A micro / nano alloying method for manufacturing high-strength and high-toughness TZM molybdenum alloys

Abstract

This invention discloses a micro-nano alloying method for manufacturing high-strength, high-toughness TZM molybdenum alloys, relating to the field of powder metallurgy. The method includes: S1, preparing materials; S2, preparing a solution; S3, adding materials to a powder homogenization device; S4, mixing materials to obtain a mixed powder; S5, drying to obtain TZM molybdenum alloy precursor powder; and S6, preparing the TZM molybdenum alloy. This invention is rationally designed. The prepared TZM molybdenum alloy mixture, after subsequent pressing, sintering, and rolling processes, yields a high-strength, high-toughness TZM molybdenum alloy with a tensile strength greater than 1100 MPa and an elongation greater than 7%, exhibiting excellent comprehensive properties. This scheme is rationally designed, with uniform alloy element addition, easy control, and suitable for various production scales, thus possessing broad application prospects.

Description

Technical Field

[0001] This invention relates to the field of powder metallurgy technology, and more specifically to the field of micro-nano alloying methods for manufacturing high-strength and high-toughness TZM molybdenum alloys. Background Technology

[0002] Molybdenum is a refractory rare metal with high-temperature strength and hardness, a high melting point, good electrical and thermal conductivity, a low coefficient of thermal expansion, and excellent thermal shock and fatigue resistance. It is widely used in metallurgy, petroleum, chemical, machinery, aerospace, steel, and nuclear energy technologies. However, its low recrystallization temperature, high brittleness, and low room-temperature strength limit its applications. Alloying is a crucial way to improve its properties, and there is an urgent need for high-strength, high-toughness molybdenum alloys in various fields. TZM molybdenum alloy, as a representative high-strength, high-toughness molybdenum alloy, requires significant improvement in product quality and manufacturing processes.

[0003] In the production of TZM molybdenum alloy using powder metallurgy, the addition of alloying elements is the most critical step among a series of processes including alloying element addition, pressing, sintering, and rolling. The uniformity of alloying element addition directly affects the performance of the product. Various methods for adding alloying elements have been widely used in material preparation. However, due to increasingly stringent requirements for the performance of the resulting materials, poor uniformity of alloying element addition can severely impair the final performance of the material. Existing patents disclose the following technologies:

[0004] Patent publication number CN1962911A, entitled "A Method for Preparing Molybdenum Alloy TZM by Powder Metallurgy," discloses the following: A method for preparing molybdenum alloy TZM by powder metallurgy uses titanium hydride and zirconium hydride particles with a Fisher particle size of 5-10 μm and a maximum particle size of no more than 10 μm to prepare TZM molybdenum alloy. This invention's method for preparing molybdenum alloy TZM using powder metallurgy adds fine-particle alloying element powders; due to the small particle size of the second phase, the diffusion during sintering is uniform; this improves the uniformity of the material structure, enhances the high-temperature performance and room-temperature brittleness of the material, and prepares a high-performance TZM molybdenum alloy.

[0005] The patent with publication number CN109371274B and patent title "A method for preparing powder metallurgy TZM molybdenum alloy" discloses the following: A method for preparing powder metallurgy TZM molybdenum alloy, which uses reduced graphene oxide as the carbon source for preparing TZM molybdenum alloy. The specific process is as follows: titanium hydride powder, zirconium hydride powder and reduced graphene oxide powder are added to anhydrous ethanol and ball-milled to obtain a mixed alloy slurry. Then, the mixed alloy slurry is added to freshly reduced molybdenum powder and mixed. Finally, the mixture is isostatically pressed and vacuum sintered to obtain TZM molybdenum alloy. This invention uses reduced graphene oxide as a carbon source, and combines ball milling to uniformly disperse and adhere the reduced graphene oxide to titanium hydride and zirconium hydride. Then, freshly reduced molybdenum powder is added, thereby forming TiC and ZrC in situ during sintering, or forming TiC and ZrC through diffusion reaction. This increases the content of dispersed carbides in TZM molybdenum alloy and reduces the content of Ti and Zr dissolved in the matrix, thereby increasing the high and low temperature strength and plasticity of TZM molybdenum alloy.

[0006] The aforementioned patent discloses two methods for preparing powder metallurgy TZM molybdenum alloy: a solid-solid addition method and a solid-liquid addition method. However, the solid-solid addition method is prone to problems such as agglomeration and the introduction of impurities, resulting in poor mixing uniformity. In contrast, the solid-liquid addition method often involves manual mixing in the laboratory, which is time-consuming, labor-intensive, and produces poor uniformity. Existing equipment often fails to ensure sufficient contact between the solid powder and the solution, leading to poor uniformity of alloy element addition and a tendency for agglomeration that drastically reduces powder performance. Ultimately, these factors result in uneven particle size and low sintering activity in the prepared product, significantly reducing the overall performance of the molybdenum alloy. Summary of the Invention

[0007] The purpose of this invention is to address the technical problems of poor uniformity of alloying element addition in TZM molybdenum alloys prepared by existing methods, which leads to uneven particle size and low sintering activity in the prepared TZM molybdenum alloy products. This invention provides a micro-nano alloying method for manufacturing high-strength and high-toughness TZM molybdenum alloys.

