WO2017162199A1 - 一种轻质高导耐热铝导线及其制备方法 - Google Patents

一种轻质高导耐热铝导线及其制备方法 Download PDF

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WO2017162199A1
WO2017162199A1 PCT/CN2017/078028 CN2017078028W WO2017162199A1 WO 2017162199 A1 WO2017162199 A1 WO 2017162199A1 CN 2017078028 W CN2017078028 W CN 2017078028W WO 2017162199 A1 WO2017162199 A1 WO 2017162199A1
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conductivity
aluminum wire
lightweight high
alloy
resistant aluminum
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French (fr)
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李红英
宾杰
高兆和
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Central South University
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Central South University
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Priority to PH12018550142A priority patent/PH12018550142B1/en
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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
    • 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
    • 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
    • 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
    • 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
    • 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

Definitions

  • the invention relates to a lightweight high-conductivity heat-resistant aluminum wire and a preparation method thereof, and belongs to the technical field of electrical materials.
  • the free electrons in the metal undergo directional motion under the applied electric field to form a current, and the abnormal point (or irregular point) of the periodicity of the lattice field hinders the directional motion of the electron and scatters the electron wave.
  • the conductivity of a metal material is closely related to the mean free path of free electrons (the average of the distance between adjacent anomalies). The smaller the mean free path of free electrons, the lower the material conductivity. Impurity elements, solid solution atoms, and crystal defects in the metal cause the lattice field to locally deviate from its periodic position, shortening the mean free path of free electrons, resulting in a decrease in metal conductivity.
  • the influence of impurities on the conductivity is closely related to the type and content of impurity elements and the state existing in the metal.
  • the inevitable impurity elements Ti, V, Cr, Mn in industrial pure aluminum have a great influence on the conductivity, especially When the high content of impurity elements is dissolved in the aluminum matrix, the electrical conductivity of the aluminum conductor is greatly reduced.
  • the solid solution atoms cause lattice distortion and destroy the periodicity of the metal Coulomb potential field, and become the scattering center of the conductive electrons.
  • the larger the molar concentration of the solid solution atoms the smaller the distance between adjacent scattering centers, and the higher the mean free path of electrons.
  • High purity Al with a purity of 99.99% has a conductivity of up to 64.94% at 20 °C IACS has a density of 2.7 g/cm3, but the strength is only 80 to 100 MPa, and the recrystallization temperature is about 150 °C.
  • Add 0.6 ⁇ 0.9wt.%Mg, 0.5 ⁇ 0.9 wt.% Si, 0.5 wt.% Fe, 0.1 wt.% Cu, 0.1 wt.% Zn 6021 alloy is a commonly used high-strength electrical aluminum alloy with tensile strength of 295 ⁇ 325MPa, but its conductivity at 20°C is only 52.5 ⁇ 55% IACS.
  • Microalloying which aims to improve the heat resistance and strength of aluminum conductors, especially when the alloy composition and ratio design are not proper, will have a very adverse effect on the electrical conductivity.
  • the technical difficulty of developing lightweight high-conductivity heat-resistant aluminum wires is difficult. It is the best balance between conductivity, heat resistance and specific strength. Generally, the relationship between electrical conductivity and heat resistance is in a trade-off relationship. In the prior art technical solutions, there are often situations in which the loss is the case, the technical solution with high conductivity, the heat resistance is not ideal, and the heat resistance is good. The conductivity is not ideal.
  • the disclosed composition is 0.06 ⁇ 0.15 Wt.% Zr, 0.15 ⁇ 0.30 wt.%Er, 0.1 ⁇ 0.2 Wt.%Fe, through the microalloying of Zr, Er, Fe, using the continuous casting and rolling process, the aluminum wire prepared, the conductivity is only 59.5 ⁇ 60.5%
  • IACS has a short-time heat-resistant temperature of 210 ° C, a long-term heat-resistant temperature of 180 ° C, and a tensile strength of 157 MPa.
