat preservation is carried out for 5-30 min; when casting ingot, a copper plate with the thickness more than or equal to 30mm is placed at the bottom of the mould. The rest is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: and step three, the homogenizing annealing is to put the high-temperature titanium alloy ingot to be heat-treated into a heat treatment furnace with the temperature of 800-950 ℃ and keep the temperature for 5-50 h. The rest is the same as one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: and step three, the homogenizing annealing is to put the high-temperature titanium alloy ingot to be heat-treated into a heat treatment furnace with the temperature of 900 ℃ and keep the temperature for 50 hours. The rest is the same as one of the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: the method for realizing the composite strengthening of the high-temperature titanium alloy by adding the zirconium nitride also comprises the following heat treatment and the following processing treatment of the zirconium-containing high-temperature titanium alloy. The rest is the same as one of the first to seventh embodiments.
The embodiment can regulate and control the performance of the material through heat treatment and hot working.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: the subsequent heat treatment comprises one or more of annealing, tempering, quenching, solid solution and aging. The rest is the same as the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: the subsequent processing treatment comprises forging, rolling, extruding, drawing or machining. The rest is the same as one of the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: the method for realizing the composite strengthening of the high-temperature titanium alloy by adding the zirconium nitride comprises the following steps:
calculating the mass percent of each element according to the nominal chemical composition Ti-6.5Al-2Zr-1Mo-1V of the TA15 alloy of the final product, and batching according to each element contained in the alloy to obtain a raw material to be melted; the total mass of the ingredients is 20kg, wherein the sponge titanium with the purity of more than or equal to 99 percent is 17.82kg, the industrial pure aluminum with the purity of more than or equal to 99 percent is 1.1kg, the molybdenum-aluminum alloy with the molybdenum content of 65 percent is 0.31kg, the aluminum-vanadium alloy with the vanadium content of 65 percent is 0.31kg, and the ZrN powder is 0.46 kg;
secondly, putting the raw materials to be melted into a water-cooled copper crucible vacuum induction melting furnace, and vacuumizing to 3.0 × 10-3Under the MPa, casting after the alloy raw material is melted and heat preservation is carried out for 10 min; placing a copper plate with the thickness of more than or equal to 30mm at the bottom of the mold when casting ingots to obtain high-temperature titanium alloy ingots to be heat-treated;
and thirdly, placing the high-temperature titanium alloy ingot to be subjected to heat treatment into a heat treatment furnace at the temperature of 900 ℃ for 50 hours, and then cooling along with the furnace to obtain the zirconium nitride reinforced TA15 alloy.
Example two: the preparation method of the zirconium-containing high-temperature titanium alloy comprises the following steps:
calculating the mass percent of each element according to the nominal chemical composition Ti-6.5Al-2Zr-1Mo-1V of the TA15 alloy of the final product, and batching according to each element contained in the alloy to obtain a raw material to be melted; the total mass of the ingredients is 20kg, Ti element is provided by sponge titanium with the purity of more than or equal to 99 percent, Zr element is provided by sponge zirconium, and the rest elements are provided by industrial pure aluminum with the purity of more than or equal to 99 percent, molybdenum-aluminum alloy with the molybdenum content of 65 percent and aluminum-vanadium alloy with the vanadium content of 65 percent;
secondly, putting the raw materials to be melted into a water-cooled copper crucible vacuum induction melting furnace, and vacuumizing to 3.0 × 10-3Under the MPa, casting after the alloy raw material is melted and heat preservation is carried out for 10 min; placing a copper plate with the thickness of more than or equal to 30mm at the bottom of the mold when casting ingots to obtain high-temperature titanium alloy ingots to be heat-treated;
and thirdly, placing the high-temperature titanium alloy ingot to be subjected to heat treatment into a heat treatment furnace at the temperature of 900 ℃ for 50 hours, and then cooling along with the furnace to obtain the TA15 alloy.
Core samples were cut by wire cutting from each of the zirconium nitride-reinforced TA15 alloy obtained in example one and the TA15 alloy obtained in example two, and room temperature tensile properties of the titanium alloy without ZrN and the titanium alloy containing ZrN were simultaneously measured by an electronic universal tensile tester. As shown in fig. 1, TA15 without ZrN had a tensile strength of 936MPa, and after ZrN was added, the mass fraction of TiN produced was 1.33% according to the reaction formula of Ti + N ═ TiN, and the tensile strength was 1066MPa, which increased the strength by approximately 13.8%.