[0008] To achieve the above objectives, the present invention specifically adopts the following technical solution:

[0009] This invention provides a micro / nano alloying method for manufacturing high-strength, high-toughness TZM molybdenum alloys, comprising the following steps:

[0010] S1. Prepare materials: Prepare molybdenum powder, alloy additives and liquid medium for later use. Alloy additives include fructose, TiH2, ZrH2, Ti(SO4)2 and Zr(NO3)4.

[0011] S2. Solution preparation: Add fructose, TiH2, ZrH2, Ti(SO4)2 and Zr(NO3)4 from step S1 to a liquid medium to prepare an alloying element solution;

[0012] S3. Material addition to powder homogenization device: The molybdenum powder in step S1 and the alloying element solution prepared in step S2 are added to the powder homogenization device. The molybdenum powder and the alloying element solution are respectively added to the circulating stirring mixing chamber and the ultrasonic atomization reaction chamber of the powder homogenization device.

[0013] S4. Material mixing to obtain mixed powder: The atomized alloying element solution is added to the circulating stirring mixing chamber in the ultrasonic atomization reaction chamber to obtain mixed powder;

[0014] S5. Drying to obtain TZM molybdenum alloy precursor powder: The mixed powder obtained in step S4 is dried to obtain TZM molybdenum alloy precursor powder with uniform alloy element addition.

[0015] S6. Preparation of TZM molybdenum alloy: The TZM molybdenum alloy precursor powder obtained in step S5 is processed by subsequent pressing, sintering and rolling processes to obtain high-strength and high-toughness TZM molybdenum alloy.

[0016] Specifically, the TZM molybdenum alloy mixture obtained using this method, after subsequent pressing, sintering, and rolling processes, produces a high-strength, high-toughness TZM molybdenum alloy with a tensile strength greater than 1100 MPa and an elongation greater than 7%, exhibiting excellent comprehensive properties. This method is rationally designed, with uniform alloy element addition, easy control, and suitable for various production scales, thus possessing broad application prospects.

[0017] Further, in step S1, the liquid medium is either water or alcohol, and the mass ratio of the liquid medium to the alloy powder is 1:20 to 1:2.

[0018] Further, in step S3, the prepared solution is poured into the ultrasonic atomization reaction chamber, the air exchange valve in the ultrasonic atomization reaction chamber is opened, the ultrasonic atomization reaction chamber is evacuated and then filled with argon gas.

[0019] Further, in step S1, the mass percentages of chemical elements in the molybdenum powder and alloy additives are as follows: Ti: 0.01%~2.5%, Zr: 0.01%~3.5%, C: 0.01%~1.50%, with the balance being molybdenum powder and unavoidable impurities, and the sum of the mass percentages of chemical elements is 100%.

[0020] Specifically, this solution has good sealing performance, preventing the introduction of foreign impurities. It is equipped with a ventilation valve, which can be used in some demanding scenarios. It supports mixing in low-oxygen or other gas atmospheres, improving the quality of alloy element addition.

[0021] Furthermore, the powder homogenization device includes a shell, a feed inlet located at the top of the shell, a medium inlet located at the top of the shell, and a discharge outlet located at the bottom of the shell. The shell contains a circulating stirring and mixing chamber and an ultrasonic atomizing reaction chamber that are interconnected. The feed inlet and the discharge outlet are connected to the top and bottom of the circulating stirring and mixing chamber, respectively, and the medium inlet is connected to the ultrasonic atomizing reaction chamber.

[0022] Specifically, this solution uniquely atomizes the alloying element solution into extremely fine droplets through an atomizer in an ultrasonic atomization reaction chamber. These droplets are then dispersed into the circulating stirring and mixing chamber through the atomization outlet, ensuring that the molybdenum powder and the alloying element solution are fully in contact and mixed. This greatly improves the uniformity of the mixture and effectively prevents powder agglomeration, further enhancing the uniformity of the mixture.

[0023] Furthermore, the circulating mixing chamber includes a processing chamber located in the middle and one or more circulating chambers arranged circumferentially on the outer wall of the processing chamber, with the bottom and top of each circulating chamber communicating with the bottom and top of the processing chamber, respectively.

[0024] Specifically, a preferred structure of a circulating stirring mixing chamber is disclosed. This preferred structure includes a central processing chamber for thoroughly mixing the alloying element solution with molybdenum powder, and one or more circulating chambers that enable the molybdenum powder located at the bottom of the processing chamber after mixing to circulate and fully contact the alloying element solution. The number of circulating chambers can be selected according to actual conditions.

[0025] Furthermore, there are two circulation chambers, which are symmetrically arranged on both sides of the processing chamber.

[0026] Specifically, the preferred number of circulation chambers in this scheme is two, and the symmetrical arrangement on both sides of the processing chamber has the advantage of simple installation.

[0027] Furthermore, each circulation chamber is equipped with a lifting mechanism for lifting materials, each circulation chamber has a rising material inlet at the bottom that communicates with the bottom of the processing chamber, and each circulation chamber has a settling material inlet at the top that communicates with the top of the processing chamber.

