A tellurium-copper alloy material and a method for manufacturing the same

Abstract

The application provides a tellurium-copper alloy material and a preparation method thereof, and relates to the technical field of tellurium-copper alloy preparation. The tellurium-copper alloy material is prepared by forming a tellurium-copper complex solution from tellurium-copper raw materials, through spray drying treatment, calcination and reduction treatment, and by doping rare earth raw materials after sintering. Through the processes of forming a tellurium-copper complex solution, spray drying treatment, doping rare earth and precisely controlling sintering, the uniformity of the alloy can be effectively improved, the grain size can be refined, the strength can be improved, and the thermoelectric performance can be improved. These improvements not only enhance the physical properties of the tellurium-copper alloy, but also expand its potential in industrial applications.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of tellurium-copper alloy preparation, in particular to a tellurium-copper alloy material and a preparation method thereof. BACKGROUND

[0002] As a kind of excellent performance copper alloy material, tellurium-copper alloy occupies an important position in the industry due to its unique physical and chemical properties. This alloy is known for its high electrical conductivity, high thermal conductivity, excellent corrosion resistance and good processing performance. The application range of tellurium-copper alloy is wide, including electronic, electrical, automotive, aerospace and other industries, especially in the field of connectors and contact materials in electronic and electrical equipment.

[0003] The existing preparation technology of tellurium-copper alloy mainly involves melting, casting, heat treatment and deformation processing steps. In the melting process, the copper ingot is first melted, the oxygen in the raw material is removed by controlling the furnace temperature and adding deoxidizing agent, then the tellurium-copper intermediate alloy is added, the alloy after melting is cast into ingot, and then the ingot is subjected to extrusion deformation processing, rolling deformation processing and heat treatment, etc. Finally, the tellurium-copper alloy material is obtained. Although these methods can produce tellurium-copper alloy with certain performance, there are still some defects in practical application.

[0004] Firstly, the uniformity of the distribution of tellurium elements, nano-ceramic phases and rare earth elements in the tellurium-copper alloy is crucial to the overall performance of the material. The uniform distribution of these elements can improve the performance of the material through various strengthening mechanisms, including solid solution strengthening, fine-grain strengthening, second phase strengthening and the purifying effect of rare earth elements. However, when using the melting method to prepare tellurium-copper alloy, it is difficult to accurately control the physical and chemical conditions during the melting process, and there is often segregation of alloy elements during solidification, resulting in uneven distribution of elements, which is particularly evident at the grain boundaries.

[0005] Secondly, when the distribution of alloy elements in the copper alloy matrix is uneven, a series of adverse consequences will be caused. For example, the continuous distribution of brittle second phases at the grain boundaries, and the significant segregation of micro-alloy elements, which not only significantly reduces the electrical conductivity and mechanical strength of the material, but also greatly increases the risk of cracking and brittle fracture during processing. In addition, this uneven distribution also weakens the strength performance and oxidation resistance of the material in high temperature environment, thereby adversely affecting the overall reliability of the material.

[0006] In summary, the main problems faced by the prior art in preparing tellurium-copper alloys include uneven distribution of elements, resulting in a decline in material performance, and the risk of cracking and brittle fracture during processing. These problems limit the potential of tellurium-copper alloys in high-performance applications, particularly in areas with extremely high requirements for material performance. Therefore, achieving uniform distribution of elements in tellurium-copper alloys is of great significance for improving material performance and expanding its application range.

[0007] In view of this, the present application is proposed. SUMMARY

[0008] The present application aims to provide a tellurium-copper alloy material and a preparation method thereof. The preparation method significantly improves the high-temperature strength and electrical conductivity of the alloy by optimizing the preparation process of the alloy, thereby obtaining a high-quality tellurium-copper alloy material with high electrical conductivity, high thermal conductivity, and high strength characteristics.

[0009] In order to achieve the above-mentioned purposes of the present application, the following technical solutions are adopted:

[0010] In a first aspect, the present application provides a preparation method of a tellurium-copper alloy material. The tellurium-copper alloy material is prepared by forming a tellurium-copper complex solution from tellurium-copper raw materials, through spray drying treatment, calcination and reduction treatment, and doping rare earth raw materials, and then sintering.

[0011] In an optional embodiment, the preparation method of the tellurium-copper alloy material comprises:

[0012] The metal chelating agent is used to prepare the metal salt and tellurium acid in the tellurium-copper raw materials to obtain the tellurium-copper complex solution;

[0013] The spray drying treatment is performed on the tellurium-copper complex solution to obtain a precursor powder;

[0014] The precursor powder is subjected to calcination and reduction treatment to obtain an Al2O3-CuTe alloy composite;

[0015] The Al2O3-CuTe alloy composite is mixed with rare earth raw materials to obtain a rare earth mixture;

[0016] The rare earth mixture is subjected to sintering treatment to obtain the tellurium-copper alloy material.

[0017] Preferably, the metal salt is a metal salt that can be dissolved in water and has no other elements remaining except the target element after thermal decomposition;

[0018] Preferably, the metal salt includes a copper ion metal salt with copper as the target element;

[0019] Preferably, the metal salt also includes an aluminum ion metal salt with aluminum as the target element;

[0020] Preferably, the copper ion metal salt comprises copper nitrate and copper acetate;

[0021] Preferably, the aluminum ion metal salt comprises aluminum nitrate and aluminum acetate;

[0022] Preferably, the tellurium copper alloy material comprises tellurium in an amount of 0.2-1.0 wt.%, Al2O3 in an amount of 0-0.5 wt.%, and the rare earth raw material in an amount of 0-0.2 wt.%.

[0023] In an optional embodiment, the preparation of the tellurium copper complex solution by using a metal chelating agent to dissolve the metal salt and tellurium acid comprises:

[0024] dissolving the metal salt and tellurium acid in water and mixing into a solution;

[0025] adding the metal chelating agent into the solution to form the tellurium copper complex solution containing metal complexes;

[0026] In an optional embodiment, the metal chelating agent comprises a hydroxyl functional group capable of forming a complex with copper ions and aluminum ions; and the metal chelating agent has a negative charge capable of adhering to the surface of the metal complex particles.

[0027] In an optional embodiment, the metal chelating agent comprises citric acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, and diethylenetriaminepentaacetic acid.

[0028] In an optional embodiment, the spray drying treatment of the tellurium copper complex solution to obtain a precursor powder comprises:

[0029] atomizing the tellurium copper complex solution to form ultrafine droplets;

[0030] drying the ultrafine droplets by hot air to obtain the precursor powder;

[0031] In an optional embodiment, the rotation speed of the atomization equipment for the atomization treatment is 4000 rpm-30000 rpm.

[0032] In an optional embodiment, the drying of the ultrafine droplets by hot air has an inlet temperature of 100°C-300°C.

[0033] In an optional embodiment, the calcination treatment and reduction treatment of the precursor powder to obtain an Al2O3-CuTe alloy composite comprises:

[0034] calcining the precursor powder in an air or oxygen atmosphere to obtain a composite oxide;

[0035] reducing the composite oxide in a reducing gas to obtain the Al2O3-CuTe alloy composite;

[0036] In an optional embodiment, the calcination time of the calcination treatment is 10 minutes to 180 minutes.

[0037] In an optional embodiment, the temperature of the calcination treatment is 100°C to 600°C.

[0038] In an optional embodiment, the temperature of the reduction treatment is 200°C to 800°C.

[0039] In an optional embodiment, the reduction time of the reduction treatment is 10 minutes to 180 minutes.

[0040] In an optional embodiment, the reducing gas of the reduction treatment comprises hydrogen, or a mixed gas of hydrogen and at least one of nitrogen and argon.

[0041] In an optional embodiment, the purity of the rare earth raw material is not less than 99%; and / or, the particle size of the rare earth raw material is less than 10 μm; and / or, the treatment time of mixing the Al2O3-CuTe alloy composite with the rare earth raw material is 1 hour to 72 hours.

[0042] In an optional embodiment, the sintering treatment of the rare earth mixture to obtain the tellurium-copper alloy material comprises:

[0043] performing a forming treatment on the rare earth mixture to obtain a block;

[0044] performing a sintering treatment on the block to obtain the tellurium-copper alloy material;

[0045] In an optional embodiment, the forming treatment comprises any one of die pressing and cold isostatic pressing.

[0046] In an optional embodiment, the pressure of the forming treatment is 50 MPa to 350 MPa.

[0047] In an optional embodiment, the pressure holding time of the forming treatment is 5 seconds to 300 seconds.

[0048] In an optional embodiment, the sintering atmosphere of the sintering treatment comprises a reducing gas or a vacuum condition; wherein the reducing gas is hydrogen, or a mixed gas of hydrogen and at least one of nitrogen and argon.

[0049] In an optional embodiment, the sintering temperature of the sintering treatment is 850°C to 1050°C.

[0050] In an optional embodiment, the holding time of the sintering treatment is 30 minutes to 180 minutes.

[0051] In an optional embodiment, after the sintering treatment of the rare earth mixture, the method further comprises:

[0052] performing a first cold rolling treatment on the tellurium-copper alloy material to obtain a deformed material;

[0053] performing a solid solution treatment, an aging treatment and a first acid pickling treatment on the deformed material to obtain a first tellurium-copper material;

[0054] In an optional embodiment, the first cold rolling treatment is a positive direction cycle cold rolling.