Example three: the method for realizing the composite strengthening of the high-temperature titanium alloy by adding the zirconium nitride comprises the following steps:
calculating the mass percent of each element according to the nominal chemical composition Ti-5.8 Al-4.0 Sn-3.5 Zr-1 Mo-0.85 Nd-0.4 Si of the final product Ti60 alloy, and batching according to each element contained in the elements to obtain a raw material to be melted; the total mass of the ingredients is 20kg, wherein the sponge titanium with the purity of more than or equal to 99 percent is 16.81kg, the high-purity aluminum with the purity of more than or equal to 99 percent is 0.06kg, the molybdenum aluminum alloy with the molybdenum content of 65 percent is 0.31kg, the aluminum tin alloy with the tin content of 55 percent is 1.4kg, the neodymium aluminum alloy with the neodymium content of 40 percent is 0.43kg, the aluminum-silicon intermediate alloy with the silicon content of 50 percent is 0.16kg, and ZrN is 0.81 kg;
secondly, putting the raw materials to be melted into a water-cooled copper crucible vacuum induction melting furnace, and vacuumizing to 3.0 × 10-3Under the MPa, casting after the alloy raw material is melted and heat preservation is carried out for 10 min; placing a copper plate with the thickness of more than or equal to 30mm at the bottom of the mold when casting ingots to obtain high-temperature titanium alloy ingots to be heat-treated;
and thirdly, placing the high-temperature titanium alloy ingot to be subjected to heat treatment into a heat treatment furnace at the temperature of 900 ℃ for 50 hours, and then cooling along with the furnace to obtain the zirconium nitride reinforced Ti60 alloy.
Example four: the preparation method of the zirconium-containing high-temperature titanium alloy comprises the following steps:
calculating the mass percent of each element according to the nominal chemical composition Ti-5.8 Al-4.0 Sn-3.5 Zr-1 Mo-0.85 Nd-0.4 Si of the final product Ti60 alloy, and batching according to each element contained in the elements to obtain a raw material to be melted; the total mass of the ingredients is 20kg, Ti element is provided by sponge titanium with the purity of more than or equal to 99 percent, Zr element is provided by sponge zirconium, and the rest elements are provided by high-purity aluminum with the purity of more than or equal to 99 percent, molybdenum-aluminum alloy with the molybdenum content of 65 percent, aluminum-tin alloy with the tin content of 55 percent, neodymium-aluminum alloy with the neodymium content of 40 percent and aluminum-silicon intermediate alloy with the silicon content of 50 percent;
secondly, putting the raw materials to be melted into a water-cooled copper crucible vacuum induction melting furnace, and vacuumizing to 3.0 × 10-3Under the MPa, casting after the alloy raw material is melted and heat preservation is carried out for 10 min; placing a copper plate with the thickness of more than or equal to 30mm at the bottom of the mold when casting ingot to obtain a part to be heatedArranging a high-temperature titanium alloy ingot;
and thirdly, placing the high-temperature titanium alloy ingot to be heat-treated into a heat treatment furnace at the temperature of 900 ℃ for 50 hours, and then cooling along with the furnace to obtain the Ti60 alloy.
Core samples were cut by wire cutting from each of the zirconium nitride-reinforced Ti60 alloy obtained in example three and the Ti60 alloy obtained in example four, and room temperature tensile properties of the titanium alloy without ZrN and the titanium alloy containing ZrN were simultaneously measured by an electronic universal tensile tester. As shown in fig. 2, the tensile strength of Ti60 without ZrN was 946MPa, and after ZrN was added, the mass fraction of TiN produced was 2.44% according to the reaction formula of Ti + N ═ TiN, and the tensile strength was 1082MPa, which was an improvement in strength of nearly 14.4%.
Example five: the method for realizing the composite strengthening of the high-temperature titanium alloy by adding the zirconium nitride comprises the following steps:
calculating the mass percent of each element according to the nominal chemical composition Ti-6Al-2Sn-4Zr-2Mo of the Ti6242 alloy of the final product, and batching according to each element contained in the alloy to obtain a raw material to be melted; the total mass of the ingredients is 20kg, wherein the sponge titanium with the purity of more than or equal to 99 percent is 17.08kg, the industrial pure aluminum with the purity of more than or equal to 99 percent is 0.65kg, the molybdenum-aluminum alloy with the molybdenum content of 65 percent is 0.62kg, the aluminum-tin alloy with the tin content of 55 percent is 0.73kg, and the ZrN powder is 0.92 kg;
secondly, putting the raw materials to be melted into a water-cooled copper crucible vacuum induction melting furnace, and vacuumizing to 3.0 × 10-3Under the MPa, casting after the alloy raw material is melted and heat preservation is carried out for 10 min; placing a copper plate with the thickness of more than or equal to 30mm at the bottom of the mold when casting ingots to obtain high-temperature titanium alloy ingots to be heat-treated;
