CN111434789A - Heat treatment type high-conductivity heat-resistant Al-Zr-Er-Yb alloy wire material and preparation method thereof - Google Patents
Heat treatment type high-conductivity heat-resistant Al-Zr-Er-Yb alloy wire material and preparation method thereof Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000010936 titanium Substances 0.000 claims abstract description 36
- 239000011572 manganese Substances 0.000 claims abstract description 35
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 35
- 239000011651 chromium Substances 0.000 claims abstract description 33
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 31
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 229910052796 boron Inorganic materials 0.000 claims abstract description 20
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- 229910052748 manganese Inorganic materials 0.000 claims abstract description 14
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- 239000010703 silicon Substances 0.000 claims abstract description 12
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- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims abstract description 10
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims abstract description 10
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 9
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- 238000005266 casting Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 33
- 238000001816 cooling Methods 0.000 claims description 29
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- 229910052742 iron Inorganic materials 0.000 claims description 21
- -1 aluminum erbium Chemical compound 0.000 claims description 20
- 238000007670 refining Methods 0.000 claims description 15
- ZGUQGPFMMTZGBQ-UHFFFAOYSA-N [Al].[Al].[Zr] Chemical compound [Al].[Al].[Zr] ZGUQGPFMMTZGBQ-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
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- 229910052761 rare earth metal Inorganic materials 0.000 description 10
- 238000003723 Smelting Methods 0.000 description 9
- DJPURDPSZFLWGC-UHFFFAOYSA-N alumanylidyneborane Chemical compound [Al]#B DJPURDPSZFLWGC-UHFFFAOYSA-N 0.000 description 9
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- 229910018580 Al—Zr Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
- B22D11/003—Aluminium alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/026—Alloys based on aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/023—Alloys based on aluminium
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- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention provides a heat treatment type high-conductivity heat-resistant Al-Zr-Er-Yb alloy wire material, which comprises the following components in percentage by weight: 0.02-0.15 Wt% of zirconium Zr, 0.01-0.2 Wt% of erbium Er, 0.01-0.25 Wt% of ytterbium Yb, 0.01-0.04 Wt% of boron B, less than or equal to 0.20 Wt% of ferrum Fe, less than or equal to 0.05 Wt% of silicon Si, less than or equal to 0.01% of (vanadium V + titanium Ti + chromium Cr + manganese Mn), and the balance of aluminum. The electric conductivity of the lead prepared by the technical scheme provided by the invention is not less than 62% IACS, the tensile strength at room temperature is not less than 160MPa, the long-term heat-resistant temperature reaches 150 ℃, and the short-term heat-resistant temperature reaches 230 ℃.
Description
Technical Field
The invention belongs to the technical field of aluminum alloy, and particularly relates to a heat-treatment type high-conductivity heat-resistant Al-Zr-Er-Yb alloy wire material and a preparation method thereof.
Background
The heat-resistant aluminum alloy conductor is a special expansion conductor with good performance, the large-capacity heat-resistant aluminum alloy conductor is adopted for expansion transformation of the existing line, and under the principle that the pole tower is not replaced as much as possible, the transmission capacity of the line can be improved, and the overall construction cost of a project can be reduced. At present, the conductivity of a product with the heat-resistant temperature of 150 ℃ of a heat-resistant aluminum alloy wire at home and abroad is only 60% IACS, so that the requirements of long-distance and large-capacity power transmission line construction engineering and power grid capacity expansion and reconstruction engineering are difficult to meet. The high-conductivity heat-resistant aluminum alloy wire can stably work at a higher operation temperature, allows the borne current to be larger, can improve the safety and stability of line operation, can reduce the construction and maintenance cost, prolongs the service life of a power transmission line, saves line corridor resources, can reduce carbon emission, and has remarkable economic and social benefits.
For the heat-resistant aluminum alloy wire, the difficulty of the technical barrier for improving the conductivity by 1 percent on the existing basis is very high. The industrial application of 60% heat-resistant aluminum wire has been realized in 1970 in japan, but the engineering application of 61% IACS using heat-resistant aluminum wire with a temperature of 150 ℃ has not been completely broken through until 2010. The conductivity of the heat-resistant aluminum wire with the market occupancy rate of 70 percent of the Japanese power transmission line is still 60 percent IACS. And the process of improving the conductivity of the common duralumin wire from 60% IACS to 61% IACS in China takes decades. The Shanghai Cable research institute Huang Chong Qi Yard makes outstanding contribution to improving the conductivity of the aluminum conductor for electricians and the aluminum conductor for rare earth electricians in China, solving the problem of wide domestic material sources and achieving industrial stable production. For Al-Zr heat-resistant aluminum wire, the electric conductivity limit is 62% IACS under the limit annealing condition of 1000 h. The heat-resistant aluminum conductor in China is in the conductivity level of 58% IACS for a long time within 20 years, so that the line loss is increased, and the comprehensive economic benefit is poor. Therefore, under the condition of lower cost, the technical difficulty of the heat-resistant aluminum alloy wire with the conductivity of more than 61% IACS and the use temperature of 150 ℃ is higher, the economic and social benefits brought by the improvement of the conductivity are huge, and the requirements of accelerating the construction of a resource-saving and environment-friendly smart power grid proposed by China are completely met.