[0055] In an optional embodiment, the first cold rolling treatment is performed 4 to 8 times, and a single cold rolling deformation is 15% to 20%.

[0056] In an optional embodiment, the solid solution temperature of the solid solution treatment is 750°C to 850°C.

[0057] In an optional embodiment, the holding time of the solid solution treatment is 10 minutes to 60 minutes.

[0058] In an optional embodiment, after the solid solution treatment, the material is quenched.

[0059] In an optional embodiment, the aging treatment temperature is 250°C to 350°C.

[0060] In an optional embodiment, the holding time of the aging treatment is 60 minutes to 180 minutes.

[0061] In an optional embodiment, the acid pickling solution of the first acid pickling treatment is a dilute nitric acid aqueous solution.

[0062] In an optional embodiment, the dilute nitric acid aqueous solution is a 10% to 20% dilute nitric acid aqueous solution.

[0063] In an optional embodiment, the first acid pickling treatment time is 20 seconds to 60 seconds.

[0064] In an optional embodiment, after the solid solution treatment, the aging treatment and the first acid pickling treatment of the deformed material, the method further comprises:

[0065] performing a second cold rolling treatment, an annealing treatment and a second acid pickling treatment on the first tellurium-copper material to obtain a second tellurium-copper material.

[0066] In an optional embodiment, the second cold rolling treatment is performed 4 to 8 times, wherein the single cold rolling deformation is 5% to 10%;

[0067] In an optional embodiment, the annealing treatment is performed at a temperature of 200°C to 300°C;

[0068] In an optional embodiment, the annealing treatment is performed for a holding time of 5 minutes to 30 minutes;

[0069] In an optional embodiment, the second pickling treatment is performed using a pickling solution of dilute nitric acid;

[0070] In an optional embodiment, the dilute nitric acid solution is a 10% to 20% dilute nitric acid solution;

[0071] In an optional embodiment, the second pickling treatment is performed for a time of 20 seconds to 60 seconds.

[0072] In a second aspect, the present application provides a tellurium-copper alloy material prepared by the method for preparing a tellurium-copper alloy material according to any one of the preceding embodiments.

[0073] Compared with the prior art, the present application has the following beneficial effects:

[0074] The preparation method provided by the present application can effectively improve the uniformity of the material and refine the grain structure during the preparation of the tellurium-copper alloy by forming a tellurium-copper complex solution and using a spray drying process. The copper-based composite powder prepared by the spray drying method can significantly affect the performance of the copper-based composite material in terms of microstructure, composition characterization, hardness, electrical conductivity, relative density, and other properties. This uniform distribution helps to improve the electrical conductivity and tensile strength of the alloy, and also improves the high-temperature oxidation resistance and high-temperature gas corrosion resistance of the alloy.

[0075] The present application uniformly disperses nano-aluminum oxide particles in the tellurium-copper alloy through a solution spray drying method, achieving significant dispersion strengthening effect, thereby improving the high-temperature strength of the material. The uniform distribution of nano-dispersed phase effectively hinders dislocation movement, enhances grain boundary stability, and thus improves the yield strength and tensile strength of the alloy. In addition, the addition of nano-aluminum oxide particles also refines the grain size, enhances the heat resistance and oxidation resistance of the alloy. These characteristics enable the tellurium-copper alloy material to exhibit excellent performance in high-temperature application fields such as aerospace, automobiles, and electronics, and the strengthening effect far exceeds that of traditional processes, providing a broader prospect for the application of alloy materials.

[0076] Doping rare earth elements is an important step in the preparation process of tellurium-copper alloy, which has a significant impact on the performance of the alloy. The addition of rare earth elements can purify the alloy, refine the structure, and effectively hinder the growth of the alloy structure at high temperature, thereby significantly improving the strength of the alloy. In addition, rare earth elements can react with impurity elements in the alloy to form slag and be removed, thereby purifying the alloy and improving the purity of the alloy, reducing the harmful effects of impurity elements on the tellurium-copper alloy.

[0077] Sintering is a key step in the preparation process of tellurium-copper alloy, which can be specifically controlled by controlling the sintering temperature and time to obtain a dense alloy material after sintering.

[0078] In addition, after sintering, other processing steps for optimizing the alloy material can also be carried out. For example, material deformation processing such as cold rolling and / or hot rolling can be used to further improve the density of the material, and the microstructure of the material can be fibrous (similar to the internal fibers of bamboo). Furthermore, this structure can be changed to an optimized structure by heat treatment, thereby optimizing the microstructure of the tellurium-copper alloy and improving its performance.

[0079] In summary, the preparation method of tellurium-copper alloy material can effectively improve the uniformity of the alloy, refine the grain, improve the strength and improve the thermoelectric performance by forming a tellurium-copper complex solution, spray drying, doping rare earth and precise control of the sintering process. These improvements not only enhance the physical properties of tellurium-copper alloy, but also expand its potential in industrial applications. BRIEF DESCRIPTION OF DRAWINGS

[0080] In order to more clearly illustrate the specific embodiments of the present application or the technical solutions in the prior art, the following will briefly introduce the drawings needed to be used in the specific embodiments or prior art description. Obviously, the drawings in the following description are some embodiments of the present application, and those skilled in the art can also obtain other drawings according to these drawings without creative labor.

[0081] Figure 1 The figure is a flowchart of the preparation method of tellurium-copper alloy material in the embodiments of the present application. DETAILED DESCRIPTION

[0082] The embodiments of the present application will be described in detail below with reference to the examples, but those skilled in the art will understand that the following examples are only used to illustrate the present application and should not be regarded as limiting the scope of the present application. If the specific conditions are not specified in the examples, the conventional conditions or the conditions recommended by the manufacturer are used. If the reagents or instruments used are not specified by the manufacturer, they are all conventional products that can be obtained by purchase.

[0083] In the embodiments of the present application, a preparation method of a tellurium-copper alloy material is provided. The tellurium-copper alloy material is prepared by forming a tellurium-copper complex solution from a tellurium-copper raw material, performing spray drying treatment, and performing calcination and reduction treatment, and doping a rare earth raw material, and then sintering.

[0084] The above-mentioned tellurium-copper raw material is a raw material used to form a tellurium-copper complex solution for preparing a tellurium-copper alloy material in the present technology. It can include a copper ion-containing compound, a tellurium ion-containing compound, and the like.

[0085] The above-mentioned tellurium-copper raw material is first formed into a tellurium-copper complex solution. By forming a tellurium-copper complex solution, tellurium and copper can be uniformly mixed at the molecular level, which is crucial for subsequent spray drying, calcination, and reduction processes. Uniform mixing helps to obtain an alloy material with uniform performance and improves the overall performance of the material. By forming a tellurium-copper complex solution, the distribution of the second phase in the alloy can be improved, and the segregation phenomenon at the grain boundaries can be reduced, thereby optimizing the microstructure of the material. This plays an important role in improving the electrical conductivity and mechanical properties of the alloy.

[0086] The above-mentioned spray drying treatment is a process in which liquid raw materials are dispersed into fine droplets by an atomizer and then contacted with a drying medium (usually hot air), thereby achieving rapid drying and obtaining a solid product.

[0087] Spray drying plays a key role in the preparation of tellurium-copper alloys. It atomizes the solution containing tellurium-copper raw materials into fine droplets and contacts them with hot air, rapidly evaporates the solvent, and leaves a dry precursor powder with uniform element distribution. This uniformity is crucial for subsequent sintering and material performance. In addition, the powder particles prepared by spray drying are fine, with an average size of about 200 nanometers, which helps to improve the sintering properties of the powder, so that the relative density of the sintered alloy is more than 98%, close to full densification. After reduction, the oxide composite powder after spray drying can form new alloy phases such as Cu x Te, etc. These new phases form nanoscale grains with the original phases, improving the electrical conductivity and tensile strength of the material. At the same time, the spray drying process also enables the uniform distribution of tellurium elements, nanoceramic phases, and rare earth elements in the tellurium-copper alloy, improving the microstructure of the material and enhancing its mechanical properties and thermal stability. Therefore, spray drying not only prepares uniform and fine precursor powder, but also forms a uniformly distributed alloy structure in the subsequent sintering and reduction processes, significantly improving the overall performance of the tellurium-copper alloy.

[0088] By adopting the preparation method in the embodiment, the tellurium copper raw material and rare earth elements in the tellurium copper alloy achieve a high degree of uniform distribution. This is due to the unique solution preparation, atomization drying and other process steps, effectively avoiding the element segregation problem commonly seen in traditional smelting methods, especially the more uniform distribution of elements at the grain boundaries, thereby significantly improving the overall performance of the material.

[0089] Due to the significant improvement in the uniformity of element distribution, the tellurium copper alloy prepared by the technical solution exhibits stronger softening resistance at high temperatures, which makes it possible for the alloy to serve under higher stress conditions, thereby widening its application range.

[0090] The uniformity of element distribution not only improves the mechanical strength of the alloy, but also maintains the excellent electrical conductivity of the tellurium copper alloy. Experimental results show that the electrical conductivity of the tellurium copper alloy material prepared by the method in the embodiment is improved by about 5%~10% compared with traditional methods, which is particularly important for applications in the electronic and electrical fields.