and thirdly, placing the high-temperature titanium alloy ingot to be subjected to heat treatment into a heat treatment furnace at the temperature of 900 ℃ for 50 hours, and then cooling along with the furnace to obtain the zirconium nitride reinforced Ti6242 alloy.
Example six: the preparation method of the zirconium-containing high-temperature titanium alloy comprises the following steps:
calculating the mass percent of each element according to the nominal chemical composition Ti-6Al-2Sn-4Zr-2Mo of the Ti6242 alloy of the final product, and batching according to each element contained in the alloy to obtain a raw material to be melted; the total mass of the ingredients is 20kg, Ti element is provided by sponge titanium with the purity of more than or equal to 99 percent, Zr element is provided by sponge zirconium, and the rest elements are provided by industrial pure aluminum with the purity of more than or equal to 99 percent, molybdenum-aluminum alloy with the molybdenum content of 65 percent and aluminum-tin alloy with the tin content of 55 percent;
secondly, putting the raw materials to be melted into a water-cooled copper crucible vacuum induction melting furnace, and vacuumizing to 3.0 × 10-3Under the MPa, casting after the alloy raw material is melted and heat preservation is carried out for 10 min; placing a copper plate with the thickness of more than or equal to 30mm at the bottom of the mold when casting ingots to obtain high-temperature titanium alloy ingots to be heat-treated;
and thirdly, placing the high-temperature titanium alloy ingot to be heat-treated into a heat treatment furnace at the temperature of 900 ℃ for 50 hours, and then cooling along with the furnace to obtain the Ti6242 alloy.
Core samples were cut by wire cutting from each of the zirconium nitride-reinforced Ti6242 alloy obtained in example five and the Ti6242 alloy obtained in example six, and room-temperature tensile properties of the titanium alloy without ZrN addition and the titanium alloy containing ZrN were simultaneously measured by an electronic universal tensile tester. As shown in fig. 3, Ti6242 without ZrN had a tensile strength of 930MPa, and after ZrN was added, the mass fraction of TiN produced was 2.72% according to the reaction formula of Ti + N ═ TiN, and the tensile strength was 1103MPa, which increased the strength by approximately 18.6%.
Example seven: the method for realizing the composite strengthening of the high-temperature titanium alloy by adding the zirconium nitride comprises the following steps:
calculating the mass percent of each element according to the nominal chemical composition Ti-6Al-2.7Sn-4Zr-0.4Mo-0.45Si of the final product Ti1100 alloy, and batching according to each element contained in the elements to obtain a raw material to be melted; the total mass of the ingredients is 20kg, wherein the sponge titanium with the purity of more than or equal to 99 percent is 17.15kg, the industrial pure aluminum with the purity of more than or equal to 99 percent is 0.65kg, the molybdenum-aluminum alloy with the molybdenum content of 65 percent is 0.12kg, the aluminum-tin alloy with the tin content of 55 percent is 0.98kg, the aluminum-silicon intermediate alloy with the silicon content of 50 percent is 0.18kg, and the ZrN powder is 0.92 kg;
secondly, putting the raw materials to be melted into a water-cooled copper crucible vacuum induction melting furnace, and vacuumizing to 3.0 × 10-3Under the MPa, casting after the alloy raw material is melted and heat preservation is carried out for 10 min; when casting ingot, a copper plate with the thickness more than or equal to 30mm is placed at the bottom of the moldObtaining a high-temperature titanium alloy ingot to be heat-treated;
and thirdly, placing the high-temperature titanium alloy ingot to be subjected to heat treatment into a heat treatment furnace at the temperature of 900 ℃ for 50 hours, and then cooling along with the furnace to obtain the zirconium nitride reinforced Ti1100 alloy.
Example eight: the preparation method of the zirconium-containing high-temperature titanium alloy comprises the following steps:
calculating the mass percent of each element according to the nominal chemical composition Ti-6Al-2.7Sn-4Zr-0.4Mo-0.45Si of the final product Ti1100 alloy, and batching according to each element contained in the elements to obtain a raw material to be melted; the total mass of the ingredients is 20kg, the Ti element is provided by sponge titanium with the purity of more than or equal to 99 percent, the Zr element is provided by sponge zirconium, and the other elements are provided by industrial pure aluminum with the purity of more than or equal to 99 percent, molybdenum-aluminum alloy with the molybdenum content of 65 percent, aluminum-tin alloy with the tin content of 55 percent and aluminum-silicon intermediate alloy with the silicon content of 50 percent;
secondly, putting the raw materials to be melted into a water-cooled copper crucible vacuum induction melting furnace, and vacuumizing to 3.0 × 10-3Under the MPa, casting after the alloy raw material is melted and heat preservation is carried out for 10 min; placing a copper plate with the thickness of more than or equal to 30mm at the bottom of the mold when casting ingots to obtain high-temperature titanium alloy ingots to be heat-treated;