Patent 201010106186.0 discloses a high-conductivity non-heat-treatment type rare earth heat-resistant aluminum alloy conductor material, which comprises the following elements in percentage by mass: 0.03 to 0.06 percent of Zr, 0.05 to 0.20 percent of Er, 0.10 to 0.25 percent of Y, 0.05 to 0.12 percent of Fe, 0.01 to 0.03 percent of Ti, less than or equal to 0.06 percent of impurity element Si, less than or equal to 0.10 percent of other impurities, and the balance of aluminum. Its conductivity is only 60% IACS. Patent 201010593503.6 provides a high-conductivity heat-resistant aluminum alloy wire and a preparation method thereof, wherein the aluminum alloy wire comprises the following chemical components in percentage by mass: 0.1 to 0.3 percent of Zr, 0.02 to 0.2 percent of Y, 0.01 to 0.15 percent of Sc, and the balance of Al and inevitable other impurity elements, and the electric conductivity after annealing is 61 percent IACS. Patent 201710765536.6 discloses a low-temperature sensitive high-conductivity aluminum alloy and a preparation method thereof, wherein the aluminum alloy comprises the following chemical components in percentage by mass: 0.02-0.08% of B, 0.05-0.20% of Yb, 0-0.10% of Sc, and the balance of Al and trace inevitable impurity elements. The as-cast alloy is annealed at 400 ℃ for 3h, and the room temperature conductivity is 60-61% IACS. However, the alloy disclosed by the patent is usually added with a noble metal element Sc, so that the ingot casting preparation process is complex, the preparation process is difficult to control, the alloy cost is high, and the alloy is not suitable for industrial large-scale popularization and application.
According to the invention, Zr, Er and Yb are compositely added into industrial pure aluminum, the reasonable Fe and Si contents and the proportion thereof are controlled, the impurity element content is accurately controlled, and a reasonable processing and preparation process is combined to obtain the high-conductivity heat-resistant aluminum alloy conductor material with the heat resistance temperature of 150 ℃, the room-temperature tensile strength of more than or equal to 160MPa and the conductivity of more than or equal to 62% IACS.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a heat-treatment type high-conductivity heat-resistant Al-Zr-Er-Yb alloy wire material and a preparation method thereof.
In order to realize the purpose of the invention, the following technical scheme is adopted:
the improvement of a heat treatment type high-conductivity heat-resistant Al-Zr-Er-Yb alloy wire material is that the alloy comprises the following components in percentage by weight:
0.02-0.15 Wt% of zirconium Zr, 0.01-0.2 Wt% of erbium Er, 0.01-0.25 Wt% of ytterbium Yb, 0.01-0.04 Wt% of boron B, less than or equal to 0.20 Wt% of iron Fe, less than or equal to 0.05 Wt% of silicon Si, wherein the sum of vanadium V, titanium Ti, chromium Cr and manganese Mn is less than or equal to 0.01%, and the balance of aluminum.
Preferably, the alloy has the following components:
0.02-0.1 Wt% of zirconium Zr, 0.01-0.15 Wt% of erbium Er, 0.01-0.2 Wt% of ytterbium Yb, 0.01-0.04 Wt% of boron B, less than or equal to 0.20 Wt% of iron Fe, less than or equal to 0.05 Wt% of silicon Si, wherein the sum of vanadium V, titanium Ti, chromium Cr and manganese Mn is less than or equal to 0.01%, and the balance of aluminum.
Preferably, the alloy has the following components:
0.02-0.08 Wt% of zirconium Zr, 0.01-0.15 Wt% of erbium Er, 0.01-0.2 Wt% of ytterbium Yb, 0.01-0.04 Wt% of boron B, less than or equal to 0.20 Wt% of iron Fe, less than or equal to 0.05 Wt% of silicon Si, wherein the sum of vanadium V, titanium Ti, chromium Cr and manganese Mn is less than or equal to 0.01%, and the balance of aluminum.
Preferably, the alloy has the following components:
zirconium Zr 0.05%, erbium Er 0.15%, ytterbium Yb 0.15%, boron B0.02%, ferrum Fe 0.1%, silicon Si 0.04%, wherein vanadium V + titanium Ti + chromium Cr + manganese Mn 0.005%, and the balance of aluminum.
In a method of making a heat-treated, high conductivity, heat resistant Al-Zr-Er-Yb alloy wire stock according to any one of claims 1 to 4, the improvement comprising the steps of:
(1) adding Al-B intermediate alloy into the aluminum ingot melt at the temperature of 660-750 ℃, stirring for 5-60min and standing for 30-300 min;
(2) adding an aluminum zirconium, aluminum erbium and aluminum ytterbium intermediate alloy into the melt obtained in the step 1), and stirring for 5-15 min;
(3) adding a refining agent into the melt obtained in the step 2), refining for 10-30min, and slagging off;
(4) keeping the temperature and standing for 30-300min after slagging off, and performing online degassing and deslagging treatment;
(5) continuously casting by using a water-cooling copper continuous casting wheel method;
(6) rolling the casting blank obtained in the step 5) into a round rod with the diameter of 9.5 mm;
(7) heating the round rod in the step 6) from room temperature to 350 ℃ for 200-;
(8) and 4-10 times of wire drawing are carried out on the aluminum alloy round rod obtained in the step 7) to obtain the aluminum alloy monofilament.