[0091] As described above, through calcination treatment, the precursor powder is heated in an air or oxygen atmosphere, causing the metal elements therein to combine with oxygen to form a composite oxide. This step helps to remove organic matter and volatile substances in the powder, and at the same time promotes the formation of metal oxides, laying a foundation for subsequent reduction treatment.

[0092] In the reduction treatment, the composite oxide is heated by passing a reducing gas (such as hydrogen or a mixture of hydrogen, nitrogen and argon) to reduce the metal oxide to metal, forming an Al2O3-CuTe alloy composite. This step is the key to achieving alloying, which ensures the uniform distribution of elements in the alloy, thereby improving the performance of the material.

[0093] As described above, rare earth refers to the general term of seventeen metal elements in the periodic table, including lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), and scandium (Sc) and yttrium (Y) closely related to lanthanide elements. The rare earth raw material in the embodiment can include but is not limited to the above-mentioned rare earth metal elements.

[0094] In the preparation of tellurium-copper alloys, the introduction of rare earth elements such as cerium-rich mischmetal is primarily aimed at refining the alloy's grain size and purifying the grain boundaries. This refinement results in a more compact fiber structure, thereby enhancing the electrical conductivity and tensile strength of the alloy. Grain refinement also helps reduce the inhomogeneity of deformation, lowers stress concentration, and thus reduces the risk of cracking. Additionally, the addition of rare earth elements significantly improves the alloy's oxidation resistance and gas corrosion resistance at high temperatures, particularly in medium to high temperature environments, where this oxidation resistance is particularly crucial.

[0095] During the smelting process, rare earth elements react with impurity elements, forming slag and being removed, thereby purifying the alloy and improving its purity. This process not only reduces the harmful effects of impurity elements but also enhances the electrical conductivity of the alloy. When the content of mischmetal in the rare earth tellurium-copper alloy is controlled at 0.02% to 0.3%, the effect of grain refinement and grain boundary purification is most significant, making the alloy perform well in terms of tensile strength, electrical conductivity, and corrosion resistance, with excellent comprehensive performance.

[0096] The addition of rare earth elements also enhances the alloy's corrosion resistance, which is crucial for extending the material's service life and improving stability. At the same time, rare earth elements significantly improve the alloy's strength and effectively inhibit the excessive growth of the alloy's structure at high temperatures. Therefore, the rare earth-doped tellurium-copper alloy plays a positive role in refining grains, improving electrical conductivity, enhancing high-temperature oxidation resistance, improving corrosion resistance, and improving mechanical properties, making it exhibit superior performance in numerous industrial applications.

[0097] In the process of preparing tellurium-copper alloy materials, sintering is a key step after doping rare earth elements. Sintering not only promotes the interaction between rare earth elements and other elements in the tellurium-copper raw material but also helps refine grains and purify grain boundaries, thereby enhancing the electrical conductivity and tensile strength of the alloy. In addition, sintering helps remove impurity elements, improve the purity of the alloy, and improve its oxidation resistance and corrosion resistance at high temperatures. By precisely controlling the sintering temperature and time, the microstructure of the alloy can be optimized to ensure the best effect of rare earth elements, making the tellurium-copper alloy exhibit excellent values in terms of tensile strength, electrical conductivity, corrosion resistance, and other aspects, with outstanding comprehensive performance, suitable for various industrial applications.

[0098] Specifically, by controlling the sintering temperature and time, a dense alloy material after sintering can be obtained. The material obtained after doping rare earth raw materials and pressing can be a material with a porous structure and a non-dense material, with a relative density of 60% to 70%, and the relative density of the material can be increased to more than 95% through sintering.

[0099] In some embodiments, with reference to Figure 1 , the method for preparing a tellurium-copper alloy material comprises:

[0100] Step S1, using a metal chelating agent to prepare the tellurium copper raw material into the metal salt and tellurium acid to obtain the tellurium copper complex solution.

[0101] The above, the tellurium copper raw material, including metal salt and tellurium acid. Among them, the metal salt can be the metal salt that can form a tellurium copper complex with tellurium acid, which can include copper-containing metal salt and the like.

[0102] This step involves mixing the tellurium copper raw material (metal salt and tellurium acid) with a metal chelating agent to form a tellurium copper complex solution. The role of the metal chelating agent is to form a stable complex with metal ions, improve the dispersion of each element in the solution, and thus the obtained tellurium copper complex solution provides a uniform precursor for subsequent spray drying treatment, which is beneficial to the formation of a uniform composition of tellurium copper alloy.

[0103] Using a metal chelating agent can improve the stability and uniformity of metal ions in the solution, reduce precipitation and aggregation, and facilitate the preparation of a mixed solution with more uniform element distribution.

[0104] Specifically, by stoichiometric calculation, copper nitrate, tellurium acid and aluminum nitrate can be mixed with a metal chelating agent in proportion, and fully stirred to form a uniform solution.

[0105] Step S2, the tellurium copper complex solution is subjected to spray drying treatment to obtain a precursor powder.

[0106] The above step converts the tellurium copper complex solution into a powder by spray drying technology. Spray drying is a process in which the solution is atomized into fine droplets, the solvent is quickly evaporated by hot air, and dry powder is left. The precursor powder obtained in this step has uniform chemical composition and small particle size, which is beneficial to the subsequent sintering and alloying process.

[0107] The above, the powder prepared by spray drying method has small particle size, which helps to improve the sintering properties of the powder, so that the relative density of the sintered alloy reaches more than 98%.

[0108] By adjusting the parameters of spray drying (such as inlet air temperature, atomizer speed, etc.), the morphology and particle size of the powder can be controlled.

[0109] Step S3, the precursor powder is subjected to calcination and reduction treatment to obtain an Al2O3-CuTe alloy composite.

[0110] The above, the precursor powder is subjected to calcination to remove organic matter and nitrate ions, and then subjected to reduction treatment to form an Al2O3-CuTe alloy composite. The Al2O3-CuTe alloy composite after calcination and reduction treatment provides a uniformly distributed alloy precursor for subsequent sintering.

[0111] Calcination and reduction treatment help to form new alloy phases such as CuTe x Te, etc. These new phases, together with the original phases, form nanoscale grains, thereby improving the electrical conductivity and tensile strength of the material.

[0112] The temperature, time, and atmosphere of calcination and reduction can be controlled to ensure complete conversion of the precursor powder into the desired alloy composite.

[0113] Step S4, mixing the Al2O3-CuTe alloy composite with rare earth raw materials to obtain a rare earth mixture.

[0114] As described above, the Al2O3-CuTe alloy composite is mixed with rare earth raw materials to form a rare earth mixture. The rare earth mixture contains the Al2O3-CuTe alloy composite and rare earth elements, providing a basis for preparing high-performance tellurium-copper alloys.

[0115] The addition of rare earth elements can purify the alloy, refine the structure, and effectively hinder the growth of the alloy structure at high temperatures, thereby significantly improving the strength of the alloy.

[0116] Uniform dispersion of the rare earth raw materials in the Al2O3-CuTe alloy composite can be achieved through physical mixing or mechanical stirring.

[0117] Step S5, sintering the rare earth mixture to obtain the tellurium-copper alloy material.

[0118] As described above, the rare earth mixture is sintered to form a dense tellurium-copper alloy material. The sintered tellurium-copper alloy material has excellent mechanical and electrical properties. The sintering process helps to bond and diffuse the particles, leading to neck formation and densification, thereby obtaining a complex network of parts with excellent mechanical properties.

[0119] Specifically, the temperature, atmosphere, and pressure of sintering can be controlled to optimize the microstructure and properties of the tellurium-copper alloy.

[0120] In this embodiment, the rare earth metal-containing alumina dispersion strengthened tellurium-copper alloy material prepared by the above method significantly improves the uniformity of element distribution, and the tellurium element, nanoceramic phase (Al2O3), and rare earth element in the tellurium-copper alloy material achieve a highly uniform distribution.

[0121] In the above steps of this embodiment, the synergistic effect is reflected in the calcination and reduction treatment and the addition of rare earth elements. Calcination and reduction treatment not only removes impurities in the precursor, but also promotes the formation of new alloy phases such as CuTe xThe addition of rare earth elements improves the performance of the material. The mixing of the rare earth elements with the Al2O3-CuTe alloy composite further improves the microstructure and performance of the alloy, and the synergistic effects of these reactions work together to make the final tellurium-copper alloy material have more excellent comprehensive performance.

[0122] In some embodiments, the metal salt is a metal salt that is soluble in water and does not leave any element other than the target element after thermal decomposition.

[0123] The above-mentioned target element is an element that needs to be prepared into a tellurium-copper alloy material to form a tellurium-copper complex solution, for example, a copper element.

[0124] In some embodiments, the metal salt includes a copper ion metal salt with copper as the target element.

[0125] In some embodiments, the metal salt further includes an aluminum ion metal salt with aluminum as the target element.

[0126] In some embodiments, the copper ion metal salt includes copper nitrate and copper acetate.

[0127] In some embodiments, the aluminum ion metal salt includes aluminum nitrate and aluminum acetate.