and thirdly, placing the high-temperature titanium alloy ingot to be heat-treated into a heat treatment furnace at the temperature of 900 ℃ for 50 hours, and then cooling along with the furnace to obtain the Ti1100 alloy.
Core samples were cut by wire cutting from each of the zirconium nitride-reinforced Ti1100 alloy obtained in example seven and the Ti1100 alloy obtained in example eight, and room temperature tensile properties of the titanium alloy without ZrN addition and the titanium alloy containing ZrN were simultaneously measured by an electronic universal tensile tester. As shown in fig. 4, the tensile strength of Ti1100 without ZrN was 916MPa, and after ZrN was added, the mass fraction of TiN produced was 2.72% according to the reaction formula of Ti + N ═ TiN, and the tensile strength was 1068MPa, and the strength was increased by almost 16.6%, while the moldability was slightly decreased.
Example nine: the method for realizing the composite strengthening of the high-temperature titanium alloy by adding the zirconium nitride comprises the following steps:
calculating the mass percent of each element according to the nominal chemical composition Ti-6Al-3Sn-10Zr-0.8Mo-1Nb-1W-0.3Si of the zirconium-containing high-temperature titanium alloy of the final product, and batching according to each element contained in the zirconium-containing high-temperature titanium alloy to obtain a raw material to be melted; the total mass of the ingredients is 20kg, wherein the purity of sponge titanium is more than or equal to 99 percent 15.45kg, the purity of industrial pure aluminum is more than or equal to 99 percent 0.43kg, the molybdenum aluminum alloy with the molybdenum content of 65 percent 0.25kg, the aluminum tin alloy with the tin content of 55 percent 1.09kg, the niobium aluminum alloy with the niobium content of 60 percent 0.33kg, the purity of pure tungsten with the purity of 99.9 percent 0.2kg, the silicon-aluminum intermediate alloy with the silicon content of 50 percent 0.12kg, and ZrN is 2.31 kg;
secondly, putting the raw materials to be melted into a water-cooled copper crucible vacuum induction melting furnace, and vacuumizing to 3.0 × 10-3Under the MPa, casting after the alloy raw material is melted and heat preservation is carried out for 10 min; placing a copper plate with the thickness of more than or equal to 30mm at the bottom of the mold when casting ingots to obtain high-temperature titanium alloy ingots to be heat-treated;
and thirdly, placing the high-temperature titanium alloy ingot to be heat-treated into a heat treatment furnace at the temperature of 900 ℃ for 50 hours, and then cooling along with the furnace to obtain the zirconium-nitride-reinforced zirconium-containing high-temperature titanium alloy.
Example ten: the preparation method of the zirconium-containing high-temperature titanium alloy comprises the following steps:
calculating the mass percent of each element according to the nominal chemical composition Ti-6Al-3Sn-10Zr-0.8Mo-1Nb-1W-0.3Si of the zirconium-containing high-temperature titanium alloy of the final product, and batching according to each element contained in the zirconium-containing high-temperature titanium alloy to obtain a raw material to be melted; the total mass of the ingredients is 20kg, the Ti element is provided by sponge titanium with the purity of more than or equal to 99 percent, the Zr element is provided by sponge zirconium, and the other elements are provided by industrial pure aluminum with the purity of more than or equal to 99 percent, molybdenum-aluminum alloy with the molybdenum content of 65 percent, aluminum-tin alloy with the tin content of 55 percent, niobium-aluminum alloy with the niobium content of 60 percent, pure tungsten with the purity of more than or equal to 99 percent and aluminum-silicon intermediate alloy with the silicon content of 50 percent;
secondly, putting the raw materials to be melted into a water-cooled copper crucible vacuum induction melting furnace, and vacuumizing to 3.0 × 10-3Under the MPa, casting after the alloy raw material is melted and heat preservation is carried out for 10 min; placing a copper plate with the thickness of more than or equal to 30mm at the bottom of the mold when casting ingots to obtain high-temperature titanium alloy ingots to be heat-treated;
and thirdly, placing the high-temperature titanium alloy ingot to be heat-treated into a heat treatment furnace at the temperature of 900 ℃ for 50 hours, and then cooling along with the furnace to obtain the zirconium-containing high-temperature titanium alloy.
Core samples were cut out by wire-cutting from each of the zirconium nitride-reinforced zirconium-containing high-temperature titanium alloy obtained in example nine and the zirconium-containing high-temperature titanium alloy obtained in example ten, and the room-temperature tensile properties of the titanium alloy without ZrN and the titanium alloy containing ZrN were simultaneously tested by an electronic universal tensile tester. As shown in FIG. 5, Ti-6Al-3Sn-10Zr-0.8Mo-1Nb-1W-0.3Si without ZrN added has a tensile strength of 937MPa, and after ZrN is added, the mass fraction of TiN generated according to the reaction formula of Ti + N ═ TiN is 6.82%, and the tensile strength is 1132MPa, which is 20.8% higher.