  • the density parameter of the alloy is not disclosed.
  • Patent No. CN103498083A the disclosed composition is 0.01 to 0.2 Wt.%Er, 0 to 0.3% wt.
  • the conductivity of the examples containing Er, Zr, and B is only 60%.
  • the IACS, and the embodiment containing only one or both of the Er and Zr elements, has a conductivity of only 58% IACS, and does not disclose the alloy density, strength, heat resistance parameters, and process parameters of continuous casting and rolling.
  • the heat resistance and specific strength of the aluminum wire are improved without lowering the electrical conductivity, and the preparation of the lightweight, high-conductivity and heat-resistant aluminum wire is a long-term pursuit in the field.
  • the object of the present invention is to overcome the deficiencies of the prior art and to provide a lightweight high-conductivity heat-resistant aluminum wire with a reasonable group distribution ratio, less alloying elements, simple and flexible process, and low production cost, and a preparation method thereof.
  • the invention produces purification, metamorphism, refinement and dispersion strengthening effect by adding a small amount of alloying elements which are less damaging to electrical conductivity, and substantially improves the resistance of the wire with respect to 99.99% of high-purity aluminum under the premise that the conductivity decreases little.
  • the heat and specific strength meet the requirements of light weight, high conductivity and heat resistance for large-capacity long-distance transmission lines.
  • the invention relates to a lightweight high-conductivity heat-resistant aluminum wire comprising the following components in mass percentage:
  • the total content of impurity elements of Ti, V, Cr and Mn is less than or equal to 0.01 wt.%, and the rest is Al;
  • the invention relates to a lightweight high-conductivity heat-resistant aluminum wire which is cooled to room temperature at a speed of 20-300 ° C / s during casting, and then rapidly annealed at 480 ° C to 500 ° C for 1-10 h.
  • the invention relates to a lightweight high-conductivity heat-resistant aluminum wire having nano-scale spherical Al3(Er, Zr) composite particles; the nano-sized spherical Al3(Er, Zr) composite particles are coherent with a matrix Ll2 structure.
  • the invention relates to a method for preparing a lightweight high-conductivity heat-resistant aluminum wire, comprising the following steps:
  • the first step heating the industrial pure aluminum ingot to Melting at 740 ° C ⁇ 780 ° C, according to the mass percentage of Zr and Er in the designed aluminum wire component, the Al-Zr and Al-Er intermediate alloys are added to the aluminum melt. After the intermediate alloy is completely melted and stirred evenly, the Zr is applied. , Er, Al alloy melt for rapid composition analysis before the furnace, and the alloy melt is reduced 720 ° C ⁇ 730 ° C insulation, while adding Al-B intermediate alloy for refining, and then standing, slag, casting, to obtain a blank;
  • the second step after the blank is annealed, it is extruded and drawn into a monofilament.
  • the invention discloses a preparation method of a lightweight high-conductivity heat-resistant aluminum wire,
  • the addition amount of the Al-B master alloy is determined by the following two parts: first, the Al-B intermediate alloy obtained by mass percentage of B in the design component; second, the mass of B is Zr, Er, Al Al-B intermediate alloy with 2-5 times the total content of impurity elements of Ti, V, Cr and Mn in the alloy melt.
  • the invention relates to a method for preparing a lightweight high-conductivity heat-resistant aluminum wire.
  • the casting method can be changed according to the configuration of the production line equipment, and the ingot can be obtained by ordinary casting or semi-continuous casting, or can be obtained by continuous casting.
  • the invention provides a method for preparing a lightweight high-conductivity heat-resistant aluminum wire. During casting, the ingot is cooled to room temperature at a rate of 20-300 ° C / s.
  • the invention relates to a method for preparing a lightweight high-conductivity heat-resistant aluminum wire, which is cast by water cooling.
  • the invention discloses a method for preparing a lightweight high-conductivity heat-resistant aluminum wire, wherein the annealing process of the blank is: an annealing temperature of 480 ° C to 500 ° C, and the furnace is cooled after being heated for 1-10 hours.