[0128] The above-mentioned copper ion metal salt can include but is not limited to copper nitrate and copper acetate, etc.; the aluminum ion metal salt can include but is not limited to aluminum nitrate and aluminum acetate, etc.; in addition, it can also include hydrates of these metal salts with crystal water, such as copper nitrate trihydrate, aluminum nitrate nonahydrate, etc.

[0129] In some embodiments, the tellurium-copper alloy material includes 0.2-1.0wt.% of tellurium, 0-0.5wt.% of Al2O3, and 0-0.2wt.% of the rare earth raw material.

[0130] In some embodiments, the step S1 uses a metal chelating agent to prepare the tellurium-copper complex solution from copper nitrate, aluminum nitrate, and telluric acid, including:

[0131] Step S11, dissolving the metal salt and telluric acid in water and mixing into a solution.

[0132] The above-mentioned step involves dissolving the metal salt and telluric acid, which are solid raw materials, in water to form a uniform solution.

[0133] For example, dissolving copper nitrate, aluminum nitrate, and telluric acid in water results in a solution containing copper, aluminum, and tellurium ions, which are uniformly distributed in the solution.

[0134] The water used can be regular water, deionized water, distilled water, double distilled water, ultrapure water, etc. For example, deionized water can be used to reduce impurities in the solution and avoid interference with subsequent reactions.

[0135] The above steps can accelerate the dissolution process by stirring or heating (if necessary) to ensure that all solid raw materials are completely dissolved.

[0136] Step S12, adding the metal chelating agent to the dissolution solution to form the tellurium-copper complex solution containing metal complexes.

[0137] As mentioned above, the metal chelating agent, such as citric acid, is added to the solution that has been formed, and reacts with the metal ions in the solution to form stable metal complexes, resulting in a tellurium-copper complex solution in which the metal ions are stably wrapped by the chelating agent, preventing ion aggregation and precipitation.

[0138] The use of chelating agents improves the stability of metal ions in the solution, helping to maintain the uniformity of the solution and providing a high-quality precursor solution for subsequent spray drying.

[0139] The amount of chelating agent added can be precisely controlled, and sufficient stirring can be used to ensure uniform reaction.

[0140] In this embodiment, the coordination of the metal chelating agent with the metal ions improves the stability of the metal ions in the solution, reducing ion aggregation and precipitation, which is crucial for subsequent spray drying and sintering processes. The formation of chelates helps to maintain the uniform distribution of components in the solution, which is crucial for the uniformity and performance of the final alloy. The use of deionized water and chelating agents helps to reduce impurities in the solution, thereby reducing impurity content in the final alloy and improving the purity and performance of the alloy.

[0141] Through the above two steps, a uniform and stable tellurium-copper complex solution is prepared, laying a good foundation for subsequent spray drying and sintering processes. This solution preparation method helps to improve the uniformity and performance of the final tellurium-copper alloy material, reducing performance differences caused by uneven distribution of raw materials.

[0142] In some embodiments, the metal chelating agent must meet the following two conditions:

[0143] (1) It contains hydroxyl functional groups that can form complexes with copper ions and aluminum ions.

[0144] (2) The structure of the substance has a negative charge that can attach to the surface of the metal complex particles.

[0145] As mentioned above, the hydroxyl functional groups (-OH) in the metal chelating agent can form complexes with metal ions (such as copper ions Cu2+ and aluminum ions Al 3+ ) to form stable coordination bonds. This coordination is achieved through the interaction between the lone pair of electrons and the empty orbital of the metal ion, resulting in the formation of stable complexes. This stability is crucial for maintaining the uniform distribution of metal ions in the solution, as it prevents the aggregation or precipitation of metal ions in the solution, ensuring the uniform distribution of elements in the tellurium-copper alloy material and the consistency of the final performance during subsequent spray drying and sintering processes.

[0146] As mentioned above, the negative charge in the metal chelating agent molecule (such as the negative charge from the carboxyl group -COOH - ) helps to increase the surface negative charge of the particles in the solution, and these negatively charged particles repel each other due to the same charge, reducing the aggregation between particles and further increasing the dispersibility. This repulsion helps to maintain the stability and uniformity of metal complexes in the solution, preventing the formation of large particles or aggregates during the preparation process, which is crucial for obtaining a uniform tellurium-copper alloy material.

[0147] By meeting these two conditions, the metal chelating agent not only improves the stability of metal ions in the solution, but also reduces particle aggregation through charge repulsion, thereby achieving more uniform element distribution and superior material performance during the preparation of tellurium-copper alloys. This uniform distribution helps to improve the electrical conductivity, mechanical properties, and high-temperature stability of the alloy, which is crucial for the application of tellurium-copper alloys in the electronics, electrical, automotive, and aerospace industries.

[0148] In some embodiments, the metal chelating agent includes citric acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, and diethylenetriamine pentaacetic acid.

[0149] For example, the metal chelating agent can be citric acid (C6H8O7), which has a reactive hydroxyl group in its molecule (-COOH) and can form stable complexes with metal ions such as Cu 2+ , Al 3+ , etc. This complexation can prevent the aggregation and precipitation of metal ions in the solution, thereby improving the dispersibility of elements in the solution.

[0150] At the same time, the citrate ion (C6H7O7-) is negatively charged, and after forming a complex with metal ions, it increases the surface negative charge of the particles in the solution. These negatively charged particles repel each other due to the same charge, reducing the aggregation between particles and also increasing the dispersibility.

[0151] In some embodiments, the step S2, the tellurium-copper complex solution is subjected to spray drying treatment to obtain a precursor powder, including:

[0152] Step S21, the tellurium copper complex solution is subjected to atomization treatment to form ultrafine droplets.

[0153] The above step involves using an atomization device (such as a spray dryer) to disperse the tellurium copper complex solution into ultrafine droplets. Atomization is the process of converting a liquid into fine droplets, which helps to increase the surface area of the liquid, preparing for the subsequent drying process, resulting in ultrafine droplets of tellurium copper complex. The size and uniformity of these droplets have a significant impact on the properties of the final powder.

[0154] Atomization treatment can make the tellurium copper complex in the solution more uniformly dispersed, laying the foundation for obtaining uniform powder.

[0155] Step S22, the ultrafine droplets are dried by hot air, i.e. the precursor powder is obtained.

[0156] In the above step, the atomized ultrafine droplets are dried by hot air to evaporate the solvent in the droplets, leaving dry powder, resulting in precursor powder, which will be used for subsequent calcination and reduction treatment.

[0157] Hot air drying is a fast drying method that can obtain dry powder in a short time, which helps to maintain the uniformity and chemical composition of the powder.

[0158] In this step, the droplets move along a spiral trajectory in the spray tower with high-temperature gas and are quickly dried to form near-spherical composite precursor powder, realizing the transformation from tellurium copper complex solution to precursor powder, providing a basis for the subsequent heat treatment step.

[0159] The synergistic effect of atomization treatment and hot air drying is to achieve uniform dispersion and rapid drying of tellurium copper complex, which is crucial for obtaining uniform precursor powder. The high-speed rotation of atomization and the high temperature of hot air drying can significantly improve the drying efficiency and shorten the production cycle. By precisely controlling the conditions of atomization and drying, the particle size and morphology of the powder can be adjusted, thereby affecting the performance of the final tellurium copper alloy material.

[0160] In some embodiments, the rotation speed of the atomization device for the atomization treatment is 4000 rpm to 30000 rpm. For example, the rotation speed can be 4000 rpm, 8000 rpm, 10000 rpm, 15000 rpm, 20000 rpm, 25000 rpm, 30000 rpm, etc.

[0161] In some embodiments, the temperature of the inlet of the hot air used for drying the ultrafine droplets is 100°C to 300°C. For example, the temperature can be 100°C, 150°C, 200°C, 250°C, 300°C, etc.

[0162] In some embodiments, the step S3 of calcining and reducing the precursor powder to obtain the Al2O3-CuTe alloy composite comprises:

[0163] The step S31 of calcining the precursor powder in an air or oxygen atmosphere to obtain a composite oxide.

[0164] In the above step, the precursor powder is heated to a certain temperature in an air or oxygen atmosphere to promote chemical reactions and physical changes, forming a composite oxide, so that the composite oxide obtained is the basis material for subsequent reduction treatment.

[0165] The calcination process helps to remove organic impurities and volatile substances in the precursor powder, while promoting the formation of metal oxides, preparing for the reduction reaction.

[0166] The step S32 of reducing the composite oxide in a reducing gas to obtain the Al2O3-CuTe alloy composite.

[0167] The above step involves exposing the composite oxide to a reducing gas to reduce the metal oxides to form the Al2O3-CuTe alloy composite. The Al2O3-CuTe alloy composite obtained is the raw material for subsequent sintering treatment. In this step, a chemical reduction reaction is carried out, and the metal oxides are reduced to metals.

[0168] The reduction process helps to reduce metal oxides to metals to form an alloy structure, which is crucial for improving the electrical conductivity and mechanical properties of the material.

[0169] In some embodiments, the calcination time of the calcination process is 10 minutes to 180 minutes. For example, the calcination time can be 10 minutes, 30 minutes, 50 minutes, 80 minutes, 100 minutes, 120 minutes, 150 minutes, 180 minutes, etc.