Claims (10)

1. A method for realizing high-temperature titanium alloy composite strengthening by adding zirconium nitride is characterized by comprising the following steps:
calculating the mass percent of each element according to the nominal chemical composition of the final product zirconium-containing high-temperature titanium alloy, and batching according to each element contained in the zirconium-containing high-temperature titanium alloy to obtain a raw material to be melted; in the material mixing process, Ti element is provided by sponge titanium, Zr element is provided by ZrN, and the rest elements are provided by pure metal or intermediate alloy;
secondly, smelting the raw materials to be smelted to obtain a high-temperature titanium alloy ingot to be heat-treated;
and thirdly, carrying out homogenizing annealing on the high-temperature titanium alloy ingot to be subjected to heat treatment, and then cooling along with the furnace to finish the composite reinforcement of the high-temperature titanium alloy.
2. The method for achieving high-temperature titanium alloy composite strengthening by adding zirconium nitride according to claim 1, wherein the method is used for Zr-containing high-temperature titanium alloy composite strengthening, and the ZrN is added in an amount of 2.3-11.36 wt.%.
3. The method for realizing the composite strengthening of the high-temperature titanium alloy by adding the zirconium nitride according to claim 1, wherein the purity of the titanium sponge in the step one is more than or equal to 99%, the purity of the ZrN is more than or equal to 99%, the purity of the pure metal is more than or equal to 99%, and the purity of the intermediate alloy is more than or equal to 99%.
4. The method for realizing the composite strengthening of the high-temperature titanium alloy by adding the zirconium nitride according to claim 1, wherein the smelting in the second step is vacuum non-consumable arc smelting, vacuum induction smelting or electron beam cold hearth smelting.
5. The method for achieving high-temperature titanium alloy composite strengthening by adding zirconium nitride according to claim 4, wherein the smelting process in the second step is that the prepared raw materials are placed into a vacuum induction smelting furnace, and the furnace is vacuumized until the vacuum degree in the furnace is less than or equal to 3.0 × 10-3Pa, pouring after the raw materials are melted and heat preservation is carried out for 5-30 min; when casting ingot, a copper plate with the thickness more than or equal to 30mm is placed at the bottom of the mould.
6. The method for realizing the composite strengthening of the high-temperature titanium alloy by adding the zirconium nitride according to claim 1, wherein the homogenizing annealing in the third step is to place the high-temperature titanium alloy ingot to be heat-treated into a heat treatment furnace with the temperature of 800-950 ℃ for 5-50 h.
7. The method for realizing composite strengthening of the high-temperature titanium alloy by adding the zirconium nitride according to claim 1, wherein the homogenizing annealing in the third step is to place the high-temperature titanium alloy ingot to be heat-treated into a heat treatment furnace with the temperature of 900 ℃ and keep the temperature for 50 h.
8. The method for achieving composite strengthening of the high-temperature titanium alloy by adding the zirconium nitride as claimed in claim 1, wherein the method for achieving composite strengthening of the high-temperature titanium alloy by adding the zirconium nitride further comprises a subsequent heat treatment and a subsequent processing treatment of the zirconium-containing high-temperature titanium alloy.
9. The method of claim 8, wherein the post heat treatment comprises one or a combination of annealing, tempering, quenching, solution treating, and aging.
10. The method of claim 8, wherein the post-processing treatment comprises forging, rolling, extruding, drawing or machining.
CN201811595900.XA 2018-12-25 2018-12-25 Method for realizing high-temperature titanium alloy composite reinforcement by adding zirconium nitride Active CN109468484B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811595900.XA CN109468484B (en) 2018-12-25 2018-12-25 Method for realizing high-temperature titanium alloy composite reinforcement by adding zirconium nitride