  • the invention relates to a method for preparing a lightweight high-conductivity heat-resistant aluminum wire, wherein the extrusion method can be changed according to the configuration of the production line equipment, and the heated ingot can be used for conventional hot extrusion or a room temperature bar blank.
  • the hot extrusion temperature is 300 ⁇ 450 ° C.
  • the invention relates to a method for preparing a lightweight high-conductivity heat-resistant aluminum wire, wherein the extrusion ratio of hot extrusion or continuous extrusion at room temperature is greater than or equal to 80, and the total deformation of extrusion is greater than or equal to 80%.
  • the invention relates to a method for preparing a lightweight high-conductivity heat-resistant aluminum wire, wherein the drawing adopts a squeeze bar material for multi-pass cold drawing, and the diameter of the drawing blank can be determined according to actual needs, in particular, according to the service strength requirement.
  • the diameter of the blank used is determined and the strength of the monofilament is regulated by different amounts of pull deformation.
  • the invention discloses a preparation method of a lightweight high-conductivity heat-resistant aluminum wire, which is subjected to multi-pass drawing after extrusion, the channel extension coefficient is 1.2 ⁇ 1.5, and the cumulative total elongation coefficient is 5.5 ⁇ 10.5, and ordinary lubricating oil or
  • the emulsion is lubricated and the emulsion can also be cooled so that the temperature of the aluminum filament does not exceed 180 °C.
  • the invention discloses a preparation method of a lightweight high-conductivity heat-resistant aluminum wire, wherein the prepared wire has a density of 2.71 g/cm3 or less and a conductivity of 62% or more at 20 °C. IACS, short-time heat-resistant temperature up to 230 ° C, long-term heat-resistant temperature up to 210 ° C, tensile strength of 165MPa or more.
  • impurities and crystal defects have a great influence on the conductivity of aluminum.
  • the impurities Ti, V, Cr, and Mn have a detrimental effect on conductivity, especially when they are present in a solid solution in the aluminum matrix.
  • the addition amount of the invention B is determined by the mass percentage of B in the designed aluminum wire component (0.035-0.06 wt.%) and the total content of the impurity elements of Ti, V, Cr and Mn in the industrial pure aluminum.
  • the addition amount of the Al-B master alloy is determined in two parts, and the B content in the alloy melt is far more than 0.06 wt.%, which is used as a refining agent and a modifier.
  • B when B is used as a refining agent, it reacts with impurities such as Ti and V which are unavoidable in industrial pure aluminum to form a boride having a large specific gravity and is removed as slag (see Fig. 2 and Fig. 3). Increase the electrical conductivity of the aluminum conductor.
  • the surplus B acts as a metamorphic agent, which produces metamorphism, which can make the Fe-rich phase continuously distributed along the grain boundary become discontinuous granular, which can improve the electrical conductivity of the aluminum wire and improve its strength and heat. Stability, at the same time, can reduce the purity requirements of pure aluminum ingots in the raw material industry, thereby greatly reducing the cost of alloy preparation.
  • the inventors have found that if the B content of the added refining agent and modifier is too small, the B content in the alloy matrix is less than 0.035%, which lowers the electrical conductivity of the material, but if an excessive amount of B is added as a refining agent and a modifier ( When the B content is 8 times of the total content of Ti and V), more coarse Al and B compounds will appear in the aluminum, which will also significantly reduce the electrical conductivity of the material.
  • the Er element tends to adsorb on the ⁇ -Al crystal nucleus, and the formation of Al3Er hinders the growth of ⁇ -Al dendrites, and the effect of refining the secondary dendritic structure is achieved.
  • the primary Al3Er is pushed to the grain boundary and completely solidified at the end of the melt.
  • a eutectic compound containing an ⁇ -Al phase and an Al3Er phase is formed.