[0028] Specifically, the disclosing method for lifting the mixed molybdenum powder within the circulation chamber is described. This lifting mechanism can be a rotating lifting disc, a screw conveyor, or any other structure capable of achieving a lifting effect. Furthermore, the settling inlet is located at the top, and the rising inlet at the bottom. This layout ensures thorough circulation of the mixed molybdenum powder, increasing the uniformity of the mixture.

[0029] Furthermore, the processing chamber is equipped with a heated crusher, a vibrating screen and a rotating disk arranged from top to bottom. The heated crusher is located at the top of the processing chamber and directly below the feed inlet. The settling inlet is located above the heated crusher. The rotating disk is located at the bottom of the processing chamber and the rising inlet is located above the rotating disk.

[0030] Specifically, a heated crusher and a vibrating screen are installed below the settling inlet in the processing chamber. The heated crusher and vibrating screen can evenly sprinkle molybdenum powder, so that the molybdenum powder can fully contact and mix with the solution, which greatly improves the uniformity of mixing and also effectively prevents powder agglomeration.

[0031] Furthermore, the ultrasonic atomization reaction chamber includes one or more atomization reaction chambers disposed on the outer wall of the processing chamber, and each atomization reaction chamber has an atomization outlet on its side wall. The atomization outlet is located below the vibrating screen, and an atomizer is disposed inside the atomization outlet.

[0032] Specifically, during operation, the mixture passing through the processing chamber repeatedly falls into the vibrating screen via the bottom rotating disk and lifting mechanism, repeatedly entering the processing chamber to mix with the prepared solution, thus achieving continuous and repetitive mixing and further improving the uniformity of mixing.

[0033] Working principle of powder homogenization device: Molybdenum powder is poured into vibrating screen through feed port, and the prepared solution is poured into ultrasonic atomization reaction chamber. The air exchange valve is opened, and after vacuuming, argon gas is introduced. The powder homogenization device is turned on, and the molybdenum powder is dispersed in the mixing chamber through vibrating screen. The prepared solution enters the mixing chamber through atomization outlet after ultrasonic atomization and is fully mixed with molybdenum powder. The initially mixed raw materials are carried to the rising turntable through the bottom rotating plate and rising to the settling port and falling into the heated crusher again. They are then repeatedly and evenly mixed through vibrating screen. After the equipment continues to run for 30 minutes, the rising port is closed and the discharge port is opened to complete the collection.

[0034] The beneficial effects of the present invention are as follows:

[0035] 1. The TZM molybdenum alloy mixture obtained by this invention, after subsequent pressing, sintering, and rolling processes, produces a high-strength, high-toughness TZM molybdenum alloy with a tensile strength greater than 1100 MPa and an elongation greater than 7%, exhibiting excellent comprehensive properties. This method is rationally designed, allows for uniform addition of alloying elements, is easy to control, and is suitable for various production scales, thus possessing broad application prospects.

[0036] 2. The invention uniquely atomizes the solution into extremely fine droplets through an atomizer, which are then dispersed into the mixing chamber through the atomization outlet. Solid powder is then evenly sprinkled down through a heated crusher and a vibrating screen, allowing the solid powder to fully contact and mix with the solution, greatly improving the uniformity of mixing and effectively preventing powder agglomeration.

[0037] 3. During operation, the mixture passing through the processing chamber of this invention repeatedly falls into the vibrating screen via the bottom rotating disk and the lifting mechanism, repeatedly entering the processing chamber to mix with the prepared solution, thereby achieving the continuity and repetition of mixing and further improving the uniformity of mixing.

[0038] 4. This invention has good sealing performance, which avoids the introduction of foreign impurities. It is equipped with a ventilation valve, which can be used in some high-requirement scenarios. It supports mixing in low oxygen or other gas atmospheres, which improves the quality of alloy element addition. Attached Figure Description

[0039] Figure 1 , Figure 3 , Figure 4 This is a scanning electron microscope image of TZM molybdenum alloy precursor powder with uniform alloying elements added according to the present invention.

[0040] Figure 2 These are scanning electron microscope images of the tensile fracture surface of TZM molybdenum alloy prepared by the method of the present invention;

[0041] Figure 5 Figure 6 , Figure 7 These are scanning electron microscope (SEM) images and energy dispersive spectroscopy (EDS) images of TZM molybdenum alloy precursor powder with uniform alloying elements according to the present invention.

[0042] Figure 8 This is a schematic diagram of the main structure of the present invention;

[0043] Figure 9 yes Figure 8 Side view;

[0044] Reference numerals: 1-feed inlet, 2-heating crusher, 3-vibrating screen, 4-processing chamber, 5-rotary disc, 6-sinking inlet, 7-lifting mechanism, 8-rising inlet, 9-base, 10-atomization outlet, 11-circulation chamber (11), 12-discharge outlet. Detailed Implementation

[0045] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The components of the embodiments of the present invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations.