Preferably, the adding amount of the refining agent in the step 3) is 0.1-0.5% of the total mass of the aluminum ingot melt.
Preferably, the casting temperature of the aluminum liquid in the continuous casting process in the step 5) is 650-750 ℃, and the cooling rate of the cast ingot is 1-50 ℃/s.
Preferably, the rolling start temperature in the step 6) is 500-580 ℃, and the rolling end temperature is 250-400 ℃.
Preferably, the diameter of the aluminum alloy monofilament in the step 8) is 4mm, the electric conductivity is more than or equal to 62% IACS, the room-temperature tensile strength is more than or equal to 160MPa, the long-term heat-resistant temperature reaches 150 ℃, and the short-term heat-resistant temperature reaches 230 ℃.
The action and mechanism of each alloy element are as follows:
b, boron B: among the many factors, the chemical composition is the most basic factor affecting the conductivity of the aluminum conductor, so reducing the effect of the impurity element on the conductivity is a key factor in improving the conductivity of the aluminum conductor. If the impurity element exists in a solid solution state, the influence on the electrical conductivity is larger. The boronizing treatment is the most effective way to improve the conductivity of the aluminum alloy, because B can react with impurity elements of Ti, V, Cr, Mn and Fe to form insoluble boride or complex compounds containing the impurity elements, the impurity elements originally dissolved in aluminum become precipitated and are deposited at the bottom of the melt, the distortion of crystal lattices in the aluminum conductor is reduced, and the conductivity of the aluminum conductor is improved.
Zr, Zr is an indispensable key element for heat-resistant aluminum alloy, the microalloying effect of Zr is closely related to the existing state of Zr, and trace Zr is added into aluminum and aluminum alloy and exists in the form of solid solution in α -Al and Al formation3Primary phase of Zr, Al3Zr(Ll2) Metastable phase, Al3Zr(D03) And (4) balancing the phases. When the Zr content is more than 0.11%, Al is generated3Zr primary phase is generated. If the amount of Zr added is too high or the control is not proper during the casting process, Zr is liable to segregate to form coarse primary Al3The Zr phase adversely affects the alloy properties.
Erbium Er and ytterbium Yb: in the aluminum alloy, the rare earth elements have the functions of purification, modification, refinement and microalloying. At present, more reports are provided about single addition of Zr or rare earth elements and the like to aluminum alloy, and Al generated by adding Sc to the aluminum alloy3The Sc second phase can effectively improve the tensile strength and creep resistance of the alloy. However, single microalloying can only produce limited performance improvements to alloys, and composite microalloying has become a research hotspot in recent years. The rare earth Er element studied recently can be compounded with Zr to precipitate Al with a shell-core structure3A (Zr, Er) phase. However, Er has limited solid solubility in aluminum alloys during solidification in conventional ingot metallurgy, with an equilibrium solid solubility of only 0.05 Wt%, resulting in precipitated Al3The volume fraction of the Er phase is limited, thus limiting the space for further enhancing its microalloying. The rare earth Yb element has similar action with Er element and can generate Al3L1 with the same Sc effect2Structural Al3The Yb phase can improve the recrystallization temperature of the aluminum alloy and can effectively play the positive roles of fine grain strengthening, dispersion strengthening and the like. The solid solubility of Yb element in aluminum matrix is high, and the equilibrium solid solubility in aluminum matrix is 0.1 Wt%. And the Yb is cheap, and the addition of a small amount of Yb element in the aluminum alloy does not greatly increase the production cost, and can be widely applied toIn industrial production. Since the diffusion coefficient of Yb is higher than that of Er and Zr, Al is precipitated in advance3Yb to promote a finer dispersion of Al3(Yb, Er, Zr) phase was precipitated. Compared with Sc, Er and Zr, the nucleation driving power of Yb is larger than that of Sc, Er and Zr under the same content, especially in a high-temperature stage. The addition of Yb can promote dispersion precipitation of Er and Zr and precipitated Al3The (Yb, Er and Zr) phase is a particle with a core/double-shell structure, wherein the Yb-rich core is wrapped by the Er-rich and Zr-rich double shells, so that the conductivity of the alloy material is ensured, and the strength of the alloy material is also ensured. Meanwhile, the unit price of Al-5 wt% Yb is 110 yuan/kg, and the addition of a small amount of Yb element does not greatly increase the production cost, so that the method can be widely applied to industrial production. Therefore, the complex addition of Er, Yb and Zr to the pure Al-Er alloy can fully exert the respective functions and achieve good alloying effect.
Silicon Si: silicon is one of main impurity elements in industrial aluminum, and Si can react with elements such as Fe, Re and the like to generate a second phase, so that the mechanical property of the aluminum alloy is improved.
Fe: aluminum contains a certain amount of iron, which is a major impurity in industrial aluminum. Iron is detrimental to the mechanical properties of cast aluminum because it usually occurs as coarse primary crystals, or as aluminum-iron-silicon compounds, which increase the hardness of aluminum to some extent but reduce the plasticity of aluminum. Studies have shown that iron can increase the strength of aluminum conductors without significantly reducing their electrical conductivity. However, it is also known that in practical production, the resistivity of the aluminum conductor is significantly increased by excessively high Fe content, so that care should be taken to control the Fe content.