  • Er can also form a compound with an impurity element such as Fe to cause purification and deterioration.
  • 6 is a second phase particle and energy spectrum analysis result in Comparative Example 2, Comparative Example 2 is not added with B, and FIG.
  • 6(b) shows that a mixed phase of Al3Er and (Al, Fe) may be formed in the crystal, or Al, Fe, Er) ternary compound, without the action of B, the Er element is more likely to form a compound with an impurity element or form an Al3X phase.
  • the advantage of the invention is the use of B and Zr Synergistic effect of Er, the elimination and metamorphism of B, the formation of phase containing Er impurity, and the suppression of the formation of coarse primary phase by rapid cooling in the casting process, so that Zr and Er are mainly substable supersaturated solids.
  • the dissolved state exists to cause a large amount of Al3(Er, Zr) composite particles coherent with the matrix to be precipitated in the subsequent annealing process, as shown in FIG.
  • the principle of precipitation of the Al3(Er, Zr) ternary phase of the invention is: during the annealing process, the faster diffusion rate of Er forms the particles first in the matrix, provides nucleation sites for the desolvation precipitation of Zr, and promotes the solid solution of Al-Zr solid solution. Decomposition, Zr with slower diffusion rate accumulates on the outer layer of Al3Er particles, forming L12-structured, nano-scale spherical Al3(Er, Zr) composite particles coherent with the matrix.
  • the nano-scale Al3(Er,Zr) composite particles precipitated in the invention have the following advantages: on one hand, the degree of solid solution of Zr and Er in the aluminum matrix is reduced, the electrical conductivity of the aluminum wire is improved, and on the other hand, the dispersion and the crystal are dispersed.
  • the coherent nano-scale Al3(Er,Zr) composite particles have pinning effect on dislocations, subgrains and grain boundaries, have obvious strengthening effect and inhibit recrystallization, and can effectively improve the strength and heat resistance of aluminum conductors. Sex.
  • the invention adopts the preparation process of casting, annealing, extrusion and drawing, can distinguish the continuous casting and rolling process of other aluminum wires, has the advantages of short production process, simple and flexible process control, and the prepared wire ensures high conductivity. Under the premise, it has good heat resistance and specific strength.
  • the rapid cooling casting of the invention has the effect of inhibiting the formation of the coarse primary phase, so that the slab has a higher supersaturated solid solubility, and provides a driving force for the second dispersed phase particles which are precipitated in the subsequent annealing process.
  • the high-temperature short-time annealing of the slab of the invention has the main function of precipitating a large amount of dispersed second phase particles, in particular, nano-scale Al3(Er, Zr) composite particles which are coherent with crystals, and the secondary effect is appropriate Eliminating the composition segregation, tissue segregation and casting stress of the billet, thereby improving the cast structure and processing performance.
  • the annealing time of the invention is shorter than that of the aluminum alloy, and the annealing time is short, and the energy consumption is reduced.
  • the invention adopts extrusion to carry out plastic deformation, has the advantages of flexible production and simple process control, and can be used for one-time extrusion of the ingot into a wire rod, or continuous casting of the steel bar blank into a smaller diameter wire blank. Compared with rolling deformation, it has a greater degree of deformation and a stronger three-direction compressive stress state, which can greatly improve the cast structure and improve the subsequent processing performance.
  • the invention adopts the extruded rod material to obtain the aluminum alloy monofilament by multi-pass cold drawing, and the rod material diameter can be determined according to actual needs, in particular, the rod material diameter can be determined according to the service strength requirement, and the deformation amount is determined by different pulling deformation amounts. Regulate the strength of the monofilament.
  • the present invention is based on the reasonable ratio of Al, B, Zr, and Er elements and the proper amount of B-containing refining agent, and is rapidly cooled, cast, high-temperature short-time annealing of the billet, and large-deformation amount of extrusion.
  • B produces purification, metamorphism and synergistic microalloying of Zr and Er
  • the prepared conductor has a conductivity of 62% or more at 20 ° C.