[0046] Therefore, the following detailed description of the embodiments of the invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the invention without inventive effort are within the scope of protection of the invention.

[0047] It should be noted that similar reference numerals and letters in the following figures indicate similar items; therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures. Furthermore, the terms "first," "second," etc., are used only to distinguish descriptions and should not be construed as indicating or implying relative importance.

[0048] In the description of the embodiments of the present invention, it should be noted that the terms "inner", "outer", "upper", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship in which the product of the invention is usually placed when in use. They are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limiting the present invention.

[0049] The powder homogenization device used in this scheme includes a shell, a feed inlet 1 located at the top of the shell, a medium inlet located at the top of the shell, and a discharge outlet 12 located at the bottom of the shell. The shell is equipped with a circulating stirring and mixing chamber and an ultrasonic atomizing reaction chamber that are interconnected. The feed inlet 1 and the discharge outlet 12 are connected to the top and bottom of the circulating stirring and mixing chamber, respectively, and the medium inlet is connected to the ultrasonic atomizing reaction chamber.

[0050] Specifically, this unique solution atomizes the alloying element solution into extremely fine droplets via an atomizer in an ultrasonic atomization reaction chamber. These droplets are then dispersed into the circulating mixing chamber through the atomization outlet 10, ensuring thorough contact and mixing of the molybdenum powder and the alloying element solution. This significantly improves the uniformity of the mixture and effectively prevents powder agglomeration, further enhancing the homogeneity of the mixing. Furthermore, the ultrasonic atomization reaction chamber can be replaced with other atomization devices.

[0051] The circulating mixing chamber includes a processing chamber 4 located in the middle and one or more circulating chambers 11 arranged circumferentially on the outer wall of the processing chamber 4. The bottom and top of each circulating chamber 11 are respectively connected to the bottom and top of the processing chamber 4.

[0052] Specifically, a preferred structure of a circulating stirring mixing chamber is disclosed. This preferred structure includes a central processing chamber 4 for fully mixing the alloying element solution with molybdenum powder, and one or more circulating chambers 11 that enable the molybdenum powder located at the bottom of the processing chamber 4 after mixing to circulate and fully contact the alloying element solution. The number of circulating chambers 11 can be selected according to the actual situation.

[0053] There are two circulation chambers 11, which are symmetrically arranged on both sides of the processing chamber 4.

[0054] Specifically, the preferred number of circulation chambers 11 in this scheme is two, and the symmetrical arrangement on both sides of the processing chamber 4 has the advantage of simple installation.

[0055] Each circulation chamber 11 is equipped with a lifting mechanism 7 for lifting materials, each circulation chamber 11 has a rising material port 8 at the bottom that communicates with the bottom of the processing chamber 4, and each circulation chamber 11 has a settling material port 6 at the top that communicates with the top of the processing chamber 4.

[0056] Specifically, a lifting mechanism 7 for the mixed molybdenum powder within the circulation chamber 11 is disclosed. The lifting mechanism 7 can be a lifting turntable, a lifting auger, or other structures capable of achieving a lifting effect. Additionally, the settling inlet 6 is located at the top, and the rising inlet 8 is located at the bottom. This layout ensures that the mixed molybdenum powder circulates fully, increasing the uniformity of the molybdenum powder mixture.

[0057] The processing chamber 4 is equipped with a heating crusher 2, a vibrating screen 3 and a rotating disk 5 arranged from top to bottom. The heating crusher 2 is located at the top of the processing chamber 4 and directly below the feed inlet 1. The settling inlet 6 is located above the heating crusher 2. The rotating disk 5 is located at the bottom of the processing chamber 4 and the rising inlet 8 is located above the rotating disk 5.

[0058] Specifically, a heated crusher 2 and a vibrating screen 3 are installed below the settling inlet 6 in the processing chamber 4. The heated crusher 2 and the vibrating screen 3 can evenly sprinkle molybdenum powder down, so that the molybdenum powder can fully contact and mix with the solution, which greatly improves the uniformity of mixing and also effectively prevents powder agglomeration.

[0059] The ultrasonic atomization reaction chamber includes one or more atomization reaction chambers disposed on the outer wall of the processing chamber 4. Each atomization reaction chamber has an atomization outlet 10 disposed on its side wall. The atomization outlet 10 is located below the vibrating screen 3, and an atomizer is disposed inside the atomization outlet 10.

[0060] Specifically, during operation, the mixture passing through the processing chamber 4 repeatedly falls into the vibrating screen 3 via the bottom rotating disk 5 and the lifting mechanism 7, repeatedly entering the processing chamber 4 to mix with the prepared solution, thus achieving the continuity and repetition of mixing, and further improving the uniformity of mixing.

[0061] Example 1

[0062] This embodiment provides a micro / nano alloying method for manufacturing high-strength, high-toughness TZM molybdenum alloys, comprising the following steps:

[0063] S1. Prepare the following materials: 1.200g fructose, 0.000g TiH2, 0.000g ZrH2, 30.000g Ti(SO4)2, 4.520g Zr(NO3)4, 1000g molybdenum powder, and 500ml deionized water.