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811595900.XA CN109468484B (en) 2018-12-25 2018-12-25 Method for realizing high-temperature titanium alloy composite reinforcement by adding zirconium nitride

Publications (2)

Publication Number Publication Date
CN109468484A CN109468484A (en) 2019-03-15
CN109468484B true CN109468484B (en) 2020-07-24

Family

ID=65676654

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811595900.XA Active CN109468484B (en) 2018-12-25 2018-12-25 Method for realizing high-temperature titanium alloy composite reinforcement by adding zirconium nitride

Country Status (1)

Country Link
CN (1) CN109468484B (en)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6551371B1 (en) * 1998-07-21 2003-04-22 Kabushiki Kaisha Toyota Chuo Kenkyusho Titanium-based composite material, method for producing the same and engine valve
JP4222157B2 (en) * 2003-08-28 2009-02-12 大同特殊鋼株式会社 Titanium alloy with improved rigidity and strength
CN106058092A (en) * 2016-06-28 2016-10-26 普定县银丰农业科技发展有限公司 Low-cost titanium alloy energy-saving vehicle storage battery shell and manufacturing method and machining method thereof
CN106435267B (en) * 2016-10-09 2019-03-22 沈阳泰恒通用技术有限公司 A kind of heat resistant and wear resistant damage titanium composite material and preparation method thereof
CN106756237B (en) * 2017-01-10 2019-02-05 沈阳泰恒通用技术有限公司 A kind of abrasion-resistant titanium basic composite material

Also Published As

Publication number Publication date
CN109468484A (en) 2019-03-15

Similar Documents

Publication Publication Date Title
US20200190634A1 (en) Method of forming a cast aluminium alloy
CN110512116B (en) Multicomponent high-alloying high Nb-TiAl intermetallic compound
US3203794A (en) Titanium-high aluminum alloys
CN102994834B (en) Heatproof magnesium alloy containing Nb
CN108251675B (en) Al-Ti-Nb-B refiner for casting aluminum-silicon alloy and preparation method and application thereof
CN102618757B (en) Heat-resistant magnesium alloy
CN102994835B (en) Heatproof magnesium alloy
CN110819873B (en) High Nb-TiAl alloy added with nano yttrium oxide and preparation method thereof
CN104018028A (en) High-aluminium and high-silicon cast titanium alloy
EP3954797B1 (en) Die-casting aluminum alloy, preparation method therefor and application thereof
EP4253584A1 (en) Aluminum alloy and aluminum alloy structural member
CN114807713A (en) Partial eutectic high-entropy alloy containing B2 primary phase and preparation method thereof
CN105861935B (en) Excellent Fe 36Ni invar alloy materials of a kind of thermoplasticity and preparation method thereof
CN114592142A (en) Medium-strength high-toughness titanium alloy with yield strength of 800MPa for ocean engineering and preparation process thereof
CN107699747A (en) A kind of high Cu contents Al Si Li Cu casting alloys and preparation method thereof
CN109468484B (en) Method for realizing high-temperature titanium alloy composite reinforcement by adding zirconium nitride
CN109161767B (en) Creep-resistant magnesium alloy containing W phase and preparation method thereof
CN114672716B (en) CoCrNi with high strength and toughness in heat treatment state2(V2B)xEutectic high-entropy alloy and preparation method thereof
EP2865773B1 (en) Aluminium casting alloy
CN109943738B (en) Aluminum-containing high-modulus rare earth magnesium alloy and preparation method thereof
CN110629081B (en) Novel heat-resistant high-strength high-plasticity corrosion-resistant Al-Cu-Mg-Zn-Ti series aluminum alloy and preparation method thereof
CN111705248A (en) Al-4.5Cu aluminum-copper alloy material and preparation method thereof
EP3138933A1 (en) Heat radiator fin comprising aluminum alloy and method for manufacturing same
JP3626507B2 (en) High strength and high ductility TiAl intermetallic compound
CN103556000A (en) Ti-Si-Al-based alloy containing RE (rare earth) and intermetallic compound reinforcing phase

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant