CN109468484B - A method of adding zirconium nitride to realize composite strengthening of high temperature titanium alloy - Google Patents

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

A method of adding zirconium nitride to realize composite strengthening of high temperature titanium alloy

technical field

The invention relates to a method for realizing composite strengthening of high-temperature titanium alloys by adding zirconium nitride.

Background technique

Titanium alloy has the advantages of low density, high specific strength, high specific modulus, non-magnetic, corrosion resistance and weldability, and is widely used in aerospace, military and other fields. In recent years, with the increasing speed of aerospace vehicles, more stringent requirements have been placed on the mechanical properties of high-temperature structural materials used in aerospace vehicles and their power systems. As a structural material used in key components in the aerospace field, room temperature or high temperature strength is an important indicator to measure the reliability of high temperature titanium alloys. Therefore, how to improve the room temperature or high temperature strength of high temperature titanium alloy is of great significance.

At present, the main strengthening methods of high-temperature titanium alloys include grain refinement strengthening, solid solution strengthening, and second phase strengthening. However, at present, a certain amount of Al, Sn, Zr, Si and other elements are added to the high temperature titanium alloy for solid solution strengthening, and at the same time, the second phase strengthening is carried out through the Ti ₃ Al phase and the silicide phase in the high temperature titanium alloy. For some high-temperature titanium alloy matrix composites, the presence of reinforcements can refine the grains and realize the superposition of fine-grain strengthening and second-phase strengthening. However, in high temperature titanium alloys, the superposition of the triple strengthening effects of solid solution strengthening, grain refinement strengthening and second phase strengthening can be achieved only by adding a refiner, and there is still a lack of literature reports.

SUMMARY OF THE INVENTION

The present invention provides a method for adding zirconium nitride to realize composite strengthening of high-temperature titanium alloys in order to solve the existing problem of low strength of existing high-temperature titanium alloys.

A method for adding zirconium nitride to realize composite strengthening of high-temperature titanium alloys is specifically carried out according to the following steps:

1. Calculate the mass percentage of each element according to the nominal chemical composition of the final product zirconium-containing high-temperature titanium alloy, and perform the batching according to the elements contained in it to obtain the raw material to be melted; in the batching process, the Ti element is provided by sponge titanium, and the Zr element is provided by ZrN Provided, the remaining elements are provided by its pure metal or master alloy;

2. Smelting the raw material to be melted to obtain a high-temperature titanium alloy ingot to be heat-treated;

3. Homogenizing and annealing the high-temperature titanium alloy ingot to be heat-treated, and then cooling with the furnace to obtain a zirconium nitride reinforced high-temperature titanium alloy containing zirconium.

The beneficial effects of the present invention are:

The invention and CN201210374505.5, a high temperature titanium alloy and its preparation method The preparation method of a novel near alpha high temperature titanium alloy proposed by this research group, the high temperature titanium alloy is prepared by increasing the Zr content and adding high melting point elements such as Nb and W The short-term use temperature is increased to 650 ° C ~ 700 ° C, and has excellent mechanical properties. The invention is applicable to all high-temperature titanium alloys containing Zr, including CN201210374505.5, a high-temperature titanium alloy and the high-temperature titanium alloy mentioned in the preparation method thereof. The superposition of the two strengthening effects of the three strengthening effects can further improve the strength of the high-temperature titanium alloy.

In the present invention, the refiner ZrN only needs to be added to the high-temperature titanium alloy to achieve grain refinement. At the same time, the alloy contains TiN synthesized by in-situ reaction and Zr element in solid solution, that is, while ensuring the solid solution strengthening of Zr element, It can realize the superposition of various strengthening methods such as fine-grain strengthening and TiN second phase strengthening, thereby significantly improving the strength of high-temperature titanium alloys. The high-temperature titanium alloy involved in the present invention can be produced by using the existing high-temperature titanium alloy smelting equipment and process, without increasing the extra preparation cost, and has important commercial value and broad application prospect.

Description of drawings

Figure 1 shows the room temperature tensile properties of the TA15 alloy without ZrN and the TA15 alloy containing ZrN;

Figure 2 shows the room temperature tensile properties of Ti60 alloy without ZrN and Ti60 alloy containing ZrN;

Figure 3 shows the room temperature tensile properties of the Ti6242 alloy without ZrN and the Ti6242 alloy containing ZrN;

Figure 4 shows the room temperature tensile properties of the Ti1100 alloy without ZrN and the Ti1100 alloy containing ZrN;

Figure 5 shows the room temperature tensile strength of Ti-6Al-3Sn-10Zr-0.8Mo-1Nb-1W-0.3Si alloy without ZrN addition and Ti-6Al-3Sn-10Zr-0.8Mo-1Nb-1W-0.3Si alloy containing ZrN elongation performance.