[0064] S2. Solution preparation: Add fructose, TiH2, ZrH2, Ti(SO4)2 and Zr(NO3)4 from step S1 to water to prepare an alloying element solution;

[0065] S3. Material addition to powder homogenization device: Add the molybdenum powder from step S1 and the alloying element solution prepared in step S2 to the powder homogenization device. Add the molybdenum powder and the alloying element solution to the circulating stirring mixing chamber and the ultrasonic atomization reaction chamber of the powder homogenization device, respectively. Pour the prepared solution into the ultrasonic atomization reaction chamber, open the air exchange valve in the ultrasonic atomization reaction chamber, evacuate the ultrasonic atomization reaction chamber and then fill it with argon gas.

[0066] S4. Material mixing to obtain mixed powder: The atomized alloy element solution is added to the circulating stirring mixing chamber in the ultrasonic atomization reaction chamber to obtain mixed powder. After the equipment continues to run for 30 minutes, the rising material port is closed and the discharge port is opened to complete the collection.

[0067] S5. Drying to obtain TZM molybdenum alloy precursor powder: The mixed powder obtained in step S4 is dried. After the alloying elements are added, the powder is placed in a drying oven and dried at 70°C for two hours to obtain TZM molybdenum alloy precursor powder with uniform alloying elements.

[0068] S6. Preparation of TZM molybdenum alloy: The TZM molybdenum alloy precursor powder obtained in step S5 is processed by subsequent pressing, sintering and rolling processes to obtain high-strength and high-toughness TZM molybdenum alloy.

[0069] In this embodiment, the scanning electron microscope image is as follows: Figure 1 As shown, the TZM molybdenum alloy precursor powder obtained by the present invention exhibits uniform alloying element addition and excellent results. Based on this TZM molybdenum alloy precursor powder, TZM molybdenum alloy is obtained through subsequent pressing, sintering, and rolling processes. The scanning electron microscope image of its tensile fracture surface is shown in the figure. Figure 2 As shown in the figure. The results show that this TZM molybdenum alloy has a tensile strength of 1139 MPa, an elongation of 7.65%, a uniform microstructure, and excellent comprehensive properties, making it a high-strength and high-toughness TZM molybdenum alloy.

[0070] Example 2

[0071] This embodiment provides a micro / nano alloying method for manufacturing high-strength, high-toughness TZM molybdenum alloys, comprising the following steps:

[0072] S1. Prepare the following materials: 1.200g fructose, 0.000g TiH2, 0.000g ZrH2, 30.000g Ti(SO4)2, 4.520g Zr(NO3)4, 1000g molybdenum powder, and 500ml alcohol.

[0073] S2. Solution preparation: Add fructose, TiH2, ZrH2, Ti(SO4)2 and Zr(NO3)4 from step S1 to alcohol to prepare a solution with added alloying elements;

[0074] S3. Material addition to powder homogenization device: Add the molybdenum powder from step S1 and the alloying element solution prepared in step S2 to the powder homogenization device. Add the molybdenum powder and the alloying element solution to the circulating stirring mixing chamber and the ultrasonic atomization reaction chamber of the powder homogenization device, respectively. Pour the prepared solution into the ultrasonic atomization reaction chamber, open the air exchange valve in the ultrasonic atomization reaction chamber, evacuate the ultrasonic atomization reaction chamber and then fill it with argon gas.

[0075] S4. Material mixing to obtain mixed powder: The atomized alloy element solution is added to the circulating stirring mixing chamber in the ultrasonic atomization reaction chamber to obtain mixed powder. After the equipment continues to run for 30 minutes, the rising material port is closed and the discharge port is opened to complete the collection.

[0076] S5. Drying to obtain TZM molybdenum alloy precursor powder: The mixed powder obtained in step S4 is dried. After the alloying elements are added, the powder is placed in a drying oven and dried at 70°C for two hours to obtain TZM molybdenum alloy precursor powder with uniform alloying elements.

[0077] S6. Preparation of TZM molybdenum alloy: The TZM molybdenum alloy precursor powder obtained in step S5 is processed by subsequent pressing, sintering and rolling processes to obtain high-strength and high-toughness TZM molybdenum alloy.

[0078] In this embodiment, the scanning electron microscope image is as follows: Figure 3 As shown, the TZM molybdenum alloy precursor powder obtained by the present invention has uniform alloy element addition and excellent effect. The TZM molybdenum alloy prepared by this scheme has a tensile strength of 1145 MPa, an elongation of 7.82%, a uniform microstructure, and excellent comprehensive performance. It is a high-strength and high-toughness TZM molybdenum alloy.

[0079] Example 3

[0080] This embodiment provides a micro / nano alloying method for manufacturing high-strength, high-toughness TZM molybdenum alloys, comprising the following steps:

[0081] S1. Prepare the following materials: 1.200g fructose, 3.200g TiH2, 0.490g ZrH2, 15.000g Ti(SO4)2, 2.260g Zr(NO3)4, 1000g molybdenum powder, and 500ml alcohol.

