Method for producing a TZM alloy doped with rare earth elements La and Y

Abstract

The present application relates to the alloy preparation technical field, specifically provide a kind of TZM alloy doped with rare earth elements La and Y and preparation method thereof.La-Y-TZM alloy is prepared by powder metallurgy (PM) and hot isostatic pressing (HIP) process.Rare earth elements La and Y are added into molybdenum powder by liquid-liquid doping technology, the phenomenon of uneven distribution of rare earth elements is improved, the formation of Ti, Zr oxide is inhibited, the introduction of HIP technology can greatly improve the density of TZM alloy, reduce segregation, control the segregation range to be about the size of powder particle size, and can significantly refine the grain size of TZM alloy, so that high densification, low segregation, fine-grained TZM alloy can be obtained, and the room temperature strength and high temperature mechanical properties are significantly improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of alloy preparation, and particularly provides a preparation method of a TZM alloy doped with rare earth elements La and Y. BACKGROUND

[0002] The most common molybdenum alloy at present is TZM alloy, that is, titanium-zirconium-molybdenum alloy, also known as molybdenum-titanium-zirconium alloy. The alloy is formed by doping a certain amount of Ti (titanium) and Zr (zirconium) into a metal molybdenum base. The alloy content is less than 1% in principle. Among refractory materials, the TZM alloy is well known for its excellent high-temperature performance, a relatively high recrystallization threshold, and relatively easy processing under room temperature conditions. However, the TZM alloy is easily oxidized, and a high oxygen content can increase the probability of the transformation of carbide into oxide. The oxide segregation at the grain boundary can greatly reduce the mechanical properties, thereby weakening the effect of second-phase strengthening, and sharply reducing the tensile strength and elongation of the material, affecting the performance of the material. In view of this problem, the current method is to develop a rare earth TZM alloy on the basis of the existing TZM alloy. Because the rare earth element has strong oxidizing properties, its addition can inhibit the formation of Ti and Zr oxides to a certain extent. The commonly used doped rare earth elements are lanthanum and yttrium.

[0003] In industry, vacuum melting and powder metallurgy are commonly used to prepare the TZM alloy. The grain of the TZM alloy blank prepared by the vacuum electric furnace melting method is generally relatively coarse and the size distribution is very uneven. The subsequent process is complex, occupies many devices, consumes a lot of resources, has high cost, and has a low yield. The powder metallurgy process generally consists of four parts: powder preparation, ball milling, blank pressing, and sintering. The TZM alloy prepared by the powder metallurgy method is mainly prepared by cold isostatic pressing. The high-purity molybdenum powder, TiH2 powder, ZrH2 powder, and graphite powder mixed according to a certain proportion are pressed into a block, and then a TZM blank product is prepared by high-temperature sintering. However, the TZM alloy prepared by the powder metallurgy method inevitably has pores, pores between powders, and cracks, which cannot be completely eliminated, and other defects, which greatly affect the performance of the alloy.

[0004] Therefore, the present application is proposed. SUMMARY

[0005] The first object of the present application is to provide a preparation method of a TZM alloy doped with rare earth elements La and Y.

[0006] The second object of the present application is to provide a TZM alloy prepared by the above preparation method.

[0007] In order to achieve the above object, the present application adopts the following technical scheme:

[0008] A preparation method of a TZM alloy doped with rare earth elements La and Y, comprising the following steps:

[0009] S1: La(NO3)3 solution and Y(NO3)3 solution are added to (NH4)2Mo4O 13 solution, and after mixing, reduction is carried out using anhydrous ethanol and H2 in sequence to obtain molybdenum powder uniformly doped with lanthanum oxide and yttrium oxide;

[0010] S2: The molybdenum powder doped with lanthanum oxide and yttrium oxide in S1, TiH2 powder, ZrH2 powder and graphite powder are put into a mixer for mixing, and vacuum drying is carried out to obtain alloy powder;

[0011] S3: The alloy powder in S2 is loaded into a ball mill for ball milling;

[0012] S4: The alloy powder after ball milling in S3 is subjected to cold isostatic pressing and sintering in sequence;

[0013] S5: The TZM alloy obtained in S4 is subjected to hot isostatic pressing, stainless steel is used as a cladding material, it is placed in a degassing furnace for air extraction and cladding, and then it is placed in a hot isostatic pressing machine, argon is used as a pressure gas, the heating temperature is 1200-1400℃, the pressure is 130-150 MPa, and after hot isostatic pressing, it is cooled to room temperature in the furnace.