Detailed ways

Embodiment 1: In this embodiment, a method for adding zirconium nitride to realize composite strengthening of high-temperature titanium alloys is specifically carried out according to the following steps:

1. Calculate the mass percentage of each element according to the nominal chemical composition of the final product zirconium-containing high-temperature titanium alloy, and perform the batching according to the elements contained in it to obtain the raw material to be melted; in the batching process, the Ti element is provided by sponge titanium, and the Zr element is provided by ZrN Provided, the remaining elements are provided by its pure metal or master alloy;

2. Smelting the raw material to be melted to obtain a high-temperature titanium alloy ingot to be heat-treated;

3. Homogenizing and annealing the high-temperature titanium alloy ingot to be heat-treated, and then cooling with the furnace to obtain a zirconium nitride reinforced high-temperature titanium alloy containing zirconium.

In this embodiment, a new type of grain refiner, ZrN, is added to refine the grains to achieve fine grain strengthening. At the same time, the Zr element in ZrN replaces Zr in the high-temperature titanium alloy to play a solid solution strengthening effect. The Ti in the combined forms a large number of finely dispersed TiN, which plays a role in the strengthening of the second phase. The amount of refiner ZrN added depends on the Zr content in the high-temperature titanium alloy. The present invention is applicable to all high-temperature titanium alloys containing Zr, and can effectively improve the mechanical properties of the high-temperature titanium alloy.

The refiner is purchased directly from industrially produced ZrN.

Embodiment 2: The difference between this embodiment and Embodiment 1 is that this method is used for composite strengthening of Zr-containing high-temperature titanium alloys, and the amount of ZrN added is 2.3-11.36 wt.%. Others are the same as the first embodiment.

Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is: the purity of the sponge titanium in step 1 is ≥99%, the purity of ZrN is ≥99%, the purity of pure metal is ≥99%, and the purity of the master alloy is ≥99%. Purity ≥99%. Others are the same as in the first or second embodiment.

Embodiment 4: The difference between this embodiment and one of Embodiments 1 to 3 is that the smelting described in step 2 is vacuum non-consumable arc smelting, vacuum consumable arc smelting, vacuum induction smelting or electron beam cooling bed Furnace smelting. Others are the same as one of Embodiments 1 to 3.

In this embodiment, placing a copper plate with a thickness of ≥30 mm at the bottom of the mold can realize the sequential solidification of the high-temperature titanium alloy ingot, thereby improving the quality of the alloy ingot.

Embodiment 5: The difference between this embodiment and one of Embodiments 1 to 4 is that the smelting process described in step 2 is: put the prepared raw materials into a vacuum induction melting furnace, and vacuumize until the degree of vacuum in the furnace≤ 3.0×10 ^-3 Pa, the raw material is melted and kept for 5-30 minutes before pouring; when pouring the ingot, place a copper plate with a thickness of ≥30mm at the bottom of the mold. Others are the same as one of Embodiments 1 to 4.

Embodiment 6: The difference between this embodiment and one of Embodiments 1 to 5 is that the homogenization annealing in step 3 is to put the high-temperature titanium alloy ingot to be heat-treated into a heat-treatment furnace with a temperature of 800-950 ° C for 5 ~50h. Others are the same as one of Embodiments 1 to 5.

Embodiment 7: The difference between this embodiment and one of Embodiments 1 to 6 is that the homogenization annealing in step 3 is to put the high temperature titanium alloy ingot to be heat treated into a heat treatment furnace with a temperature of 900°C for 50 hours. Others are the same as one of Embodiments 1 to 6.

Embodiment 8: The difference between this embodiment and one of Embodiments 1 to 7 is that the method for adding zirconium nitride to realize the composite strengthening of a high-temperature titanium alloy further includes subsequent heat treatment and subsequent processing of the zirconium-containing high-temperature titanium alloy. Others are the same as one of Embodiments 1 to 7.

In this embodiment, the properties of the material can be regulated through heat treatment and thermal processing.