  • IACS long-term heat-resistant temperature up to 210 ° C, short-time heat-resistant temperature up to 230 ° C, tensile strength of 165 MPa or more, density ( ⁇ 2.71g / cm3) and pure aluminum density of 2.7g / cm3 is relatively close, can improve transmission lines Capacity and reduced transmission line loss, with good anti-sag characteristics and heat resistance, can increase the spacing of transmission line towers and improve the safety and stability of long-distance, large-capacity transmission lines and service life.
  • the invention has short production process, simple and flexible process control and low requirement, and the number of alloying elements added is small and the content is low, which saves the amount of expensive rare earth elements, has no strict requirements on raw material impurity content and slab quality, and energy consumption is not High, therefore, also has the advantage of lower production costs.
  • Figure 1 (a) is an as-cast metallographic structure of Example 1,
  • Figure 1 (b) is the as-cast metallographic structure of Example 2,
  • Figure 1 (c) is an as-cast metallographic structure of Example 3;
  • Figure 2 is a photograph showing the microstructure of the smelting slag of Example 2 of the present invention
  • Figure 3 is a result of energy spectrum analysis of the mass point in Figure 2;
  • Figure 4 (a) is a photograph of the metallographic structure of the alloy of Comparative Example 2
  • Figure 4 (b) is a photograph of the metallographic structure of the alloy of Example 2,
  • Figure 4 (c) is a photograph of the metallographic structure of the alloy of Comparative Example 1;
  • Figure 5 (a) is a low-magnification TEM photograph of the alloy of Example 2,
  • Figure 5 (b) is a high-magnification TEM photograph of the alloy of Example 2,
  • Figure 5 (c) is a high resolution TEM morphology of Al3 (Er, Zr) composite particles in the alloy of Example 2;
  • Figure 6 (a) is the microstructure of the alloy annealed alloy of Comparative Example 2,
  • Figure 6 (b) is the result of phase energy spectrum analysis of the precipitate at point A in the mark of Figure 6 (a),
  • Figure 6 (c) is the result of phase energy spectrum analysis of the precipitate at point B in the mark of Figure 6 (a),
  • Figure 6 (d) is the result of phase energy spectrum analysis of the precipitate at point C in the mark of Figure 6 (a);
  • Figure 1 (a), Figure 1 (b), Figure 1 (c) It can be seen that the combined addition of Zr and Er elements has obvious grain refining effect, and the larger the content of Zr and Er elements, the more obvious the grain refining effect.
  • FIG 2 Figure 3
  • the microstructure and energy spectrum analysis results of the slag shown in Example 2 can be seen that there is another phase different from the white AlFe phase, and the phase exhibits the characteristics of brighter white around the darker periphery, and the energy spectrum analysis results show
  • This phase is a phase containing Al, B, Ti, and V, indicating that the impurities Ti and V do form a compound with B and enter the slag, which is one of the important reasons for improving the electrical conductivity of the alloy.
  • a clear Ashby-Brown stress contrast can be observed around the precipitated phase shown in Figure 5(a).
  • the precipitated phase still maintains good coherence with the matrix.
  • the shell and core of the precipitated phase shown in Figure 5(b) show The obvious contrast difference, the area shown in Fig. 5(c) can be divided into three parts: the matrix, the shell of the precipitated phase, and the core of the precipitated phase.
  • the electron diffraction spot of the selected area of the shell of the precipitated phase corresponds to the L12 structure, and the precipitate phase shell corresponds.
  • the diffraction intensity is stronger than that of the core, and it is determined to be an internal rich Er, external shell Zr-rich Al3 (Er1-xZrx) Composite phase.
  • Figure 5 (a), Figure 5 (b), Figure 5 (c) demonstrates that a large number of nanoscale Al3 (Er, Zr) coherent with the matrix is precipitated during the annealing of the alloy of the present invention.