V, Mn, Cr, Ti: the elements are impurity elements in the alloy, and have great influence on the conductivity of the aluminum alloy. When impurity elements such as Ti, V, Mn, and Cr in the aluminum conductor exist in a solid solution state, free electrons in the conductor material are easily absorbed and the incomplete electron layer is filled. This reduction in the number of conduction electrons results in a reduction in the conductivity of the aluminum conductor. Studies have shown that the detrimental effect per 1% (Cr + Ti + Mn + V) is 5 times the detrimental effect per 1% silicon on the conductivity of aluminium. Therefore, the strict control of the contents of the elements has important practical application significance for ensuring the quality of the aluminum conductor.
Compared with the closest prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) the invention comprehensively considers the influence effect of the content of each element on the performance and regulates and controls the proportion of each element. The influence of B, Zr coexistence on alloy components and impurity content and performance is effectively solved, the electrical conductivity of the material is improved by compositely adding Zr, Er and Yb elements, and meanwhile, the content of the residual B element in the aluminum water after boronization treatment and the content of impurity elements such as V, Ti, Cr, Mn and the like in the furnace water are accurately controlled, so that the components and the impurity content of the alloy melt meet the design requirements of the alloy.
(2) The invention adopts a rapid solidification mode in the casting process, and increases the solid solubility of the rare earth micro-alloy elements Er and Yb in the aluminum matrix by increasing the cooling rate of the ingot during solidification, thereby improving the precipitation driving force of the heat-resistant dispersed phase in the later heat treatment process and effectively solving the technical bottleneck of lower solid solubility of the elements Er and Yb in the aluminum matrix.
(3) The invention adopts a multi-stage annealing heat treatment process. According to the characteristics of Zr and rare earth element composite micro-alloying, the heat-resistant phase Al which is compositely precipitated is promoted in a multi-stage heating mode3The precipitation of (Yb, Er and Zr) promotes the formation of large amount of nano-scale heat-resistant phase particles which are dispersed and distributed in the matrix, and the strength and the heat resistance of the aluminum conductor are improved under the condition of not reducing the conductivity of the aluminum conductor to the maximum extent.
(4) According to the invention, noble metal elements such as Sc and Ag are not required to be added, so that the produced aluminum alloy wire has the advantages of simple casting process, simple wire preparation process, low cost and the like, and can be widely used for high-conductivity heat-resistant aluminum alloy wires for electric power engineering and automobile light weight.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
The method is characterized in that an industrial pure aluminum ingot with the purity of more than 99.7 percent (wherein Fe is less than or equal to 0.1 percent and Si is less than or equal to 0.05 percent) is used as a raw material, the industrial pure aluminum is firstly put into a smelting furnace to be melted, alloy liquid is kept at the temperature of 750-760 ℃, and an aluminum-boron intermediate alloy is added for boronization treatment. Then adding an aluminum zirconium, aluminum erbium and aluminum ytterbium intermediate alloy, wherein the intermediate alloy comprises the following components in percentage by weight: 0.06 percent of Zr; 0.15 percent of Er; yb 0.1%; 0.02 percent of B; 0.1 percent of Fe; 0.04 percent of Si; v + Ti + Cr + Mn is 0.005%; the balance being aluminum. After the intermediate alloy is melted, cooling the alloy melt to 730 ℃, preserving the heat, and sequentially stirring, refining, standing and slagging off, wherein the casting temperature is 690-750 ℃. Continuously casting by using a water-cooled copper continuous casting wheel method, and obtaining the heat-resistant aluminum alloy conductor material by continuous casting and rolling, wherein the cooling rate of the cast ingot is 10 ℃/s. The rolling temperature of the casting blank is 530 ℃ and 540 ℃, the finishing temperature is 350 ℃, and phi 9.5 aluminum rods are rolled. And (3) carrying out two-stage annealing heat treatment on the aluminum rod, heating to 300 ℃, preserving heat for 10h, then heating to 450 ℃, preserving heat for 10h, and carrying out air cooling. And (3) performing cold drawing on the material, and preparing the aluminum alloy wire material with the thickness of 4mm by drawing for 7-9 times.