Embodiment 9: The difference between this embodiment and one of Embodiments 1 to 8 is that the subsequent heat treatment includes one or a combination of annealing, tempering, quenching, solutionizing and aging. Others are the same as one of Embodiments 1 to 8.

Embodiment 10: The difference between this embodiment and one of Embodiments 1 to 9 is that the subsequent processing includes forging, rolling, extrusion, drawing or machining. Others are the same as one of Embodiments 1 to 9.

Adopt the following examples to verify the beneficial effects of the present invention:

Embodiment 1: A method for adding zirconium nitride to realize composite strengthening of high-temperature titanium alloys is specifically carried out according to the following steps:

1. Calculate the mass percentage of each element according to the nominal chemical composition Ti-6.5Al-2Zr-1Mo-1V of the final product TA15 alloy, and carry out the ingredients according to the elements contained in it to obtain the raw material to be melted; the total mass of the ingredients is 20kg, of which 17.82kg of titanium sponge with a purity of ≥99%, 1.1kg of industrial pure aluminum with a purity of ≥99%, 0.31kg of molybdenum-aluminum alloy with a molybdenum content of 65%, 0.31kg of aluminum-vanadium alloy with a vanadium content of 65%, and 0.46kg of ZrN powder;

2. Put the raw material to be melted into the water-cooled copper crucible vacuum induction melting furnace, evacuate to 3.0×10 ^-3 MPa, and pour the alloy raw material after melting for 10 minutes; place a piece of thickness ≥30mm at the bottom of the mold when pouring the ingot The copper plate is obtained to obtain a high-temperature titanium alloy ingot to be heat-treated;

3. Put the high-temperature titanium alloy ingot to be heat-treated into a heat-treatment furnace with a temperature of 900° C. for 50 hours, and then cool with the furnace to obtain a zirconium nitride-enhanced TA15 alloy.

Embodiment 2: a kind of preparation method of zirconium-containing high-temperature titanium alloy is specifically carried out according to the following steps:

1. Calculate the mass percentage of each element according to the nominal chemical composition Ti-6.5Al-2Zr-1Mo-1V of the final product TA15 alloy, and carry out the ingredients according to the elements contained in it to obtain the raw materials to be melted; the total mass of the ingredients is 20kg, Ti The elements are provided by titanium sponge with a purity of ≥99%, the Zr element is provided by sponge zirconium, and the remaining elements are provided by industrial pure aluminum with a purity of ≥99%, molybdenum-aluminum alloy with a molybdenum content of 65%, and an aluminum-vanadium alloy with a vanadium content of 65%;

2. Put the raw material to be melted into the water-cooled copper crucible vacuum induction melting furnace, evacuate to 3.0×10 ^-3 MPa, and pour the alloy raw material after melting for 10 minutes; place a piece of thickness ≥30mm at the bottom of the mold when pouring the ingot The copper plate is obtained to obtain a high-temperature titanium alloy ingot to be heat-treated;

3. Put the high-temperature titanium alloy ingot to be heat-treated into a heat-treatment furnace with a temperature of 900° C. for 50 hours, and then cool with the furnace to obtain a TA15 alloy.

The core samples of the zirconium nitride reinforced TA15 alloy obtained in Example 1 and the TA15 alloy obtained in Example 2 were cut by wire cutting, and the titanium alloy without ZrN and the titanium alloy containing ZrN were simultaneously tested by electronic universal tensile testing machine. Room temperature tensile properties of titanium alloys. As shown in Figure 1, the tensile strength of TA15 without ZrN is 936MPa, and after adding ZrN, according to the reaction formula of Ti+N=TiN, the mass fraction of TiN is 1.33%, and its tensile strength is 1066MPa, the strength is improved up nearly 13.8%.