[0170] In some embodiments, the temperature of the calcination process is 100°C to 600°C; for example, the temperature can be 100°C, 200°C, 300°C, 400°C, 500°C, 600°C, etc.

[0171] In some embodiments, the temperature of the reduction process is 200°C to 800°C; for example, the temperature can be 200°C, 300°C, 400°C, 500°C, 600°C, 700°C, 800°C, etc.

[0172] In some embodiments, the reduction time of the reduction process is 10 minutes to 180 minutes; for example, it can be 10 minutes, 30 minutes, 50 minutes, 80 minutes, 100 minutes, 150 minutes, 180 minutes, etc.

[0173] In some embodiments, the reducing gas for the reduction treatment comprises any one of the following:

[0174] (1) hydrogen gas;

[0175] (2) a mixture of hydrogen gas and nitrogen gas;

[0176] (3) a mixture of hydrogen gas and argon gas;

[0177] (4) a mixture of hydrogen gas, nitrogen gas and argon gas.

[0178] In order to avoid introducing unnecessary impurities during the preparation process, the pure hydrogen gas or the mixture gas used can be high-purity gas.

[0179] In some embodiments, the purity of the rare earth raw material is not less than 99%; and / or, the particle size of the rare earth raw material is less than 10 μm; and / or, the mixing time of the Al2O3-CuTe alloy composite and the rare earth raw material is 1 hour to 72 hours. For example, the mixing time can be 1 hour, 6 hours, 12 hours, 15 hours, 24 hours, 36 hours, 48 hours, 60 hours, 72 hours, etc.

[0180] The uniform mixing of the rare earth powder and the Al2O3-CuTe alloy composite powder can be achieved by various methods, such as a blender, a ball mill, a mixer, etc. It can include but is not limited to a double-motion three-dimensional mixer, a rolling ball mill, a high-energy ball mill, a stirring ball mill, a V-type mixer, etc.

[0181] In some embodiments, the step S5, the sintering treatment of the rare earth mixture to obtain the tellurium-copper alloy material, comprises:

[0182] Step S51, the rare earth mixture is subjected to a forming treatment to obtain a block.

[0183] Step S52, the block is subjected to a sintering treatment to obtain the tellurium-copper alloy material.

[0184] The powder forming treatment is an important step in the powder metallurgy process, which involves compressing metal or ceramic powder into the desired shape and size by physical means. The purpose of this process is to manufacture a powder body with a specific shape and size for subsequent sintering or other heat treatment processes. The purpose is to manufacture a powder body with a specific shape to facilitate subsequent processing and to improve the density and strength of the powder body to withstand the pressure during handling and sintering.

[0185] In step S51, the rare earth mixture is formed into a block through a certain molding process to facilitate subsequent sintering treatment, and the obtained block is the preliminary shape of sintering treatment, which provides a physical basis for sintering. The molding process can ensure that the density and shape of the rare earth mixture meet the sintering requirements, which helps to improve the sintering efficiency and the performance of the final material.

[0186] As mentioned above, in step S52, the molded block is sintered under a certain atmosphere and temperature to form a dense tellurium-copper alloy material, so that the obtained tellurium-copper alloy material block has the required physical and chemical properties, such as high electrical conductivity and good mechanical properties. The sintering process can significantly improve the density and strength of the material, reduce porosity, and improve the overall performance of the material.

[0187] In some embodiments, the molding process includes any one of pressing and cold isostatic pressing.

[0188] As mentioned above, pressing is a powder molding technique, which is usually carried out at room temperature. In the pressing process, the powder is filled into a mold, and then shaped by applying external pressure. This pressure can be unidirectional, bidirectional or multidirectional, depending on the mold and the way the pressure is applied.

[0189] As mentioned above, cold isostatic pressing (CIP) is a powder molding technique, in which the powder is pressed without heating. In the cold isostatic pressing process, the powder is placed in a flexible container (such as a rubber bag), and then the pressure is transmitted through a liquid medium (such as water or oil) to uniformly press the powder in all directions.

[0190] In some embodiments, the pressure of the molding process is 50 MPa ~ 350 Mpa. For example, the pressure can be 50 Mpa, 80 Mpa, 100 Mpa, 150 Mpa, 200 Mpa, 250 Mpa, 300 Mpa, 350 Mpa, etc.

[0191] In some embodiments, the holding time of the molding process is 5 seconds ~ 300 seconds. For example, the holding time can be 5 seconds, 10 seconds, 50 seconds, 100 seconds, 150 seconds, 200 seconds, 250 seconds, 300 seconds, etc.

[0192] In some embodiments, the sintering atmosphere of the sintering process includes a reducing gas or a vacuum condition; wherein the reducing gas is hydrogen, or a mixed gas composed of hydrogen and at least one of nitrogen and argon. The reducing gas can be the same as or different from the gas in the aforementioned reduction process.

[0193] Specifically, the reducing gas for the reducing treatment includes any one of the following gases:

[0194] (1) hydrogen;

[0195] (2) a mixed gas of hydrogen and nitrogen;

[0196] (3) a mixed gas of hydrogen and argon;

[0197] (4) a mixed gas of hydrogen, nitrogen and argon.

[0198] In order to avoid introducing unnecessary impurities in the preparation process, high-purity gas can be used in the pure hydrogen or mixed gas.

[0199] In some embodiments, the sintering temperature of the sintering treatment is 850-1050°C.

[0200] In some embodiments, the holding time of the sintering treatment is 30-180 minutes.

[0201] In some embodiments, after the step S5, the step S5 further includes:

[0202] Step S6: performing a first cold rolling treatment on the tellurium-copper alloy material to obtain a deformed material.

[0203] The cold rolling treatment of the sintered tellurium-copper alloy material can further refine the grain structure of the material and increase its density, so as to obtain a cold-rolled deformed tellurium-copper alloy material with more refined grains and more uniform structure.

[0204] The cold rolling treatment can significantly increase the strength and hardness of the material, while reducing the thickness and size of the material. Specifically, uniform deformation of the material can be achieved by controlling the number of cold rolling and the amount of single cold rolling deformation, and by adopting the method of orthogonal direction cyclic cold rolling.

[0205] Step S7: performing a solid solution treatment, an aging treatment and a first acid pickling treatment on the deformed material to obtain a primary tellurium-copper material.

[0206] The solid solution treatment is a metal heat treatment process, and its main purpose is to improve the plasticity and toughness of the alloy and to prepare the structure for the subsequent aging treatment. In the solid solution treatment process, the alloy is heated to an appropriate temperature and maintained for a sufficient time to make the soluble phase fully dissolve into the solid solution matrix, and then rapidly cooled to room temperature to form a supersaturated solid solution. This treatment can improve the strength and corrosion resistance of the alloy, and help to eliminate stress and soften for further processing or forming.

[0207] The above-mentioned aging treatment is a kind of metal heat treatment process, mainly applied to alloy workpieces, especially after solid solution treatment, cold plastic deformation or casting, forging. The purpose of this process is to change the performance, shape and size of the workpiece over time at high temperature or room temperature.

[0208] The above-mentioned first pickling treatment and the second pickling treatment in the subsequent step are both surface treatment methods for the material, aiming to remove the oxide on the surface of the alloy material. The conditions and methods of the two pickling treatments can be consistent or different.

[0209] The above-mentioned deformed material after cold rolling is heated to a certain temperature and kept for a certain time, and then quenched to form a solid solution. The obtained tellurium-copper alloy material after solid solution treatment has more uniform distribution of alloy elements inside. Solid solution treatment helps to improve the corrosion resistance and mechanical properties of the material, and creates conditions for aging treatment.

[0210] The temperature and time of solid solution treatment and the cooling speed of quenching can be controlled to obtain the best solid solution effect.

[0211] In some embodiments, the first cold rolling treatment is orthogonal direction cyclic cold rolling.

[0212] The above-mentioned orthogonal direction cyclic cold rolling is a special cold rolling process, which involves the process of alternating cold rolling deformation in two perpendicular directions.

[0213] In some embodiments, the number of times of the first cold rolling treatment is 4-8 times; for example, the number of times can be 4, 5, 6, 7, 8, etc. Among them, the single cold rolling deformation amount is 15%-20%; for example, it can be 15%, 16%, 17%, 18%, 19%, 20%, etc.

[0214] In some embodiments, the solid solution temperature of the solid solution treatment is 750-850℃; for example, the solid solution temperature can be 750℃, 780℃, 800℃, 820℃, 830℃, 850℃, etc.

[0215] In some embodiments, the holding time of the solid solution treatment is 10-60 minutes; for example, the holding time can be 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes, etc.

[0216] In some embodiments, after the solid solution treatment, the material is subjected to quenching treatment.

[0217] As mentioned above, quenching is a step after solution treatment, and its purpose is to "freeze" the solute atoms in the solid solution by rapid cooling to prevent the precipitation of the second phase, so as to obtain the maximum supersaturation. This rapid cooling operation helps to obtain the highest strength and the best corrosion resistance. The quenching medium can be water, oil or other special organic medium.