[0082] S2. Solution preparation: Add fructose, TiH2, ZrH2, Ti(SO4)2 and Zr(NO3)4 from step S1 to alcohol to prepare a solution with added alloying elements;

[0083] S3. Material addition to powder homogenization device: Add the molybdenum powder from step S1 and the alloying element solution prepared in step S2 to the powder homogenization device. Add the molybdenum powder and the alloying element solution to the circulating stirring mixing chamber and the ultrasonic atomization reaction chamber of the powder homogenization device, respectively. Pour the prepared solution into the ultrasonic atomization reaction chamber, open the air exchange valve in the ultrasonic atomization reaction chamber, evacuate the ultrasonic atomization reaction chamber and then fill it with argon gas.

[0084] S4. Material mixing to obtain mixed powder: The atomized alloy element solution is added to the circulating stirring mixing chamber in the ultrasonic atomization reaction chamber to obtain mixed powder. After the equipment continues to run for 30 minutes, the rising material port is closed and the discharge port is opened to complete the collection.

[0085] S5. Drying to obtain TZM molybdenum alloy precursor powder: The mixed powder obtained in step S4 is dried. After the alloying elements are added, the powder is placed in a drying oven and dried at 80°C for two hours to obtain TZM molybdenum alloy precursor powder with uniform alloying elements.

[0086] S6. Preparation of TZM molybdenum alloy: The TZM molybdenum alloy precursor powder obtained in step S5 is processed by subsequent pressing, sintering and rolling processes to obtain high-strength and high-toughness TZM molybdenum alloy.

[0087] In this embodiment, the scanning electron microscope image is as follows: Figure 4 As shown, the TZM molybdenum alloy precursor powder obtained by the present invention has uniform alloy element addition and excellent effect. The TZM molybdenum alloy prepared by this scheme has a tensile strength of 1121 MPa, an elongation of 7.26%, a uniform microstructure, and excellent comprehensive performance. It is a high-strength and high-toughness TZM molybdenum alloy.

[0088] Example 4

[0089] This embodiment provides a micro / nano alloying method for manufacturing high-strength, high-toughness TZM molybdenum alloys, comprising the following steps:

[0090] S1. Prepare the following materials: 1.200g fructose, 0.000g TiH2, 0.000g ZrH2, 30.000g Ti(SO4)2, 4.520g Zr(NO3)4, 1000g molybdenum powder, and 500ml deionized water.

[0091] S2. Solution preparation: Add fructose, TiH2, ZrH2, Ti(SO4)2 and Zr(NO3)4 from step S1 to alcohol to prepare a solution with added alloying elements;

[0092] S3. Material addition to powder homogenization device: Add the molybdenum powder from step S1 and the alloying element solution prepared in step S2 to the powder homogenization device. Add the molybdenum powder and the alloying element solution to the circulating stirring mixing chamber and the ultrasonic atomization reaction chamber of the powder homogenization device, respectively. Pour the prepared solution into the ultrasonic atomization reaction chamber, open the air exchange valve in the ultrasonic atomization reaction chamber, evacuate the ultrasonic atomization reaction chamber and then fill it with argon gas.

[0093] S4. Material mixing to obtain mixed powder: The atomized alloy element solution is added to the circulating stirring mixing chamber in the ultrasonic atomization reaction chamber to obtain mixed powder. After the equipment continues to run for 120 minutes, the rising material port is closed and the discharge port is opened to complete the collection.

[0094] S5. Drying to obtain TZM molybdenum alloy precursor powder: The mixed powder obtained in step S4 is dried. After the alloying elements are added, the powder is placed in a drying oven and dried at 70°C for two hours to obtain TZM molybdenum alloy precursor powder with uniform alloying elements.

[0095] S6. Preparation of TZM molybdenum alloy: The TZM molybdenum alloy precursor powder obtained in step S5 is processed by subsequent pressing, sintering and rolling processes to obtain high-strength and high-toughness TZM molybdenum alloy.

[0096] In this embodiment, the scanning electron microscope image and energy dispersive spectroscopy (EDS) image are as follows: Figure 5 As shown, the TZM molybdenum alloy precursor powder obtained by the present invention has uniform alloy element addition and excellent effect. The TZM molybdenum alloy prepared by this scheme has a tensile strength of 1125 MPa, an elongation of 7.53%, a uniform microstructure, and excellent comprehensive performance. It is a high-strength and high-toughness TZM molybdenum alloy.

[0097] Example 5

[0098] This embodiment provides a micro / nano alloying method for manufacturing high-strength, high-toughness TZM molybdenum alloys, comprising the following steps:

[0099] S1. Prepare the following materials: 1.200g fructose, 0.000g TiH2, 0.000g ZrH2, 30.000g Ti(SO4)2, 4.520g Zr(NO3)4, 1000g molybdenum powder, and 500ml deionized water.

[0100] S2. Solution preparation: Add fructose, TiH2, ZrH2, Ti(SO4)2 and Zr(NO3)4 from step S1 to alcohol to prepare a solution with added alloying elements;

[0101] S3. Material addition to powder homogenization device: Add the molybdenum powder from step S1 and the alloying element solution prepared in step S2 to the powder homogenization device. Add the molybdenum powder and the alloying element solution to the circulating stirring mixing chamber and the ultrasonic atomization reaction chamber of the powder homogenization device, respectively. Pour the prepared solution into the ultrasonic atomization reaction chamber, open the air exchange valve in the ultrasonic atomization reaction chamber, evacuate the ultrasonic atomization reaction chamber and then fill it with argon gas.