Embodiment 3: A method of adding zirconium nitride to realize composite strengthening of high-temperature titanium alloys is specifically carried out according to the following steps:

1. Calculate the mass percentage of each element according to the nominal chemical composition of the final product Ti60 alloy Ti–5.8Al–4.0Sn–3.5Zr–1Mo–0.85Nd–0.4Si, and perform the ingredients according to the elements contained in it to obtain the raw material to be melted. The total mass of ingredients is 20kg, including 16.81kg of titanium sponge with a purity of ≥99%, 0.06kg of high-purity aluminum with a purity of ≥99%, 0.31kg of molybdenum-aluminum alloy with a molybdenum content of 65%, and 1.4 kg of aluminum-tin alloy with a tin content of 55%. kg, 0.43kg of neodymium-aluminum alloy with 40% neodymium content, 0.16kg of aluminum-silicon master alloy with 50% silicon content, and 0.81kg of ZrN;

2. Put the raw material to be melted into the water-cooled copper crucible vacuum induction melting furnace, evacuate to 3.0×10 ^-3 MPa, and pour the alloy raw material after melting for 10 minutes; place a piece of thickness ≥30mm at the bottom of the mold when pouring the ingot The copper plate is obtained to obtain a high-temperature titanium alloy ingot to be heat-treated;

3. Put the high-temperature titanium alloy ingot to be heat-treated into a heat-treatment furnace with a temperature of 900° C. for 50 hours, and then cool with the furnace to obtain a Ti60 alloy reinforced by zirconium nitride.

Embodiment 4: a kind of preparation method of zirconium-containing high-temperature titanium alloy is specifically carried out according to the following steps:

1. Calculate the mass percentage of each element according to the nominal chemical composition of the final product Ti60 alloy Ti–5.8Al–4.0Sn–3.5Zr–1Mo–0.85Nd–0.4Si, and perform the ingredients according to the elements contained in it to obtain the raw material to be melted. ; The total mass of ingredients is 20kg, Ti element is provided by sponge titanium with a purity of ≥99%, Zr element is provided by sponge zirconium, the rest elements are provided by high-purity aluminum with a purity of ≥99%, molybdenum-aluminum alloy with a molybdenum content of 65%, and a tin content of 55% aluminum-tin alloy, neodymium-aluminum alloy with 40% neodymium content, and aluminum-silicon master alloy with 50% silicon content;

2. Put the raw material to be melted into the water-cooled copper crucible vacuum induction melting furnace, evacuate to 3.0×10 ^-3 MPa, and pour the alloy raw material after melting for 10 minutes; place a piece of thickness ≥30mm at the bottom of the mold when pouring the ingot The copper plate is obtained to obtain a high-temperature titanium alloy ingot to be heat-treated;

3. Put the high-temperature titanium alloy ingot to be heat-treated into a heat-treatment furnace with a temperature of 900° C. for 50 hours, and then cool with the furnace to obtain a Ti60 alloy.

The core samples of the zirconium nitride reinforced Ti60 alloy obtained in Example 3 and the Ti60 alloy obtained in Example 4 were cut by wire cutting, and the titanium alloy without ZrN and the titanium alloy containing ZrN were simultaneously tested by electronic universal tensile testing machine. Room temperature tensile properties of titanium alloys. As shown in Figure 2, the tensile strength of Ti60 without ZrN is 946MPa, and after adding ZrN, according to the reaction formula of Ti+N=TiN, the mass fraction of TiN is 2.44%, and its tensile strength is 1082MPa, and the strength is improved. up nearly 14.4%.

Embodiment 5: A method of adding zirconium nitride to realize composite strengthening of high-temperature titanium alloys is specifically carried out according to the following steps:

1. Calculate the mass percentage of each element according to the nominal chemical composition Ti-6Al-2Sn-4Zr-2Mo of the final product Ti6242 alloy, and carry out the ingredients according to the elements contained in it to obtain the raw material to be melted; the total mass of the ingredients is 20kg, of which the purity ≥99% sponge titanium 17.08kg, purity ≥99% industrial pure aluminum 0.65kg, molybdenum content 65% molybdenum aluminum alloy 0.62kg, tin content 55% aluminum-tin alloy 0.73kg, ZrN powder 0.92kg;

2. Put the raw material to be melted into the water-cooled copper crucible vacuum induction melting furnace, evacuate to 3.0×10 ^-3 MPa, and pour the alloy raw material after melting for 10 minutes; place a piece of thickness ≥30mm at the bottom of the mold when pouring the ingot The copper plate is obtained to obtain a high-temperature titanium alloy ingot to be heat-treated;

3. Put the high-temperature titanium alloy ingot to be heat-treated into a heat-treatment furnace with a temperature of 900° C. for 50 hours, and then cool with the furnace to obtain a Ti6242 alloy reinforced by zirconium nitride.