[0014] Further, the content of lanthanum oxide and yttrium oxide in the molybdenum powder doped with lanthanum oxide and yttrium oxide in S1 is 0.5% w / w.

[0015] Further, after reduction of anhydrous ethanol in S1, molybdenum trioxide powder containing lanthanum oxide and yttrium oxide is obtained by calcination, and then secondary reduction is carried out under the action of H2 to obtain molybdenum powder uniformly doped with lanthanum oxide and yttrium oxide.

[0016] Further, in S2, the content of TiH2 powder is 0.40%-0.60% w / w, the content of ZrH2 powder is 0.06%-0.10% w / w, the content of graphite powder is 0.03%-0.05% w / w, and the balance is the molybdenum powder doped with lanthanum oxide and yttrium oxide.

[0017] Further, the mixing time in S2 is 1.5-2.5h.

[0018] Further, the ball milling conditions in S3 are as follows: the diameter of the milling ball is 5-10mm, the ball-to-material ratio is 1.5-2:1, the material filling rate is 70%, the ball milling speed is set to 250-300r / min, and the ball milling time is 1.5-2.5h.

[0019] Further, after ball milling, the alloy powder is vacuum sealed and then subjected to cold isostatic pressing.

[0020] Further, the pressure for cold isostatic pressing in S4 is 130-170Mpa.

[0021] Further, the sintering condition in the S4 includes: pressureless sintering under H2 protection, 2000-2100 DEG C sintering for 2.5-3.5h.

[0022] The TZM alloy prepared by the preparation method.

[0023] Compared with the prior art, the technical effect of the present application is:

[0024] The present application adopts powder metallurgy technology (PM), and rare earth elements La and Y are used as doping elements of the TZM alloy. The formed rare earth oxides can prevent the grain growth in the powder sintering process, and thus can play a certain fine-grain strengthening role. Meanwhile, La and Y have strong oxidizing property, and the doping of La and Y can form uniformly dispersed particles in the TZM alloy, play a dispersion strengthening role, and improve the segregation of C and O at the grain boundary, so that the recrystallization temperature of the TZM is further improved. In addition, by combining La and Y with O, the formation of Ti and Zr oxides is inhibited, and the rare earth element oxides (strong oxidizing property) can be formed, and then the second phase particles are generated, so as to fully play the precipitation strengthening role of Ti and Zr and improve the comprehensive performance of the TZM.

[0025] It is found that different doping methods can also affect the internal organizational structure of the TZM alloy. The present application adopts liquid-liquid doping. The advantage of this method is that the contact area of the rare earth elements with the matrix material is larger, and the mixing of the rare earth elements and Mo in the form of ions can effectively improve the uneven distribution of the second phase particles. In this way, more uniform and smaller second phase particles can be obtained, and the distribution is also more uniform.