Example 2
The method is characterized in that an industrial pure aluminum ingot with the purity of more than 99.7 percent (wherein Fe is less than or equal to 0.1 percent and Si is less than or equal to 0.05 percent) is used as a raw material, the industrial pure aluminum is firstly put into a smelting furnace to be melted, alloy liquid is kept at the temperature of 750-760 ℃, and an aluminum-boron intermediate alloy is added for boronization treatment. Then adding an aluminum zirconium, aluminum erbium and aluminum ytterbium intermediate alloy, wherein the intermediate alloy comprises the following components in percentage by weight: 0.05 percent of Zr; 0.1% of Er; yb 0.15%; 0.02 percent of B; 0.1 percent of Fe; 0.04 percent of Si; v + Ti + Cr + Mn is 0.005%; the balance being aluminum. After the intermediate alloy is melted, cooling the alloy melt to 730 ℃, preserving the heat, and sequentially stirring, refining, standing and slagging off, wherein the casting temperature is 690-720 ℃. Continuously casting by using a water-cooled copper continuous casting wheel method, and obtaining the heat-resistant aluminum alloy conductor material by continuous casting and rolling, wherein the cooling rate of the cast ingot is 10 ℃/s. The rolling temperature of the casting blank is 530 ℃ and 540 ℃, the finishing temperature is 350 ℃, and phi 9.5 aluminum rods are rolled. And (3) carrying out two-stage annealing heat treatment on the aluminum rod, heating to 300 ℃, preserving heat for 10h, then heating to 450 ℃, preserving heat for 10h, and carrying out air cooling. And (3) performing cold drawing on the material, and preparing the aluminum alloy wire material with the thickness of 4mm by drawing for 7-9 times.
Example 3
The method is characterized in that an industrial pure aluminum ingot with the purity of more than 99.7 percent (wherein Fe is less than or equal to 0.1 percent and Si is less than or equal to 0.05 percent) is used as a raw material, the industrial pure aluminum is firstly put into a smelting furnace to be melted, alloy liquid is kept at the temperature of 750-760 ℃, and an aluminum-boron intermediate alloy is added for boronization treatment. Then adding an aluminum zirconium, aluminum erbium and aluminum ytterbium intermediate alloy, wherein the intermediate alloy comprises the following components in percentage by weight: 0.05 percent of Zr; 0.15 percent of Er; yb 0.15%; 0.03 percent of B; 0.06 percent of Fe; 0.03 percent of Si; v + Ti + Cr + Mn is 0.005%; the balance being aluminum. After the intermediate alloy is melted, cooling the alloy melt to 730 ℃, preserving the heat, and sequentially stirring, refining, standing and slagging off, wherein the casting temperature is 690-720 ℃. Continuously casting by using a water-cooled copper continuous casting wheel method, and obtaining the heat-resistant aluminum alloy conductor material by continuous casting and rolling, wherein the cooling rate of the cast ingot is 10 ℃/s. The rolling temperature of the casting blank is 530 ℃ and 540 ℃, the finishing temperature is 350 ℃, and phi 9.5 aluminum rods are rolled. And (3) carrying out two-stage annealing heat treatment on the aluminum rod, heating to 350 ℃, preserving heat for 10 hours, then heating to 450 ℃, preserving heat for 10 hours, and cooling in air. And (3) performing cold drawing on the material, and preparing the aluminum alloy wire material with the thickness of 4mm by drawing for 7-9 times.
Example 4
The method is characterized in that an industrial pure aluminum ingot with the purity of more than 99.7 percent (wherein Fe is less than or equal to 0.1 percent and Si is less than or equal to 0.05 percent) is used as a raw material, the industrial pure aluminum is firstly put into a smelting furnace to be melted, alloy liquid is kept at the temperature of 750-760 ℃, and an aluminum-boron intermediate alloy is added for boronization treatment. Then adding an aluminum zirconium, aluminum erbium and aluminum ytterbium intermediate alloy, wherein the intermediate alloy comprises the following components in percentage by weight: 0.05 percent of Zr; 0.15 percent of Er; yb 0.1%; 0.02 percent of B; 0.06 percent of Fe; 0.04 percent of Si; v + Ti + Cr + Mn is 0.005%; the balance being aluminum. After the intermediate alloy is melted, cooling the alloy melt to 730 ℃, preserving the heat, and sequentially stirring, refining, standing and slagging off, wherein the casting temperature is 690-720 ℃. Continuously casting by using a water-cooled copper continuous casting wheel method, and obtaining the heat-resistant aluminum alloy conductor material by continuous casting and rolling, wherein the cooling rate of the cast ingot is 10 ℃/s. The rolling temperature of the casting blank is 530 ℃ and 540 ℃, the finishing temperature is 350 ℃, and phi 9.5 aluminum rods are rolled. And (3) carrying out two-stage annealing heat treatment on the aluminum rod, heating to 350 ℃, preserving heat for 10 hours, then heating to 450 ℃, preserving heat for 10 hours, and cooling in air. And (3) performing cold drawing on the material, and preparing the aluminum alloy wire material with the thickness of 4mm by drawing for 7-9 times.
Example 5
The method is characterized in that an industrial pure aluminum ingot with the purity of more than 99.7 percent (wherein Fe is less than or equal to 0.1 percent and Si is less than or equal to 0.05 percent) is used as a raw material, the industrial pure aluminum is firstly put into a smelting furnace to be melted, alloy liquid is kept at the temperature of 750-760 ℃, and an aluminum-boron intermediate alloy is added for boronization treatment. Then adding an aluminum zirconium, aluminum erbium and aluminum ytterbium intermediate alloy, wherein the intermediate alloy comprises the following components in percentage by weight: 0.05 percent of Zr; 0.1% of Er; yb 0.15%; 0.02 percent of B; 0.1 percent of Fe; 0.04 percent of Si; v + Ti + Cr + Mn is 0.005%; the balance being aluminum. After the intermediate alloy is melted, cooling the alloy melt to 730 ℃, preserving the heat, and sequentially stirring, refining, standing and slagging off, wherein the casting temperature is 690-720 ℃. Continuously casting by using a water-cooled copper continuous casting wheel method, and obtaining the heat-resistant aluminum alloy conductor material by continuous casting and rolling, wherein the cooling rate of the cast ingot is 10 ℃/s. The rolling temperature of the casting blank is 530 ℃ and 540 ℃, the finishing temperature is 350 ℃, and phi 9.5 aluminum rods are rolled. And (3) carrying out two-stage annealing heat treatment on the aluminum rod, heating to 350 ℃, preserving heat for 10 hours, then heating to 450 ℃, preserving heat for 10 hours, and cooling in air. And (3) performing cold drawing on the material, and preparing the aluminum alloy wire material with the thickness of 4mm by drawing for 7-9 times.