[0102] S4. Material mixing to obtain mixed powder: The atomized alloy element solution is added to the circulating stirring mixing chamber in the ultrasonic atomization reaction chamber to obtain mixed powder. After the equipment continues to run for 30 minutes, the rising material port is closed and the discharge port is opened to complete the collection.

[0103] S5. Drying to obtain TZM molybdenum alloy precursor powder: The mixed powder obtained in step S4 is dried. After the alloying elements are added, the powder is placed in a drying oven and dried at 200°C for two hours to obtain TZM molybdenum alloy precursor powder with uniform alloying elements.

[0104] S6. Preparation of TZM molybdenum alloy: The TZM molybdenum alloy precursor powder obtained in step S5 is processed by subsequent pressing, sintering and rolling processes to obtain high-strength and high-toughness TZM molybdenum alloy.

[0105] In this embodiment, the scanning electron microscope image and energy dispersive spectroscopy (EDS) image are as follows: Figure 6 As shown, the TZM molybdenum alloy precursor powder obtained by the present invention has uniform alloy element addition and excellent effect. The TZM molybdenum alloy prepared by this scheme has a tensile strength of 1150MPa, an elongation of 7.62%, a uniform microstructure, and excellent comprehensive performance. It is a high-strength and high-toughness TZM molybdenum alloy.

[0106] Example 6

[0107] This embodiment provides a micro / nano alloying method for manufacturing high-strength, high-toughness TZM molybdenum alloys, comprising the following steps:

[0108] S1. Prepare the following materials: 1.200g fructose, 0.000g TiH2, 0.000g ZrH2, 30.000g Ti(SO4)2, 4.520g Zr(NO3)4, 500g molybdenum powder, and 500ml deionized water.

[0109] S2. Solution preparation: Add fructose, TiH2, ZrH2, Ti(SO4)2 and Zr(NO3)4 from step S1 to alcohol to prepare a solution with added alloying elements;

[0110] S3. Material addition to powder homogenization device: Add the molybdenum powder from step S1 and the alloying element solution prepared in step S2 to the powder homogenization device. Add the molybdenum powder and the alloying element solution to the circulating stirring mixing chamber and the ultrasonic atomization reaction chamber of the powder homogenization device, respectively. Pour the prepared solution into the ultrasonic atomization reaction chamber, open the air exchange valve in the ultrasonic atomization reaction chamber, evacuate the ultrasonic atomization reaction chamber and then fill it with argon gas.

[0111] S4. Material mixing to obtain mixed powder: The atomized alloy element solution is added to the circulating stirring mixing chamber in the ultrasonic atomization reaction chamber to obtain mixed powder. After the equipment continues to run for 30 minutes, the rising material port is closed and the discharge port is opened to complete the collection.

[0112] S5. Drying to obtain TZM molybdenum alloy precursor powder: The mixed powder obtained in step S4 is dried. After the alloying elements are added, the powder is placed in a drying oven and dried at 70°C for two hours to obtain TZM molybdenum alloy precursor powder with uniform alloying elements.

[0113] S6. Preparation of TZM molybdenum alloy: The TZM molybdenum alloy precursor powder obtained in step S5 is processed by subsequent pressing, sintering and rolling processes to obtain high-strength and high-toughness TZM molybdenum alloy.

[0114] In this embodiment, the scanning electron microscope image and energy dispersive spectroscopy (EDS) image are as follows: Figure 7 As shown, the TZM molybdenum alloy precursor powder obtained by the present invention has uniform alloy element addition and excellent effect. The TZM molybdenum alloy prepared by this scheme has a tensile strength of 1119 MPa, an elongation of 7.51%, a uniform microstructure, and excellent comprehensive performance. It is a high-strength and high-toughness TZM molybdenum alloy.

[0115] Comparative Example 1

[0116] The patent with publication number CN109371274B discloses the following: a method for preparing powder metallurgy TZM molybdenum alloy. The method uses reduced graphene oxide as the carbon source for preparing TZM molybdenum alloy. The specific process is as follows: titanium hydride powder, zirconium hydride powder and reduced graphene oxide powder are added to anhydrous ethanol and ball-milled to obtain a mixed alloy slurry. Then, the mixed alloy slurry is added to freshly reduced molybdenum powder and mixed. Finally, the mixture is isostatically pressed and vacuum sintered to obtain TZM molybdenum alloy.

[0117] In this comparative example, the prepared TZM molybdenum alloy had a tensile strength of 865 MPa, an elongation of 5.75%, and an uneven microstructure.