[0026] In addition, the hot isostatic pressing (HIP) is used to further improve the density of the PM TZM alloy, construct a high-density substructure, reduce the segregation, control the segregation range to be about the size of the powder particle, play a role of substructure strengthening and optimization of performance, and can significantly refine the grain size of the alloy. Therefore, the TZM alloy with high densification, low segregation and fine grain can be obtained, and the room temperature strength-plasticity matching and high-temperature mechanical properties are significantly improved. BRIEF DESCRIPTION OF DRAWINGS

[0027] The various technical features of the present application and the relationship between them will be further described below with reference to the accompanying drawings. The drawings are exemplary, some technical features are not shown in actual proportion, and some technical features in the drawings can be omitted, which are conventional in the technical field to which the present application belongs and are not essential for understanding and implementing the present application, or additional technical features are shown, which are not essential for understanding and implementing the present application. That is, the combination of various technical features shown in the drawings is not used to limit the present application. In addition, the same reference signs refer to the same contents throughout the present application. The specific drawings are as follows:

[0028] Figure 1 is a powder morphology diagram of the TZM alloy material after step 3 in the embodiment of the present application;

[0029] Figure 2 is a powder particle size statistical diagram of the TZM alloy material after step 3 in the embodiment of the present application;

[0030] Figure 3 is an XRD diagram of the powder of the TZM alloy material after step 3 in the embodiment of the present application;

[0031] Figure 4 is an Euler diagram of the TZM alloy material after step 6 in the embodiment of the present application;

[0032] Figure 5 is a grain size statistical diagram of the TZM alloy material after step 6 in the embodiment of the present application;

[0033] Figure 6 is a room temperature tensile fracture diagram of the TZM alloy material after step 6 in the embodiment of the present application;

[0034] Figure 7 is a 600℃ tensile fracture diagram of the TZM alloy material after step 6 in the embodiment of the present application;

[0035] Figure 8 is an Euler diagram of the TZM alloy material after step 5 in the embodiment of the present application;

[0036] Figure 9 is a grain size statistical diagram of the TZM alloy material after step 5 in the embodiment of the present application;

[0037] Figure 10 is a room temperature tensile fracture diagram of the TZM alloy material after step 5 in the embodiment of the present application;

[0038] Figure 11 is a 600℃ tensile fracture diagram of the TZM alloy material after step 5 in the embodiment of the present application. DETAILED DESCRIPTION

[0039] Hereinafter, a specific embodiment of the present application will be described in detail.

[0040] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. If there is a conflict between the meanings of terms in the specification and the meanings of the terms as understood by those skilled in the art, the meanings of the terms as understood by those skilled in the art shall prevail. In addition, the terms used in the present specification are used only for the purpose of describing the embodiments of the present application, and are not intended to limit the present application.

[0041] Titanium-zirconium-molybdenum alloy (TZM alloy) is the most common molybdenum-based alloy, in which Mo (molybdenum) is used as a matrix, and trace elements such as Ti (titanium), Zr (zirconium) and C (carbon) can form Mo-Ti, Mo-Zr interstitial solid solution and Ti, Zr carbide second phase particles, which play a role of solid solution strengthening and second phase strengthening, so compared with pure Mo, the recrystallization temperature is higher, and the high-temperature mechanical properties are also more excellent.

[0042] Hot isostatic pressing (HIP) generally refers to placing a workpiece (blank, casting, etc.) in a closed container, filling the container with a pressure medium, and the pressure medium is generally nitrogen or argon, under the combined action of high temperature and high pressure, the density of the alloy is higher than that of pressureless sintering. The heating temperature is generally 0.7-0.9 times the melting point.

[0043] The first aspect of the present application provides a preparation method of a TZM alloy doped with rare earth elements La and Y, which comprises the following steps:

[0044] S1: La(NO3)3 solution and Y(NO3)3 solution are added to (NH4)2Mo4O 13 solution, and then reduced with anhydrous ethanol and H2 in sequence to obtain molybdenum powder uniformly doped with lanthanum oxide and yttrium oxide.

[0045] S2: The molybdenum powder doped with lanthanum oxide and yttrium oxide in S1, TiH2 powder, ZrH2 powder and graphite powder are put into a mixer for mixing, and then vacuum drying is performed to obtain alloy powder.

[0046] S3: The alloy powder in S2 is loaded into a ball mill for ball milling.

[0047] S4: The alloy powder after ball milling in S3 is sequentially subjected to cold isostatic pressing and sintering.