Comparative example 1
The method is characterized in that an industrial pure aluminum ingot with the purity of more than 99.7 percent (wherein Fe is less than or equal to 0.1 percent and Si is less than or equal to 0.05 percent) is used as a raw material, the industrial pure aluminum is firstly put into a smelting furnace to be melted, alloy liquid is kept at the temperature of 750-760 ℃, and an aluminum-boron intermediate alloy is added for boronization treatment. Then adding an aluminum-zirconium and aluminum-erbium intermediate alloy, wherein the aluminum-zirconium and aluminum-erbium intermediate alloy comprises the following components in percentage by weight: 0.15 percent of Zr; 0.1% of Er; 0.02 percent of B; 0.13 percent of Fe0; 0.04 percent of Si; v + Ti + Cr + Mn is 0.01%; the balance being aluminum. After the intermediate alloy is melted, cooling the alloy melt to 730 ℃, preserving the heat, and sequentially stirring, refining, standing and slagging off, wherein the casting temperature is 690-720 ℃. The heat-resistant aluminum alloy conductor material is obtained by continuous casting by a water-cooled copper continuous casting wheel method and continuous casting and rolling. The rolling temperature of the casting blank is 530 ℃ and 540 ℃, the finishing temperature is 350 ℃, and phi 9.5 aluminum rods are rolled. And (3) annealing the aluminum rod, heating to 400 ℃, preserving heat for 10 hours, and cooling in air. And (3) performing cold drawing on the material, and preparing the aluminum alloy wire material with the thickness of 4mm by drawing for 7-9 times.
Comparative example 2
The method is characterized in that an industrial pure aluminum ingot with the purity of more than 99.7 percent (wherein Fe is less than or equal to 0.1 percent and Si is less than or equal to 0.05 percent) is used as a raw material, the industrial pure aluminum is firstly put into a smelting furnace to be melted, alloy liquid is kept at the temperature of 750-760 ℃, and an aluminum-boron intermediate alloy is added for boronization treatment. Then adding an aluminum-zirconium and aluminum-erbium intermediate alloy, wherein the aluminum-zirconium and aluminum-erbium intermediate alloy comprises the following components in percentage by weight: 0.1 percent of Zr; 0.15 percent of Er; 0.02 percent of B; 0.13 percent of Fe0; 0.04 percent of Si; v + Ti + Cr + Mn is 0.01%; the balance being aluminum. After the intermediate alloy is melted, cooling the alloy melt to 730 ℃, preserving the heat, and sequentially stirring, refining, standing and slagging off, wherein the casting temperature is 690-720 ℃. The heat-resistant aluminum alloy conductor material is obtained by continuous casting by a water-cooled copper continuous casting wheel method and continuous casting and rolling. The rolling temperature of the casting blank is 530 ℃ and 540 ℃, the finishing temperature is 350 ℃, and phi 9.5 aluminum rods are rolled. And (3) annealing the aluminum rod, heating to 400 ℃, preserving heat for 10 hours, and cooling in air. And (3) performing cold drawing on the material, and preparing the aluminum alloy wire material with the thickness of 4mm by drawing for 7-9 times.
Comparative example 3
The method is characterized in that an industrial pure aluminum ingot with the purity of more than 99.7 percent (wherein Fe is less than or equal to 0.1 percent and Si is less than or equal to 0.05 percent) is used as a raw material, the industrial pure aluminum is firstly put into a smelting furnace to be melted, alloy liquid is kept at the temperature of 750-760 ℃, and an aluminum-boron intermediate alloy is added for boronization treatment. Then adding an aluminum zirconium intermediate alloy, wherein the aluminum zirconium intermediate alloy comprises the following components in percentage by weight: 0.1 percent of Zr; 0.02 percent of B; 0.13 percent of Fe; 0.04 percent of Si; v + Ti + Cr + Mn is 0.01%; the balance being aluminum. After the intermediate alloy is melted, cooling the alloy melt to 730 ℃, preserving the heat, and sequentially stirring, refining, standing and slagging off, wherein the casting temperature is 690-720 ℃. Continuously casting by a water-cooling copper continuous casting wheel method, and obtaining the heat-resistant aluminum alloy conductor material by continuous casting and continuous rolling. The rolling temperature of the casting blank is 530 ℃ and 540 ℃, the finishing temperature is 350 ℃, and phi 9.5 aluminum rods are rolled. And (3) annealing the aluminum rod, heating to 400 ℃, preserving heat for 10 hours, and cooling in air. And (3) performing cold drawing on the material, and preparing the aluminum alloy wire material with the thickness of 4mm by drawing for 7-9 times.