Embodiment 6: a kind of preparation method of zirconium-containing high-temperature titanium alloy is specifically carried out according to the following steps:

1. Calculate the mass percentage of each element according to the nominal chemical composition Ti-6Al-2Sn-4Zr-2Mo of the final product Ti6242 alloy, and carry out the ingredients according to the elements contained in it to obtain the raw material to be melted; the total mass of the ingredients is 20kg, and the Ti element It is provided by sponge titanium with a purity of ≥99%, Zr element is provided by sponge zirconium, and the remaining elements are provided by industrial pure aluminum with a purity of ≥99%, molybdenum-aluminum alloy with a molybdenum content of 65%, and aluminum-tin alloy with a tin content of 55%;

2. Put the raw material to be melted into the water-cooled copper crucible vacuum induction melting furnace, evacuate to 3.0×10 ^-3 MPa, and pour the alloy raw material after melting for 10 minutes; place a piece of thickness ≥30mm at the bottom of the mold when pouring the ingot The copper plate is obtained to obtain a high-temperature titanium alloy ingot to be heat-treated;

3. Put the high-temperature titanium alloy ingot to be heat-treated into a heat-treatment furnace with a temperature of 900° C. for 50 hours, and then cool with the furnace to obtain a Ti6242 alloy.

The core samples of the zirconium nitride reinforced Ti6242 alloy obtained in Example 5 and the Ti6242 alloy obtained in Example 6 were cut by wire cutting, and the titanium alloy without ZrN and the titanium alloy containing ZrN were simultaneously tested by electronic universal tensile testing machine. Room temperature tensile properties of titanium alloys. As shown in Figure 3, the tensile strength of Ti6242 without ZrN is 930MPa, and after adding ZrN, according to the reaction formula of Ti+N=TiN, the mass fraction of TiN is 2.72%, and its tensile strength is 1103MPa, the strength is improved up nearly 18.6%.

Embodiment 7: A method of adding zirconium nitride to realize composite strengthening of high-temperature titanium alloys is specifically carried out according to the following steps:

1. Calculate the mass percentage 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 carry out ingredients according to the elements contained in it to obtain the raw materials to be melted; the total mass of ingredients 20kg, including 17.15kg of titanium sponge with a purity of ≥99%, 0.65kg of industrial pure aluminum with a purity of ≥99%, 0.12kg of molybdenum-aluminum alloy with a molybdenum content of 65%, 0.98kg of aluminum-tin alloy with a tin content of 55%, and a silicon content of 0.98kg It is 0.18kg of 50% Al-Si master alloy and 0.92kg of ZrN powder;

2. Put the raw material to be melted into the water-cooled copper crucible vacuum induction melting furnace, evacuate to 3.0×10 ^-3 MPa, and pour the alloy raw material after melting for 10 minutes; place a piece of thickness ≥30mm at the bottom of the mold when pouring the ingot The copper plate is obtained to obtain a high-temperature titanium alloy ingot to be heat-treated;

3. Put the high-temperature titanium alloy ingot to be heat-treated into a heat-treatment furnace with a temperature of 900° C. for 50 hours, and then cool with the furnace to obtain a Ti1100 alloy reinforced by zirconium nitride.

Embodiment 8: a kind of preparation method of zirconium-containing high-temperature titanium alloy is specifically carried out according to the following steps:

1. Calculate the mass percentage 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 carry out ingredients according to the elements contained in it to obtain the raw materials to be melted; the total mass of ingredients It is 20kg, Ti element is provided by sponge titanium with a purity of ≥99%, Zr element is provided by sponge zirconium, and other elements are provided by industrial pure aluminum with a purity of ≥99%, molybdenum-aluminum alloy with a molybdenum content of 65%, and aluminum with a tin content of 55%. Tin alloys, aluminum-silicon master alloys with a silicon content of 50% are provided;

2. Put the raw material to be melted into the water-cooled copper crucible vacuum induction melting furnace, evacuate to 3.0×10 ^-3 MPa, and pour the alloy raw material after melting for 10 minutes; place a piece of thickness ≥30mm at the bottom of the mold when pouring the ingot The copper plate is obtained to obtain a high-temperature titanium alloy ingot to be heat-treated;

3. Put the high-temperature titanium alloy ingot to be heat-treated into a heat-treatment furnace with a temperature of 900° C. for 50 hours, and then cool with the furnace to obtain a Ti1100 alloy.