[0048] S5: The TZM alloy obtained in S4 is subjected to hot isostatic pressing, stainless steel is used as a cladding material, placed in a degassing furnace for degassing and cladding, and then placed in a hot isostatic pressing machine, argon is used as a pressure gas, the heating temperature is 1200-1400℃, the pressure is 130-150MPa, and the hot isostatic pressing is cooled to room temperature in the furnace.

[0049] The present application aims at some problems in the preparation of TZM alloy by conventional powder metallurgy process, and proposes a preparation method of TZM alloy doped with rare earth elements La and Y, i.e. preparing La-Y-TZM alloy by powder metallurgy (PM) + hot isostatic pressing (HIP). The present application has the following two advantages: firstly, the rare earth elements La and Y have strong oxidizing property, and the addition of La and Y can form La2O3 and Y2O3, and further generate second phase particles, thereby playing a role of dispersion strengthening, and can also reduce the probability of the transformation of Ti and Zr carbides in the TZM alloy into oxides, and fully play the role of precipitation strengthening; secondly, the introduction of HIP technology can greatly improve the density of the TZM alloy, reduce the segregation of the TZM alloy, control the segregation range to be about the size of the powder particle, and thus obtain the TZM alloy with high alloying and low segregation, and introduce high-density substructure, thereby playing a role of substructure strengthening and optimizing the performance.

[0050] In some embodiments, the rare earth elements La and Y are doped into the ammonium molybdate solution in the form of nitrate solution. Specifically, La(NO3)3 solution and Y(NO3)3 solution are added into the (NH4)2Mo4O 13 The solution is stirred uniformly, anhydrous ethanol is added for mixing after uniform stirring, the addition of alcohol can provide a certain reduction environment, and after uniform mixing, spray drying is performed to prepare precursor powder, and then calcination is performed to obtain molybdenum trioxide powder containing lanthanum oxide and yttrium oxide, and finally the obtained powder is subjected to secondary reduction under the action of H2 to obtain molybdenum powder uniformly doped with lanthanum oxide and yttrium oxide.

[0051] In the preferred embodiments, the content of lanthanum oxide and yttrium oxide in the molybdenum powder doped with lanthanum oxide and yttrium oxide in S1 is 0.5% w / w.

[0052] In some embodiments, the TiH2 powder in S2 is 0.40% to 0.60% w / w, the ZrH2 powder is 0.06% to 0.10% w / w, the graphite powder is 0.03% to 0.05% w / w, and the balance is the molybdenum powder doped with lanthanum oxide and yttrium oxide.

[0053] In some embodiments, the mixing time in S2 is 1.5 to 2.5 h, and preferably 2 h. The vacuum drying conditions are as follows: the uniformly mixed alloy powder is placed in a vacuum drying oven for drying, the temperature is 70°C, and the time is 4 h.

[0054] In some embodiments, the ball milling conditions in S3 are as follows: the diameter of the milling ball is 5 to 10 mm, the ball-to-material ratio is 1.5 to 2:1, the material filling rate is 70%, the ball milling speed is set to 250 to 300 r / min, and the ball milling time is 1.5 to 2.5 h, which can make the alloy powder mixing more uniform.

[0055] In some embodiments, after ball milling, the alloy powder is vacuum sealed and then cold isostatic pressed. Preferably, the pressure of cold isostatic pressing in S4 is 130-170 MPa, and more preferably 150 MPa.

[0056] In some embodiments, the sintering conditions in S4 include: pressureless sintering in H2 protection at 2000-2100℃ for 2.5-3.5h, and preferably at 2050℃ for 3h. H2 has two effects in powder sintering, first, it prevents oxidation by isolating air, although molybdenum is not easy to oxidize at room temperature, but it will oxidize at about 400℃, and the oxidation rate will greatly increase above 600℃, which is mainly because the generated molybdenum trioxide (MoO3) will volatilize, thereby causing weight loss; the other effect of H2 is to reduce part of the MoO3 generated on the surface of the TZM alloy blank during sintering to Mo.