Comparative example 4
The method is characterized in that an industrial pure aluminum ingot with the purity of more than 99.7 percent (wherein Fe is less than or equal to 0.1 percent and Si is less than or equal to 0.05 percent) is used as a raw material, the industrial pure aluminum is firstly put into a smelting furnace to be melted, alloy liquid is kept at the temperature of 750-760 ℃, and an aluminum-boron intermediate alloy is added for boronization treatment. Then adding an aluminum-zirconium intermediate alloy and an aluminum-erbium intermediate alloy, wherein the components and the weight percentage are as follows: 0.02 percent of Zr; 0.03% of Er; 0.02 percent of B; 0.13 percent of Fe; 0.04 percent of Si; v + Ti + Cr + Mn is 0.01%; the balance being aluminum. After the intermediate alloy is melted, cooling the alloy melt to 730 ℃, preserving the heat, and sequentially stirring, refining, standing and slagging off, wherein the casting temperature is 690-720 ℃. The heat-resistant aluminum alloy conductor material is obtained by continuous casting by a water-cooled copper continuous casting wheel method and continuous casting and rolling. The rolling temperature of the casting blank is 530 ℃ and 540 ℃, the finishing temperature is 350 ℃, and phi 9.5 aluminum rods are rolled. And (3) annealing the aluminum rod, heating to 400 ℃, preserving heat for 10 hours, and cooling in air. And (3) performing cold drawing on the material, and preparing the 4mm aluminum alloy wire material through drawing for 7-9 passes.
Tables 1 and 2 show the alloy compositions and the conductive, room temperature tensile mechanical and heat resistance test results of the wires of examples 1 to 5 and comparative example, respectively. From the results, it can be seen that the heat resistance of the material is reduced after the Zr element is reduced to 0.02 Wt%, and the performance loss rate of the material after the short-time heat preservation for 1h at the high temperature of 230 ℃ is only 85%, and the use temperature of the wire material at 150 ℃ cannot be reached. While adding too much Zr element, as in comparative example 1, Zr element increases the conductivity of the conductor material and decreases sharply to 58% IACS. The conductivity is also reduced by increasing the total amount of the impurity elements V + Ti + Cr + Mn. The added B element can effectively purify the aluminum water, boride with higher density is formed by reaction with impurity elements Mn, Ti and V, and the boride is finally precipitated at the bottom of the furnace after standing, and impurity particles in the aluminum water can be effectively removed by adding converter procedures.
The composite addition of rare earth elements Er and Yb has the effects of purifying and modifying the melt, reducing Fe and Si elements in an aluminum matrix and promoting Al in a heat-resistant phase3The precipitation of (Yb, Er and Zr) promotes the formation of a large amount of nano-scale heat-resistant phase particles which are dispersed and distributed in the matrix, and the strength and the heat resistance of the aluminum conductor are improved under the condition that the conductivity of the aluminum conductor is not reduced to the maximum extent. Compared with the single addition of rare earth element Er, the composite addition of Er/Yb element can further increase the microalloy elements dissolved in the aluminum matrix, thereby improving the heat-resistant phase Al3The precipitation driving force of M (Er, Yb) promotes more fine and dispersed heat-resistant phases to be distributed in the matrix. The second phase of nanometer level is distributed on the base body of the alloy material,compared with the solid solution state, the micro-alloying element exists in the form, the influence on the conductivity of the alloy is much smaller, and the heat resistance of the material can be greatly improved. In a word, by adding proper amounts of Er and Yb elements, the alloy has high room-temperature conductivity, high-temperature residual rate and excellent high-temperature conductivity.
TABLE 1 alloy compositions (Wt%)
| Alloy composition | Zr | Er | Yb | B | Fe | Si | V+Ti+Cr+Mn |
| Example 1 | 0.06 | 0.15 | 0.1 | 0.02 | 0.1 | 0.04 | 0.005 |
| Example 2 | 0.05 | 0.1 | 0.15 | 0.02 | 0.1 | 0.04 | 0.005 |
| Example 3 | 0.05 | 0.1 | 0.15 | 0.03 | 0.06 | 0.03 | 0.005 |
| Example 4 | 0.05 | 0.15 | 0.1 | 0.02 | 0.06 | 0.04 | 0.005 |
| Example 5 | 0.05 | 0.1 | 0.15 | 0.02 | 0.1 | 0.04 | 0.005 |
| Comparative example 1 | 0.15 | 0.1 | - | 0.02 | 0.13 | 0.04 | 0.01 |
| Comparative example 2 | 0.1 | 0.15 | - | 0.02 | 0.13 | 0.04 | 0.01 |
| Comparative example 3 | 0.1 | - | - | 0.02 | 0.13 | 0.04 | 0.01 |
| Comparative example 4 | 0.02 | 0.03 | - | 0.02 | 0.13 | 0.04 | 0.01 |
TABLE 2 obtained monofilament Properties of inventive and comparative examples
As shown in the above table, the elongation of the high-conductivity heat-resistant monofilament provided by the invention is more than or equal to 3.5%, the electric conductivity is more than or equal to 62% IACS, the tensile strength is more than or equal to 160MPa, and the strength residual rate of the high-conductivity heat-resistant monofilament kept at 230 ℃ for 1 hour is more than or equal to 90%, which indicates that the high-conductivity heat-resistant monofilament provided by the invention can meet the requirement of operating at 150 ℃ for a long time.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (9)
1. The heat treatment type high-conductivity heat-resistant Al-Zr-Er-Yb alloy wire material is characterized in that the alloy comprises the following components in percentage by weight:
0.02-0.15 Wt% of zirconium Zr, 0.01-0.2 Wt% of erbium Er, 0.01-0.25 Wt% of ytterbium Yb, 0.01-0.04 Wt% of boron B, less than or equal to 0.20 Wt% of iron Fe, less than or equal to 0.05 Wt% of silicon Si, wherein the sum of vanadium V, titanium Ti, chromium Cr and manganese Mn is less than or equal to 0.01%, and the balance of aluminum.