[0118] The table below compares the performance of Examples 1-6 and Comparative Example 1. It can be seen that the TZM molybdenum alloy prepared according to this method has higher tensile strength and better elongation. The TZM molybdenum alloy mixture obtained using this method, after subsequent pressing, sintering, and rolling processes, produces a high-strength, high-toughness TZM molybdenum alloy with a tensile strength greater than 1100 MPa and an elongation greater than 7%, exhibiting excellent comprehensive performance. This method is rationally designed, with uniform alloy element addition, easy control, and suitable for various production scales, thus possessing broad application prospects.

[0119]

Claims

1. A micro / nano alloying method for manufacturing high-strength, high-toughness TZM molybdenum alloys, characterized in that, Includes the following steps: S1. Material Preparation: Prepare molybdenum powder, alloy additives, and a liquid medium. The alloy additives include fructose, TiH2, ZrH2, Ti(SO4)2, and Zr(NO3)4. The liquid medium is either water or alcohol, with a mass ratio of liquid medium to alloy powder of 1:20 to 1:

2. The mass percentages of chemical elements in the molybdenum powder and alloy additives are as follows: Ti: 0.01%–2.5%, Zr: 0.01%–3.5%, C: 0.01%–1.50%, with the balance being molybdenum powder and unavoidable impurities. The sum of the mass percentages of chemical elements is 100%. S2. Solution preparation: Add fructose, TiH2, ZrH2, Ti(SO4)2 and Zr(NO3)4 from step S1 to a liquid medium to prepare an alloying element solution; S3. Material addition to powder homogenization device: The molybdenum powder in step S1 and the alloying element solution prepared in step S2 are added to the powder homogenization device. The molybdenum powder and the alloying element solution are respectively added to the circulating stirring mixing chamber and the ultrasonic atomization reaction chamber of the powder homogenization device. S4. Material mixing to obtain mixed powder: The atomized alloying element solution is added to the circulating stirring mixing chamber in the ultrasonic atomization reaction chamber to obtain mixed powder; S5. Drying to obtain TZM molybdenum alloy precursor powder: The mixed powder obtained in step S4 is dried to obtain TZM molybdenum alloy precursor powder with uniform alloy element addition. S6. Preparation of TZM molybdenum alloy: The TZM molybdenum alloy precursor powder obtained in step S5 is processed by subsequent pressing, sintering and rolling processes to obtain high-strength and high-toughness TZM molybdenum alloy. The powder homogenization device includes a shell, a feed inlet (1) located at the top of the shell, a medium inlet located at the top of the shell, and a discharge outlet (12) located at the bottom of the shell. The shell contains a circulating stirring and mixing chamber and an ultrasonic atomizing reaction chamber that are interconnected. The feed inlet (1) and the discharge outlet (12) are connected to the top and bottom of the circulating stirring and mixing chamber, respectively. The medium inlet is connected to the ultrasonic atomizing reaction chamber.

2. The micro / nano alloying method for manufacturing high-strength, high-toughness TZM molybdenum alloy according to claim 1, characterized in that, In step S3, the prepared solution is poured into the ultrasonic atomization reaction chamber, the air exchange valve in the ultrasonic atomization reaction chamber is opened, the ultrasonic atomization reaction chamber is evacuated and then filled with argon gas.

3. The micro / nano alloying method for manufacturing high-strength, high-toughness TZM molybdenum alloy according to claim 2, characterized in that, The circulating mixing chamber includes a processing chamber (4) located in the middle and one or more circulating chambers (11) arranged circumferentially on the outer wall of the processing chamber (4). The bottom and top of each circulating chamber (11) are respectively connected to the bottom and top of the processing chamber (4).

4. The micro / nano alloying method for manufacturing high-strength, high-toughness TZM molybdenum alloy according to claim 3, characterized in that, There are two circulation chambers (11), which are symmetrically arranged on both sides of the processing chamber (4).

5. A micro / nano alloying method for manufacturing high-strength, high-toughness TZM molybdenum alloys according to claim 3 or 4, characterized in that, Each of the circulating chambers (11) is provided with a lifting mechanism (7) for lifting materials, and each of the circulating chambers (11) is provided with a rising material port (8) communicating with the bottom of the processing chamber (4) at the bottom, and each of the circulating chambers (11) is provided with a settling material port (6) communicating with the top of the processing chamber (4) at the top.

6. The micro / nano alloying method for manufacturing high-strength, high-toughness TZM molybdenum alloy according to claim 5, characterized in that, The processing chamber (4) is provided with a heating crusher (2), a vibrating screen (3) and a rotating disk (5) arranged from top to bottom. The heating crusher (2) is located at the top of the processing chamber (4) and directly below the feed inlet (1). The settling inlet (6) is located above the heating crusher (2). The rotating disk (5) is located at the bottom of the processing chamber (4). The rising inlet (8) is located above the rotating disk (5).

7. A micro / nano alloying method for manufacturing high-strength, high-toughness TZM molybdenum alloys according to claim 6, characterized in that, The ultrasonic atomization reaction chamber includes one or more atomization reaction chambers disposed on the outer wall of the processing chamber (4). Each atomization reaction chamber has an atomization outlet (10) disposed on its side wall. The atomization outlet (10) is located below the vibrating screen (3). An atomizer is disposed inside the atomization outlet (10).

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