The core samples of the zirconium nitride reinforced Ti1100 alloy obtained in Example 7 and the Ti1100 alloy obtained in Example 8 were cut by wire cutting, and the titanium alloy without ZrN and the titanium alloy containing ZrN were simultaneously tested by electronic universal tensile testing machine. Room temperature tensile properties of titanium alloys. As shown in Figure 4, the tensile strength of Ti1100 without ZrN is 916MPa, and after adding ZrN, according to the reaction formula of Ti+N=TiN, the mass fraction of TiN is 2.72%, and its tensile strength is 1068MPa, the strength is improved up nearly 16.6%, while shaping slightly decreased.

Embodiment 9: A method of adding zirconium nitride to realize composite strengthening of high-temperature titanium alloys is specifically carried out according to the following steps:

1. Calculate the mass percentage of each element according to the nominal chemical composition Ti-6Al-3Sn-10Zr-0.8Mo-1Nb-1W-0.3Si of the final product zirconium-containing high-temperature titanium alloy, and perform the ingredients according to the elements contained in it to obtain the Melting raw materials; the total mass of ingredients is 20kg, including 15.45kg of titanium sponge with a purity of ≥99%, 0.43kg of industrial pure aluminum with a purity of ≥99%, 0.25kg of molybdenum-aluminum alloy with a molybdenum content of 65%, and aluminum-tin with a tin content of 55%. 1.09kg of alloy, 0.33kg of niobium-aluminum alloy with 60% niobium content, 0.2kg of pure tungsten with 99.9% purity, 0.12kg of aluminum-silicon master alloy with 50% silicon content, and 2.31kg of ZrN;

2. Put the raw material to be melted into the water-cooled copper crucible vacuum induction melting furnace, evacuate to 3.0×10 ^-3 MPa, and pour the alloy raw material after melting for 10 minutes; place a piece of thickness ≥30mm at the bottom of the mold when pouring the ingot The copper plate is obtained to obtain a high-temperature titanium alloy ingot to be heat-treated;

3. Put the high-temperature titanium alloy ingot to be heat-treated into a heat-treatment furnace with a temperature of 900° C. for 50 hours, and then cool with the furnace to obtain a high-temperature titanium alloy containing zirconium reinforced by zirconium nitride.

Embodiment ten: a kind of preparation method of zirconium-containing high-temperature titanium alloy is specifically carried out according to the following steps:

1. Calculate the mass percentage of each element according to the nominal chemical composition Ti-6Al-3Sn-10Zr-0.8Mo-1Nb-1W-0.3Si of the final product zirconium-containing high-temperature titanium alloy, and perform the ingredients according to the elements contained in it to obtain the Melting raw materials; the total mass of ingredients is 20kg, the Ti element is provided by sponge titanium with a purity of ≥99%, the Zr element is provided by sponge zirconium, and the remaining elements are provided by industrial pure aluminum with a purity of ≥99%, molybdenum-aluminum alloy with a molybdenum content of 65%, tin Al-tin alloy with a content of 55%, niobium-aluminum alloy with a niobium content of 60%, pure tungsten with a purity of ≥99%, and aluminum-silicon master alloy with a silicon content of 50%;

2. Put the raw material to be melted into the water-cooled copper crucible vacuum induction melting furnace, evacuate to 3.0×10 ^-3 MPa, and pour the alloy raw material after melting for 10 minutes; place a piece of thickness ≥30mm at the bottom of the mold when pouring the ingot The copper plate is obtained to obtain a high-temperature titanium alloy ingot to be heat-treated;

3. Put the high-temperature titanium alloy ingot to be heat-treated into a heat-treatment furnace with a temperature of 900° C. for 50 hours, and then cool with the furnace to obtain a high-temperature titanium alloy containing zirconium.

The core samples of the zirconium nitride-reinforced zirconium-containing high-temperature titanium alloy obtained in Example 9 and the zirconium-containing high-temperature titanium alloy obtained in Example 10 were cut by wire cutting, and the samples without ZrN were simultaneously tested by an electronic universal tensile testing machine. Room temperature tensile properties of titanium alloys and titanium alloys containing ZrN. As shown in Figure 5, the tensile strength of Ti-6Al-3Sn-10Zr-0.8Mo-1Nb-1W-0.3Si without ZrN is 937MPa, and after adding ZrN, TiN is formed according to the reaction formula of Ti+N=TiN Its mass fraction is 6.82%, its tensile strength is 1132MPa, and the strength is increased by 20.8%.

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.

Images