[0218] As mentioned above, the reasons for quenching after solution treatment mainly include improving the strength and hardness of the material, which is crucial for many engineering applications; rapid cooling can inhibit the re-precipitation of the dissolved second phase during solution treatment, maintaining the supersaturated solid solution state, which is necessary for obtaining certain special physical and chemical properties; for some alloys such as stainless steel, quenching can also improve its corrosion resistance; in addition, quenching prepares for subsequent aging treatment, so that the supersaturated solid solution can occur during aging treatment, thereby further enhancing the hardness and strength of the alloy.

[0219] In some embodiments, the temperature of the aging treatment is 250°C to 350°C. For example, the temperature can be 250°C, 280°C, 300°C, 350°C, etc.

[0220] In some embodiments, the holding time of the aging treatment is 60 minutes to 180 minutes; for example, the holding time can be 60 minutes, 80 minutes, 100 minutes, 120 minutes, 150 minutes, 180 minutes, etc.

[0221] In some embodiments, the acid pickling solution of the first acid pickling treatment is a dilute nitric acid aqueous solution;

[0222] In some embodiments, the dilute nitric acid aqueous solution is a 10% to 20% dilute nitric acid aqueous solution; for example, the concentration of the dilute nitric acid aqueous solution can be 10%, 15%, 20%, etc.

[0223] In some embodiments, the time of the first acid pickling treatment is 20 seconds to 60 seconds. For example, it can be 20 seconds, 30 seconds, 40 seconds, 50 seconds, 60 seconds, etc.

[0224] In some embodiments, after the step S7, the deformed material is subjected to solution treatment, aging treatment and first acid pickling treatment to obtain a primary tellurium-copper material, the method further comprises:

[0225] Step S8, the primary tellurium-copper material is subjected to second cold rolling treatment, annealing treatment and second acid pickling treatment to obtain a secondary tellurium-copper material.

[0226] In some embodiments, the second cold rolling treatment is performed 4 to 8 times; for example, the number of times can be 4, 5, 6, 7, 8, and the like. In some embodiments, the single cold rolling deformation is 5% to 10%; for example, the single cold rolling deformation can be 5%, 6%, 7%, 8%, 9%, 10%, and the like.

[0227] In some embodiments, the annealing treatment is performed at a temperature of 200°C to 300°C; for example, the annealing treatment can be performed at a temperature of 200°C, 220°C, 250°C, 280°C, 300°C, and the like.

[0228] In some embodiments, the annealing treatment is performed for a holding time of 5 minutes to 30 minutes; for example, the annealing treatment can be performed for a holding time of 5 minutes, 8 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, and the like.

[0229] In some embodiments, the second acid pickling treatment is performed using a dilute nitric acid aqueous solution.

[0230] In some embodiments, the dilute nitric acid aqueous solution is a 10% to 20% dilute nitric acid aqueous solution; for example, the concentration of the dilute nitric acid aqueous solution can be 10%, 15%, 20%, and the like.

[0231] In some embodiments, the second acid pickling treatment is performed for a time of 20 seconds to 60 seconds; for example, the second acid pickling treatment can be performed for a time of 20 seconds, 30 seconds, 40 seconds, 50 seconds, 60 seconds, and the like.

[0232] In some embodiments, a tellurium-copper alloy material is provided, which is prepared by the method described in any one of the preceding embodiments.

[0233] Embodiment 1

[0234] In this embodiment, the preparation of the tellurium-copper alloy material is performed by the following method.

[0235] Experimental method:

[0236] (1) 18802 g of copper nitrate trihydrate, 36 g of telluric acid, 55 g of aluminum nitrate nonahydrate, and 1000 g of citric acid were added to 30 kg of deionized water, the water temperature was 90°C, and stirring was performed for 60 minutes;

[0237] (2) The solution was atomized into ultra-fine droplets in a spray drying tower and rapidly dried using hot air, the atomizing disc rotation speed was set to 18000 rpm, the feeding speed was set to 5 kg / h, and the inlet air temperature was set to 180°C, to obtain a precursor powder;

[0238] (3) The precursor powder was placed in a corundum boat, the material layer thickness was about 5 mm, the calcination temperature was 350°C, and the calcination time was 60 minutes, to obtain a composite oxide.

[0239] (4) Put the composite oxide powder into a corundum boat, and reduce in a tube furnace, the thickness of the material layer is about 5 mm, the reducing atmosphere is 75% hydrogen + 25% nitrogen, the gas purity is greater than 99.99%, the reducing temperature is 400°C, and the holding time is 90 minutes, to obtain an Al2O3-CuTe alloy composite;

[0240] (5) Put 0.9 g of yttrium powder and 3000 g of Al2O3-CuTe alloy composite into a double-motion three-dimensional mixer for mixing, the barrel rotation speed is 20 rpm, the blade rotation speed is 60 rpm, and the mixing time is 24 h, to obtain a rare earth mixture;

[0241] (6) Form the Y-Al2O3-CuTe alloy composite powder (rare earth mixture) into a block by cold isostatic pressing, the forming pressure is 180 MPa, and the holding time is 90 s, to obtain a block;

[0242] (7) Put the block into a hydrogen furnace for sintering, the sintering temperature is 930°C, and the holding time is 60 min, to obtain a sintered tellurium-copper alloy material;

[0243] (8) First cold rolling treatment: cyclically cold roll the sintered blank (sintered tellurium-copper alloy material) in the orthogonal direction for 6 times, and the single deformation amount is 20%, to obtain a deformed material;

[0244] (9) Solid solution treatment is performed on the deformed material, the temperature is 800°C, and the holding time is 20 min, and then the blank is quenched in water;

[0245] (10) Ageing treatment is performed on the quenched deformed material, the ageing temperature is 280°C, and the holding time is 90 min;

[0246] (11) First pickling treatment: pickling treatment is performed on the aged deformed material in a 15% dilute nitric acid aqueous solution, the pickling time is 40 s, to obtain a first tellurium-copper material;

[0247] (12) Second cold rolling treatment: unidirectionally cold roll the first tellurium-copper material for 6 times, and the single cold rolling deformation amount is 8%;

[0248] (13) Annealing treatment is performed on the first tellurium-copper material after the second cold rolling treatment, the annealing temperature is 230°C, and the holding time is 10 min, to obtain a second tellurium-copper material, i.e. an yttrium-containing alumina dispersion strengthened tellurium-copper alloy material.

[0249] The tellurium-copper alloy material prepared in this embodiment has the following alloy composition: Te: 0.40 wt.%, Al2O3: 0.15 wt.%, Y: 0.03 wt.%, and the balance being Cu.

[0250] The tensile strength of the tellurium-copper alloy material is 455 MPa, the electrical conductivity is 92% IACS, the thermal conductivity is 362 W / (m·K), the elongation is 11%, the hardness is 60 HRB, and the softening temperature is 810℃, which has good mechanical properties, electrical conductivity, thermal conductivity and high softening temperature.

[0251] Example 2

[0252] In this embodiment, the preparation of the tellurium-copper alloy material is carried out by the following method.

[0253] Experimental method:

[0254] (1) 22560 g of copper nitrate trihydrate, 43 g of telluric acid, 66 g of aluminum nitrate nonahydrate and 1200 g of citric acid were added to 40 kg of deionized water, the water temperature was 80℃, and stirring was carried out for 120 minutes;

[0255] (2) The solution was atomized into ultra-fine droplets in a spray drying tower and rapidly dried by hot air, the atomizing disc speed was set to 22000 rpm, the feeding speed was set to 6 kg / h, and the inlet temperature was set to 150℃, to obtain a precursor powder;

[0256] (3) The precursor powder was placed in a corundum boat, the layer thickness was about 6 mm, the calcination temperature was 400℃, and the calcination time was 40 minutes, to obtain a composite oxide;

[0257] (4) The composite oxide powder was placed in a corundum boat and reduced in a tube furnace, the layer thickness was about 6 mm, the reducing atmosphere was hydrogen with a purity of more than 99.99%, the reduction temperature was 500℃, and the holding time was 60 minutes, to obtain an Al2O3-CuTe alloy composite;

[0258] (5) 2.4 g of lanthanum powder was mixed with 3000 g of Al2O3-CuTe alloy composite powder in a double-motion three-dimensional mixer, the barrel speed was 25 rpm, the blade speed was 70 rpm, and the mixing time was 36 h, to obtain a rare earth mixture;

[0259] (6) The La-Al2O3-CuTe alloy composite powder was formed into a block by cold isostatic pressing at a pressure of 200 MPa for 70 s, to obtain a block;

[0260] (7) The tellurium-copper alloy block was sintered in a hydrogen furnace at a sintering temperature of 1000℃ for 90 min, to obtain a sintered tellurium-copper alloy material;

[0261] (8) First cold rolling treatment: the sintered blank was cyclically cold rolled in the orthogonal direction for 8 times with a single deformation amount of 15%, to obtain a deformed material;

[0262] (9) solid solution treatment of the deformed material at a temperature of 850°C for 15 min, and then quenching the blank in water;

[0263] (10) aging treatment of the quenched deformed material at an aging temperature of 250°C for 120 min;

[0264] (11) first pickling treatment: pickling the aged deformed material in a 20% dilute nitric acid aqueous solution for 20 s to obtain a first tellurium copper material;

[0265] (12) second cold rolling treatment: unidirectional cold rolling the first tellurium copper material for 8 times with a single cold rolling deformation of 6%;

[0266] (13) annealing the first tellurium copper material after the second cold rolling treatment at an annealing temperature of 250°C for 15 min to obtain a second tellurium copper material, i.e., a rare earth metal-containing aluminum oxide dispersion strengthened tellurium copper alloy material.