[0057] In some embodiments, the main purpose of hot isostatic pressing in S5 is to further improve the density of the PM TZM alloy, the HIP process uses stainless steel as a cladding material, is placed in a degassing furnace for vacuuming and cladding, and then is placed in a hot isostatic pressing machine, argon is used as the pressure gas, the heating temperature is 1300℃, and the pressure is 140 MPa, and after hot isostatic pressing, the furnace is cooled to room temperature.

[0058] The present application will be further described in conjunction with specific embodiments, and the advantages and characteristics of the present application will be more clearly described with the description. However, these embodiments are only exemplary and do not constitute any limitation on the scope of the present application. Those skilled in the art should understand that the details and forms of the technical solutions of the present application can be modified or replaced without departing from the spirit and scope of the present application, and such modifications and replacements all fall within the protection scope of the present application.

[0059] Embodiments

[0060] The present application provides a preparation method of a TZM alloy doped with rare earth elements La and Y, which mainly comprises the following steps:

[0061] Step 1: manufacturing molybdenum powder doped with lanthanum oxide and yttrium oxide, adding La(NO3)3 solution and Y(NO3)3 solution in a certain proportion (10g lanthanum nitrate + 10g yttrium nitrate) into (NH4)2Mo4O 13 solution (1800g) and stirring uniformly, then adding an appropriate amount of anhydrous ethanol for mixing, the addition of alcohol can provide a certain reduction environment, after mixing uniformly, spray drying is performed to prepare a precursor powder, then calcination is performed to obtain molybdenum trioxide powder containing lanthanum oxide and yttrium oxide, and finally the obtained powder is subjected to secondary reduction under the action of H2 to obtain molybdenum powder uniformly doped with lanthanum oxide and yttrium oxide.

[0062] Step 2: mixing powder, the Mo powder doped with lanthanum oxide and yttrium oxide, TiH2 powder, ZrH2 powder and graphite powder are put into a mixer according to the following proportions (mass percentage): TiH2 powder 0.40-0.60% (4-6g), ZrH2 powder 0.06-0.10% (0.6-1g), graphite powder 0.03-0.05% (0.3-0.5g), and the rest is Mo powder doped with lanthanum oxide and yttrium oxide, the content of lanthanum oxide in the Mo powder is 0.5%, and the content of yttrium oxide is 0.5%.

[0063] Step 3: ball milling, the vacuum dried alloy powder is loaded into a ball mill for ball milling, the diameter of the grinding ball is 5-10mm, the ball-to-material ratio is 1.5-2:1, the material filling rate is 70%, the ball milling speed is set to 250-300r / min, the ball milling time is 2h, after ball milling, the alloy powder is discharged and sieved, the alloy powder and the grinding ball are separated, and finally the vacuum packaging machine is used for vacuum sealing and labeling.

[0064] As shown in Figures 1-3 , the powder particle size distribution is relatively concentrated, mainly distributed between 0.5-2μm, and individual size can reach 5μm, the overall size is relatively small, and there is a certain agglomeration phenomenon; the XRD detection result shows a single peak of Mo, but this does not mean that carbide or oxide does not exist, it may be because the content of other elements is lower than the detection lower limit of the equipment, so it is not detected.

[0065] Step 4: cold isostatic pressing, the cold isostatic pressing pressure of TZM alloy is 150MPa, and the pressed blank is sintered.

[0066] Step 5: sintering, the powder sintering process is 2050℃ sintering for 3h, and H2 protection is used in the sintering process. H2 has two effects in powder sintering, first, it isolates air to prevent oxidation, although molybdenum is not easy to oxidize at room temperature, but it will oxidize at about 400℃, and the oxidation rate will greatly increase above 600℃, this is mainly because the generated molybdenum trioxide (MoO3) will volatilize, resulting in weight loss; the other effect of H2 is to reduce part of the MoO3 generated on the surface of the TZM alloy blank during sintering to Mo.