  • FIG. 6(a)-(d) are the results of the second phase particles and energy spectrum analysis in Comparative Example 2, and FIG. 6(b) shows that the intra-crystal A point may be a mixed phase of Al3Er and (Al, Fe), and it is also possible It is a (Al, Fe, Er) ternary compound, and Fig. 6(c) shows that the grain boundary B point particle phase is an Al3Er phase, and Fig. 6(d) shows that the grain boundary C point acicular phase is an Al3Fe phase.
  • Comparative Example 2 did not add B, The Er element is more likely to form a compound with an impurity element or form an Al3X phase, which proves that the B element promotes the precipitation of the Al3(Er1-xZrx) ternary composite phase.
  • the aluminum wire prepared in Example 2 of the present invention has a conductivity of 62% at 20 ° C. IACS, the short-term heat-resistant temperature reaches 230 ° C (230 ° C insulation 1h tensile strength residual rate of up to 92%, tensile strength of 165MPa, can be used as a strong support material for the superior performance of the wire of the present invention.
  • B The intermediate alloy is refined so that the mass percentage of each element is: B is 0.035 wt.%, Zr is 0.1 wt.%, and Er is 0.21. Wt.%, the sum of impurity elements such as Ti, V, Cr, Mn is 0.001 wt.%, Al is the balance. Then, stirring, standing, slag, and water-cooling casting are sequentially performed. The bad material was cooled at 480 ° C for 10 h, then cooled at 420 ° C. The extrusion ratio was 89.7, and the extrusion deformation was 98.7%. The round aluminum rod of ⁇ 9.5 was obtained and pulled through 5 passes. ⁇ 4.0mm aluminum wire. Conductivity, tensile strength, heat resistance and density test of aluminum wires, the results are shown in the table 1 is shown.
  • the intermediate alloy is used as raw material. After the industrial pure aluminum is melted at 760 °C, Al-Zr and Al-Er intermediate alloy are added. After the intermediate alloy is completely melted and stirred, the rapid composition analysis of the Zr, Er and Al alloy melts is carried out. And the alloy melt is reduced to 730 ° C, and then added to Al-2.5% according to the total content of impurity elements Ti and V in the alloy melt 3.5 times and the mass percentage of B in the alloy.
  • B The intermediate alloy is refined so that the mass percentage of each element is: B is 0.05 wt.%, Zr is 0.1 wt.%, Er is 0.21 wt.%, and the sum of impurity elements such as Ti, V, Cr, Mn is 0.001 wt.%, Al is the balance. Then, stirring, standing, slag, and water-cooling casting are sequentially performed. The bad material was cooled at 490 °C for 8 h, then cooled at 420 °C, the extrusion ratio was 89.7, and the extrusion deformation was 98.7%. The round aluminum rod of ⁇ 9.5 was obtained and pulled through 5 passes. ⁇ 4.0mm aluminum wire. Conductivity, tensile strength, heat resistance and density test of aluminum wires. The results are shown in Table 2. Shown.
  • B is 0.06 wt.%
  • Zr is 0.2 wt.%
  • Er is 0.4 wt.%
  • the sum of impurity elements such as Ti, V, Cr, Mn is 0.001 Wt.%
  • Al is the margin.
  • stirring, standing, slag, and water-cooling casting are sequentially performed.
  • the billet was kept at 500 ° C for 1 h and then cooled with a furnace, then hot extruded at 420 ° C, the extrusion ratio was 89.7, and the extrusion deformation was 98.7%, and a round aluminum rod of ⁇ 9.5 was obtained, which was drawn into ⁇ 4 by 5 passes. .0mm aluminum wire.
  • B is 0.10 wt.%
  • Zr is 0.1 wt.%
  • Er is 0.21 wt.%
  • the sum of impurity elements such as Ti, V, Cr, Mn is 0.001 wt.%
  • Al is the balance.
  • stirring, standing, slag, and water-cooling casting are sequentially performed.