[0267] The alloy composition of the tellurium copper alloy material prepared in this example is: Te: 0.40 wt.%, Al2O3: 0.15 wt.%, La: 0.08 wt.%, and the balance is Cu. The tensile strength of the tellurium copper alloy material is 486 MPa, the electrical conductivity is 96% IACS, the thermal conductivity is 380 W / (m·K), the elongation is 19%, the hardness is 63 HRB, and the softening temperature is 860°C, which has good mechanical properties, electrical conductivity, thermal conductivity and high softening temperature.

[0268] Example 3

[0269] In this example, the preparation of a tellurium copper alloy material is carried out by the following method.

[0270] Experimental method:

[0271] (1) 18762 g of copper nitrate trihydrate, 45 g of telluric acid, 92 g of aluminum nitrate nonahydrate and 1300 g of citric acid are added to 35 kg of deionized water, the water temperature is 85°C, and stirring is carried out for 90 minutes;

[0272] (2) The solution is atomized into ultra-fine droplets in a spray drying tower and rapidly dried by hot air, the atomizing disc speed is set to 13000 rpm, the feeding speed is set to 3 kg / h, and the inlet temperature is set to 130°C to obtain a precursor powder;

[0273] (3) The precursor powder is placed in a corundum boat with a layer thickness of about 10 mm, calcined at a temperature of 450°C for 30 minutes to obtain a composite oxide;

[0274] (4) Put the composite oxide powder into a corundum boat, and reduce in a tube furnace, the thickness of the material layer is about 10 mm, the reducing atmosphere is 70% hydrogen + 30% argon, the gas purity is greater than 99.99%, the reducing temperature is 600°C, and the holding time is 40 minutes, to obtain an Al2O3-CuTe alloy composite;

[0275] (5) Put 1.5 g of cerium powder and 3000 g of Al2O3-CuTe alloy composite powder into a rolling ball mill for mixing, in order to avoid the introduction of non-volatile impurities caused by friction, a polyurethane ball mill tank is used, and a pure copper material is used as the grinding ball, the ball-to-material ratio is 5:1, and the ball milling time is 48 h, to obtain a rare earth mixture;

[0276] (6) The Ce-Al2O3-CuTe alloy composite powder is formed into a block by cold isostatic pressing, the forming pressure is 150 MPa, and the holding time is 120 s, to obtain a block;

[0277] (7) Put the tellurium copper alloy block into a hydrogen furnace for sintering, the sintering temperature is 1050°C, and the holding time is 80 min, to obtain a sintered tellurium copper alloy material;

[0278] (8) First cold rolling treatment: the sintered blank is cyclically cold rolled in the orthogonal direction for 5 times, and the single deformation amount is 18%, to obtain a deformed material;

[0279] (9) The deformed material is subjected to solid solution treatment at a temperature of 760°C for 40 min, and then the blank is quenched in water;

[0280] (10) The deformed material after quenching treatment is subjected to aging treatment at an aging temperature of 320°C for 60 min;

[0281] (11) First pickling treatment: the deformed material after aging treatment is pickled in a 20% dilute nitric acid aqueous solution for 15 s, to obtain a first tellurium copper material;

[0282] (12) Second cold rolling treatment: the first tellurium copper material is unidirectionally cold rolled for 5 times, and the single cold rolling deformation amount is 10%;

[0283] (13) The first tellurium copper material after the second cold rolling treatment is annealed at a temperature of 280°C for 10 min.

[0284] The alloy composition of the tellurium-copper alloy material prepared in the embodiment is: Te: 0.50 wt.%, Al2O3: 0.25 wt.%, Ce: 0.05 wt.%, and the balance is Cu. The tensile strength of the tellurium-copper alloy material is 518 MPa, the electrical conductivity is 92% IACS, the thermal conductivity is 361 W / (m·K), the elongation is 13%, the hardness is 68 HRB, and the softening temperature is 895°C, and the mechanical properties, electrical conductivity, thermal conductivity and high softening temperature are good.

[0285] Example 4

[0286] In the embodiment, the following method is used to prepare the tellurium-copper alloy material.

[0287] Experimental method:

[0288] (1) 22514 g of copper nitrate trihydrate, 54 g of telluric acid, 110 g of aluminum nitrate nonahydrate and 1500 g of citric acid were added to 35 kg of deionized water, the water temperature was 90°C, and stirring was carried out for 120 minutes;

[0289] (2) The solution was atomized into ultra-fine droplets in a spray drying tower and rapidly dried with hot air, the atomizing disc rotation speed was set to 26000 rpm, the feeding speed was set to 8 kg / h, and the inlet temperature was set to 200°C to obtain a precursor powder;

[0290] (3) The precursor powder was placed in a corundum boat, the layer thickness was about 5 mm, the calcination temperature was 400°C, and the calcination time was 120 minutes to obtain a composite oxide;

[0291] (4) The composite oxide powder was placed in a corundum boat and reduced in a tube furnace, the layer thickness was about 5 mm, the reducing atmosphere was hydrogen with a purity of greater than 99.99%, the reduction temperature was 700°C, and the holding time was 30 minutes to obtain an Al2O3-CuTe alloy composite;

[0292] (5) 3.2 g of lanthanum powder was mixed with 4000 g of Al2O3-CuTe alloy composite powder in a V-type mixer at a rotation speed of 45 rpm for 24 h to obtain a rare earth mixture;

[0293] (6) The La-Al2O3-CuTe alloy composite powder was formed into a block by a hydraulic press at a forming pressure of 300 MPa and a pressure holding time of 10 s to obtain a block;

[0294] (7) The tellurium-copper alloy block was sintered in a hydrogen furnace at a sintering temperature of 850°C for 120 min to obtain a deformed material;

[0295] (8) The sintered blank is cyclically cold-rolled in the orthogonal direction for 4 times, and the single deformation amount is 20%;

[0296] (9) The deformed material is subjected to solid solution treatment at a temperature of 750 °C for 60 min, and then the blank is quenched in water;

[0297] (10) The deformed material after quenching is subjected to aging treatment at an aging temperature of 300 °C for 120 min;

[0298] (11) The deformed material after aging is subjected to pickling treatment in a 15% dilute nitric acid aqueous solution for 30 s, to obtain a first tellurium copper material;

[0299] (12) The tellurium copper alloy block after S11 is unidirectionally cold-rolled for 8 times, and the single cold rolling deformation amount is 5%;

[0300] (13) The first tellurium copper material after the second cold rolling treatment is subjected to annealing treatment at an annealing temperature of 200 °C for 25 min, to obtain a second tellurium copper material, i.e. an aluminum oxide dispersion strengthened tellurium copper alloy material containing rare earth metals.

[0301] The alloy composition of the tellurium copper alloy material prepared in this embodiment is: Te: 0.50 wt.%, Al2O3: 0.25 wt.%, La: 0.08 wt.%, and the balance is Cu. The tensile strength of the tellurium copper alloy material is 515 MPa, the electrical conductivity is 94% IACS, the thermal conductivity is 375 W / (m·K), the elongation is 16%, the hardness is 67 HRB, and the softening temperature is 900 °C, which has good mechanical properties, electrical conductivity, thermal conductivity and high softening temperature.

[0302] Example 5

[0303] In this embodiment, the preparation of the tellurium copper alloy material is carried out by the following method.

[0304] Experimental method:

[0305] (1) 18781 g of copper nitrate trihydrate, 27 g of telluric acid, 129 g of aluminum nitrate nonahydrate and 1000 g of citric acid are added to 40 kg of deionized water, the water temperature is 90 °C, and stirring is carried out for 90 minutes;

[0306] (2) The solution is atomized into ultra-fine droplets in a spray drying tower and rapidly dried by hot air, the atomizing disc rotation speed is set to 15000 rpm, the feeding speed is set to 5 kg / h, and the inlet temperature is set to 170 °C, to obtain a precursor powder;

[0307] (3) Put the precursor powder into a corundum boat, the thickness of the material layer is about 6 mm, the calcination temperature is 450°C, and the calcination time is 90 minutes to obtain the composite oxide;

[0308] (4) Put the composite oxide powder into a corundum boat, and reduce in a tube furnace, the thickness of the material layer is about 6 mm, the reducing atmosphere is 70% hydrogen + 30% nitrogen, the gas purity is greater than 99.99%, the reduction temperature is 500°C, and the holding time is 120 minutes to obtain the Al2O3-CuTe alloy composite;

[0309] (5) Mix 2.0 g of lanthanum powder with 4000 g of Al2O3-CuTe alloy composite powder in a double-motion three-dimensional mixer, the barrel rotation speed is 20 rpm, the blade rotation speed is 80 rpm, and the mixing time is 12 h to obtain a rare earth mixture;

[0310] (6) Form the La-Al2O3-CuTe alloy composite powder into a block by using a hydraulic press, the forming pressure is 350 MPa, and the pressure holding time is 10 s to obtain a block;

[0311] (7) Sinter the tellurium-copper alloy block in a hydrogen furnace, the sintering temperature is 900°C, and the holding time is 150 min to obtain a sintered tellurium-copper alloy material;

[0312] (8) First cold rolling treatment: cyclically cold roll the sintered blank in the orthogonal direction 8 times with a single deformation amount of 8% to obtain a deformed material;

[0313] (9) Solid solution treatment of the deformed material at a temperature of 800°C for 20 min, and then quench the blank in water;

[0314] (10) Ageing treatment of the quenched deformed material at an ageing temperature of 280°C for 180 min;

[0315] (11) First acid pickling treatment: acid pickling of the aged deformed material in a 15% dilute nitric acid aqueous solution for 30 s to obtain a first tellurium-copper material;

[0316] (12) Second cold rolling treatment: unidirectional cold rolling of the tellurium-copper alloy block after S11 for 6 times with a single cold rolling deformation amount of 8%;

[0317] (13) Annealing treatment of the first tellurium-copper material after the second cold rolling treatment at an annealing temperature of 280°C for 20 min to obtain a second tellurium-copper material, i.e. an alumina dispersion strengthened tellurium-copper alloy material containing rare earth metals.