[0067] After this step, the material is detected (results as shown in Figures 8-11The particle size of the molybdenum powder doped with rare earth elements La and Y is mainly distributed between 0.5-2 μm, and the density of the sintered alloy reaches 94.2%, the average grain size is 40 μm, and the maximum grain size is 43.8 μm; the average hardness of the PM TZM alloy is 166 HV, the average tensile strength of the TZM alloy at room temperature is 426 MPa, the elongation after fracture is 3%, which indicates that the plasticity of the TZM alloy at room temperature is poor, and the ductile-brittle transition temperature of the TZM alloy is higher than room temperature; the tensile strength at 600°C is 398 MPa, the elongation after fracture is 19%, and the reduction of area is 58%; the compressive stress of the TZM alloy at 1050°C is 325 MPa, at 1100°C is 289 MPa, at 1150°C is 246 MPa, and at 1200°C is 217 MPa.

[0068] Step 6: hot isostatic pressing. The main purpose of the hot isostatic pressing is to further improve the density of the PM TZM alloy. The HIP process uses stainless steel as a cladding material, is placed in a degassing furnace for vacuumizing and welding of the cladding, and then is placed in a hot isostatic pressing machine, argon is used as the pressure gas, the heating temperature is 1300°C, and the pressure is 140 MPa. After the hot isostatic pressing, the sample is cooled to room temperature in the furnace.

[0069] The performance parameters of the TZM alloy doped with rare earth elements La and Y prepared in this example are as follows: the particle size of the molybdenum powder doped with rare earth elements La and Y is mainly distributed between 0.5-2 μm, the density of the hot isostatic pressed alloy reaches 95.6%, the average grain size is 18.7 μm, and the maximum grain size is 19.8 μm; the average hardness of the PM+HIP TZM alloy is 188 HV, the tensile strength at room temperature is 502 MPa, and the elongation after fracture is 5%, which may be related to the closure of small pores, the tensile strength at 600°C is 456 MPa, the elongation after fracture is 15%, and the reduction of area is 43%; the compressive stress of the TZM alloy at 1050°C is 392 MPa, at 1100°C is 366 MPa, at 1150°C is 318 MPa, and at 1200°C is 288 MPa.

[0070] From Figure 6 and Figure 10 It can be seen that: the fracture mode of the TZM alloy at room temperature before and after the HIP is intergranular fracture; micron-sized defects exist on the fracture surface, and some defects are caused by the shedding of the second phase; after the hot isostatic pressing, the nanometer-sized pore defects are closed to some extent; the fracture characteristics before and after the HIP are similar, a small amount of cleavage planes formed by the transgranular fracture exist on the fracture surface, and most of the fractures are intergranular; after the HIP, the tensile properties are improved to some extent due to the closure of the pore defects in the PM process.

[0071] From Figure 7 and Figure 11It can be seen that the fracture mode of TZM alloy at high temperature before and after HIP is ductile fracture, the tensile temperature is much higher than the ductile-brittle transition temperature of TZM alloy; the fracture characteristics are similar, the dimple size is different, the smaller one is 2-5 μm, the larger one is 20-30 μm, in addition, there are still a small amount of cleavage planes, there are dense tear ridges, and some larger dimples have second phase particles, the high temperature tensile properties after HIP are improved.

[0072] The Gemini SEM 500 scanning electron microscope is used to observe the TZM powder, and the specific operation is to spread a small amount of TZM alloy powder on the conductive glue, and blow off the powder that is not firmly combined with the air blower. Then the Image-Tool software is used to measure the powder particle size, and the measurement results are processed by Origin software to obtain the particle size distribution graph of TZM powder.

[0073] The hardness test is carried out on THVP-50 Vickers hardness tester, the test load is 10 Kg, before the hardness test, the sample is polished well, the upper and lower surfaces of the sample are kept flat, and the hardness tester is calibrated with a standard block before testing.