2. The heat-treated high-conductivity heat-resistant Al-Zr-Er-Yb alloy wire material according to claim 1, wherein the alloy comprises the following components:
0.02-0.1 Wt% of zirconium Zr, 0.01-0.15 Wt% of erbium Er, 0.01-0.2 Wt% of ytterbium Yb, 0.01-0.04 Wt% of boron B, less than or equal to 0.20 Wt% of iron Fe, less than or equal to 0.05 Wt% of silicon Si, wherein the sum of vanadium V, titanium Ti, chromium Cr and manganese Mn is less than or equal to 0.01%, and the balance of aluminum.
3. The heat-treated high-conductivity heat-resistant Al-Zr-Er-Yb alloy wire material according to claim 2, wherein the alloy comprises the following components:
0.02-0.08 Wt% of zirconium Zr, 0.01-0.15 Wt% of erbium Er, 0.01-0.2 Wt% of ytterbium Yb, 0.01-0.04 Wt% of boron B, less than or equal to 0.20 Wt% of iron Fe, less than or equal to 0.05 Wt% of silicon Si, wherein the sum of vanadium V, titanium Ti, chromium Cr and manganese Mn is less than or equal to 0.01%, and the balance of aluminum.
4. The heat-treated high-conductivity heat-resistant Al-Zr-Er-Yb alloy wire material according to claim 3, wherein the alloy comprises the following components:
zirconium Zr 0.05%, erbium Er 0.15%, ytterbium Yb 0.15%, boron B0.02%, ferrum Fe 0.1%, silicon Si 0.04%, wherein vanadium V + titanium Ti + chromium Cr + manganese Mn 0.005%, and the balance of aluminum.
5. A method for preparing the heat-treated high-conductivity heat-resistant Al-Zr-Er-Yb alloy wire material as claimed in any one of claims 1 to 4, wherein the method comprises the following steps:
(1) adding Al-B intermediate alloy into the aluminum ingot melt at the temperature of 660-750 ℃, stirring for 5-60min and standing for 30-300 min;
(2) adding an aluminum zirconium, aluminum erbium and aluminum ytterbium intermediate alloy into the melt obtained in the step 1), and stirring for 5-15 min;
(3) adding a refining agent into the melt obtained in the step 2), refining for 10-30min, and slagging off;
(4) keeping the temperature and standing for 30-300min after slagging off, and performing online degassing and deslagging treatment;
(5) continuously casting by using a water-cooling copper continuous casting wheel method;
(6) rolling the casting blank obtained in the step 5) into a round rod with the diameter of 9.5 mm;
(7) heating the round rod in the step 6) from room temperature to 350 ℃ for 200-;
(8) and 4-10 times of wire drawing are carried out on the aluminum alloy round rod obtained in the step 7) to obtain the aluminum alloy monofilament.
6. The method for preparing a heat-treated high-conductivity heat-resistant Al-Zr-Er alloy wire material according to claim 5, wherein the refining agent is added in the step 3) in an amount of 0.1-0.5% of the total mass of the aluminum ingot melt.
7. The method for preparing the heat-treated high-conductivity heat-resistant Al-Zr-Er alloy wire material as claimed in claim 5, wherein the casting temperature of the aluminum liquid in the step 5) continuous casting process is 650-750 ℃, and the cooling rate of the ingot is 1-50 ℃/s.
8. The method for preparing the heat-treated Al-Zr-Er alloy wire material with high conductivity and heat resistance as claimed in claim 5, wherein the rolling start temperature in the step 6) is 500-580 ℃ and the rolling end temperature is 250-400 ℃.
9. The method for preparing the heat-treated high-conductivity heat-resistant Al-Zr-Er alloy lead material as claimed in claim 5, wherein in the step 8), the diameter of the aluminum alloy monofilament is 4mm, the conductivity is not less than 62% IACS, the room temperature tensile strength is not less than 160MPa, the long-term heat-resistant temperature reaches 150 ℃, and the short-term heat-resistant temperature reaches 230 ℃.
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| WO2024144428A1 (en) * | 2022-12-26 | 2024-07-04 | Общество с ограниченной ответственностью "Институт легких материалов и технологий" | Aluminium-based alloy and item made of same |
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