[0318] The alloy composition of the tellurium-copper alloy material prepared in the embodiment is: Te: 0.30 wt.%, Al2O3: 0.35 wt.%, La: 0.05 wt.%, and the balance is Cu. The tensile strength of the tellurium-copper alloy material is 575 MPa, the electrical conductivity is 90% IACS, the thermal conductivity is 351 W / (m·K), the elongation is 10%, the hardness is 73 HRB, and the softening temperature is 930°C, and the tellurium-copper alloy material has good mechanical properties, electrical conductivity, thermal conductivity and high softening temperature.

[0319] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, and not to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacement to part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for producing a tellurium-copper alloy material, characterized by comprising: The application relates to a preparation method of a tellurium-copper alloy material. ​ The method comprises the following steps: preparing a tellurium-copper complex solution by using a metal chelating agent to prepare metal salts and tellurium acid in tellurium-copper raw materials, wherein the metal salts and the tellurium acid are dissolved in water to form a dissolving solution; the metal chelating agent is added into the dissolving solution to form the tellurium-copper complex solution containing metal complexes; the metal chelating agent contains hydroxyl groups capable of forming complexes with copper ions and aluminum ions; the metal chelating agent has negative charges capable of adhering to the surface of the metal complex particles; the metal chelating agent comprises citric acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid and diethylenetriamine pentaacetic acid; the metal salts comprise copper ion metal salts and aluminum ion metal salts; the copper ion metal salts comprise copper nitrate and copper acetate; the aluminum ion metal salts comprise aluminum nitrate and aluminum acetate; the tellurium-copper complex solution is subjected to spray drying treatment to obtain a precursor powder, wherein the tellurium-copper complex solution is subjected to atomization treatment to form ultra-micro droplets; the ultra-micro droplets are dried by hot air to obtain the precursor powder; the rotation speed of an atomization device for the atomization treatment is 4000 rpm-30000 rpm; the temperature of an air inlet for drying the ultra-micro droplets by hot air is 100 DEG C-300 DEG C; the precursor powder is subjected to calcination treatment and reduction treatment to obtain an Al2O3-CuTe alloy composite, wherein the precursor powder is subjected to calcination treatment in an air or oxygen atmosphere to obtain a composite oxide; the composite oxide is subjected to reduction treatment by being introduced into a reducing gas to obtain the Al2O3-CuTe alloy composite; the calcination time of the calcination treatment is 10 minutes-180 minutes; the temperature of the calcination treatment is 100 DEG C-600 DEG C; the temperature of the reduction treatment is 200 DEG C-800 DEG C; the reduction time of the reduction treatment is 10 minutes-180 minutes; the reducing gas of the reduction treatment comprises hydrogen or a mixed gas formed by at least one of nitrogen and argon and hydrogen; the Al2O3-CuTe alloy composite is mixed with rare earth raw materials to obtain a rare earth mixture; the rare earth mixture is subjected to sintering treatment to obtain the tellurium-copper alloy material; the tellurium-copper alloy material contains tellurium with a content of 0.2-1.0 wt.%, Al2O3 with a content of 0-0.5 wt.% and the rare earth raw materials with a content of 0-0.2 wt.%; the rare earth raw materials comprise rare earth metal elements. The purity of the rare earth raw materials is not less than 99%. The particle size of the rare earth raw materials is less than 10 mu m. The treatment time for mixing the Al2O3-CuTe alloy composite with the rare earth raw materials is 1 hour-72 hours.

2. The method for preparing the tellurium-copper alloy material as described in claim 1, characterized in that, The sintering treatment of the rare earth mixture to obtain the tellurium-copper alloy material comprises the following steps: performing forming treatment on the rare earth mixture to obtain a block; and performing sintering treatment on the block to obtain the tellurium-copper alloy material.

3. The method for preparing the tellurium-copper alloy material as described in claim 1, characterized in that, The forming treatment method comprises any one of die pressing and cold isostatic pressing.

4. The method for preparing the tellurium-copper alloy material as described in claim 1, characterized in that, The pressure of the forming treatment is 50 MPa-350 MPa.

5. The method for preparing the tellurium-copper alloy material as described in claim 1, characterized in that, ​ ​ ​ 6. The method for preparing the tellurium-copper alloy material as described in claim 5, characterized in that, ​ 7. The method for preparing the tellurium-copper alloy material as described in claim 5, characterized in that, ​ 8. The method for preparing the tellurium-copper alloy material as described in claim 5, characterized in that, The pressure maintaining time of the forming treatment is 5-300 seconds.

9. The method for preparing the tellurium-copper alloy material as described in claim 5, characterized in that, The sintering atmosphere of the sintering treatment comprises a reducing gas or vacuum condition; wherein the reducing gas is hydrogen, or a mixed gas of at least one of nitrogen and argon and hydrogen.

10. The method for preparing the tellurium-copper alloy material as described in claim 5, characterized in that, The sintering temperature of the sintering treatment is 850-1050℃.

11. The method for preparing the tellurium-copper alloy material as described in claim 5, characterized in that, The holding time of the sintering treatment is 30-180 minutes.

12. The method for preparing the tellurium-copper alloy material as described in claim 1, characterized in that, After the sintering treatment of the rare earth mixture to obtain the tellurium-copper alloy material, the method further comprises: carrying out a first cold rolling treatment on the tellurium-copper alloy material to obtain a deformed material; carrying out a solid solution treatment, an aging treatment and a first acid pickling treatment on the deformed material to obtain a primary tellurium-copper material.

13. The method for preparing the tellurium-copper alloy material as described in claim 12, characterized in that, The number of times of the first cold rolling treatment is 4-8; wherein the single cold rolling deformation is 15-20%.

14. The method for preparing the tellurium-copper alloy material as described in claim 12, characterized in that, The solid solution temperature of the solid solution treatment is 750-850℃.

15. The method for preparing the tellurium-copper alloy material as described in claim 12, characterized in that, The holding time of the solid solution treatment is 10-60 minutes.

16. The method for preparing the tellurium-copper alloy material as described in claim 12, characterized in that, After the solid solution treatment, the material is quenched.

17. The method for preparing the tellurium-copper alloy material as described in claim 12, characterized in that, The aging treatment temperature is 250-350℃.

18. The method for preparing the tellurium-copper alloy material as described in claim 12, characterized in that, The holding time of the aging treatment is 60-180 minutes.

19. The method for preparing the tellurium-copper alloy material as described in claim 12, characterized in that, The acid pickling solution of the first acid pickling treatment is a dilute nitric acid aqueous solution; The dilute nitric acid aqueous solution is a 10-20% dilute nitric acid aqueous solution.

20. The method for preparing the tellurium-copper alloy material as described in claim 12, characterized in that, The time of the first acid pickling treatment is 20-60 seconds.

21. The method for preparing the tellurium-copper alloy material as described in claim 12, characterized in that, After the solid solution treatment, the aging treatment and the first acid pickling treatment of the deformed material to obtain the primary tellurium-copper material, the method further comprises: carrying out a second cold rolling treatment, an annealing treatment and a second acid pickling treatment on the primary tellurium-copper material to obtain a secondary tellurium-copper material.

22. The method for preparing the tellurium-copper alloy material as described in claim 21, characterized in that, The number of times of the second cold rolling treatment is 4-8; wherein the single cold rolling deformation is 5-10%.

23. The method for preparing the tellurium-copper alloy material as described in claim 21, characterized in that, The annealing treatment temperature is 200-300℃.

24. The method for preparing the tellurium-copper alloy material as described in claim 21, characterized in that, The holding time of the annealing treatment is 5-30 minutes.

25. The method for preparing the tellurium-copper alloy material as described in claim 21, characterized in that, The acid pickling solution of the second acid pickling treatment is a dilute nitric acid aqueous solution; The dilute nitric acid aqueous solution is a 10-20% dilute nitric acid aqueous solution.

26. The method for preparing the tellurium-copper alloy material as described in claim 21, characterized in that, The time of the second acid pickling treatment is 20-60 seconds.

27. A tellurium-copper alloy material, characterized by, The tellurium-copper alloy material is prepared by the method of any one of claims 1-26.

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