[0074] The room temperature tensile and 600℃ high temperature tensile are carried out on CMT5205 electronic universal testing machine, the manufacturer is Metzler industrial systems Co., Ltd., which is equipped with constant temperature furnace and nitrogen protection, which can prevent the sample from oxidizing during tensile; the tensile sample is bar type, the high temperature tensile heating rate is 25℃ / min, the nitrogen valve is opened when the furnace temperature is about 200℃, and the tensile test is carried out after 10 min of heat preservation, in order to ensure the consistency of experimental results, the rate of all tensile experiments is 1mm / min.

[0075] The hot compression test is completed by Gleeble-3800 thermal simulation testing machine, the sample is heated to the deformation temperature at a speed of 20℃ / s before deformation, the experimental temperature is 1050℃, 1100℃, 1150℃ and 1200℃ respectively; the deformation rate is 0.01s-1; the compression starts after 3 min of temperature equalization, and the sample is gas quenched immediately after the experiment to preserve the high temperature deformation structure, the hot compression sample is 10mm in diameter and 15mm in height, the surface is polished, the test is axial single pass compression, and the deformation amount is 60%.

Claims

1. A method for producing a TZM alloy doped with rare earth elements La and Y, characterized by, The method comprises the following steps: S1: La(NO3)3 solution and Y(NO3)3 solution are added to (NH4)2Mo4O 13 solution, and after mixing, reduction is carried out using anhydrous ethanol and H2 in sequence to obtain lanthanum oxide and yttrium oxide uniformly doped molybdenum powder; The content of lanthanum oxide and yttrium oxide in the molybdenum powder doped with lanthanum oxide and yttrium oxide in S1 is 0.5% w / w; S2: The molybdenum powder doped with lanthanum oxide and yttrium oxide in S1, TiH2 powder, ZrH2 powder and graphite powder are put into a mixer for mixing, and then vacuum drying is performed to obtain an alloy powder; The TiH2 powder is 0.40%-0.60% w / w, the ZrH2 powder is 0.06%-0.10% w / w, the graphite powder is 0.03%-0.05% w / w, and the balance is the molybdenum powder doped with lanthanum oxide and yttrium oxide; S3: The alloy powder in S2 is loaded into a ball mill for ball milling; The ball milling conditions are as follows: the diameter of the milling ball is 5-10 mm, the ball-to-material ratio is 1.5-2:1, the material filling rate is 70%, the ball milling speed is set to 250-300 r / min, and the ball milling time is 1.5-2.5 h; S4: The alloy powder after ball milling in S3 is sequentially subjected to cold isostatic pressing and sintering; The sintering conditions include: using H2 protection, sintering at 2000-2100℃ for 2.5-3.5 h by pressureless sintering; S5: The TZM alloy obtained in S4 is subjected to hot isostatic pressing, stainless steel is used as the cladding material, the cladding is welded after being degassed in a degassing furnace, and then the cladding is placed in a hot isostatic pressing machine, argon is used as the pressure gas, the heating temperature is 1200-1400℃, the pressure is 130-150 MPa, and the cladding is cooled to room temperature in the furnace after hot isostatic pressing.

2. The production method according to claim 1, characterized by, The molybdenum trioxide powder containing lanthanum oxide and yttrium oxide is obtained by roasting the molybdenum trioxide powder after reduction with anhydrous ethanol in S1, and then the molybdenum powder uniformly doped with lanthanum oxide and yttrium oxide is obtained by secondary reduction under the action of H2.

3. The preparation method according to claim 1, characterized in that, The mixing time in S2 is 1.5-2.5 h.

4. The method of claim 1, wherein, After ball milling, the alloy powder is vacuum sealed and then subjected to cold isostatic pressing.

5. The preparation method according to claim 1, characterized in that, The pressure for cold isostatic pressing in S4 is 130-170 MPa.

6. The TZM alloy prepared by the preparation method of any one of claims 1-5.

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