  • the billet was chilled at 490 ° C for 8 h, then cooled with the furnace, then hot extruded at 420 ° C, the extrusion ratio was 89.7, and the extrusion deformation was 98.7%, and a round aluminum rod of ⁇ 9.5 was obtained, which was drawn through multiple passes. ⁇ 4.0mm aluminum wire.
  • the conductivity, tensile strength, heat resistance and density of the aluminum wires were tested. The results are shown in Table 4.
  • the raw materials are more than pure 99.7% industrial pure aluminum ingot, Al-11.34% Zr master alloy, Al-4.7% Er intermediate alloy.
  • the industrial pure aluminum is melted at 760 ° C
  • the Al-Zr, Al-Er intermediate alloy is added.
  • the Zr, Er, and Al alloy melts are subjected to rapid composition analysis before the furnace, and the alloy is melted.
  • the body was cooled to 730 ° C, and the mixture was stirred, stood still, slag, and water-cooled.
  • the ingot was kept at 500 ° C for 1 h and then cooled with a furnace, then hot extruded at 420 ° C, the extrusion ratio was 89.7, and the extrusion deformation was 98.7%, and a round aluminum rod of ⁇ 9.5 was obtained, which was drawn through 5 passes. ⁇ 4.0mm aluminum wire.
  • the aluminum alloy wires obtained by the three embodiments of the present invention have a density of less than or equal to 2.71 g/cm 3 and a conductivity of 62% or more at a normal temperature of 20 ° C.
  • IACS has a short-term heat-resistant temperature of 230 ° C and a long-term heat-resistant temperature of 210 ° C.
  • Comparative Example 1 was added with an excess of B.
  • the other components were the same as those of Example 1 and Example 2.
  • the annealing process was the same as that of Example 2, and Comparative Example 2 was the same as Example 3 except that the B element was not added.
  • the conductivity of each of the comparative examples was lower than 61% IACS, and the residual rate of strength after annealing at 230 ° C for 1 hour was less than 90%, and the residual rate of strength after annealing at 230 ° C for 400 hours was also less than 90%. From the performance parameters obtained in the above examples and comparative examples, it can be known that B as a refining agent and a modifier is too small, resulting in a B content in the alloy matrix of less than 0.035 wt.%, or an excessive addition amount, such as adding Ti. B with a total V content of 8 times will reduce the electrical conductivity and heat resistance of the wire.

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Abstract

一种轻质高导耐热铝导线及其制备方法，包含B：0.035～0.06wt.％、0.1-0.2wt.％Zr、0.1-0.3wt.％Er，不可避免杂质以及余量Al，制备步骤为熔炼、炉前快速成分分析、精炼、快速冷却铸造、坯料退火、挤压、拉拨。铝导线在20℃的电导率大于等于62％IACS。

Description

一种轻质高导耐热铝导线及其制备方法 技术领域
本发明涉及一种轻质高导耐热铝导线及其制备方法，属于电工材料技术领域。
背景技术
根据能源互联的战略部署，我国电网将实现“西电东送，南北互供、全国联网”，输电线路距离远、输电容量大、自然环境复杂，为了降低输送线损、减少线路建设成本、节约紧张的走廊资源，对输电导线提出了更高的要求，既要有高电导率，又要有良好的耐热性能和抗弧垂特性。因此，研发一种具有高导电率、良好的耐热性能、密度小的铝导线，成为业内亟需解决的技术难题。
金属中的自由电子在外加电场作用下发生定向运动形成电流，而晶格场周期性的异常点（或不规则点）会阻碍电子的定向运动并对电子波产生散射作用。金属材料的导电性跟自由电子的平均自由程（相邻异常点间距的平均值）紧密相关，自由电子的平均自由程越小，材料电导率越低。金属中的杂质元素、固溶原子以及晶体缺陷都会导致晶格场局部偏离其周期性位置，缩短自由电子的平均自由程，从而导致金属电导率的降低。杂质对电导率的影响与杂质元素的种类、含量、在金属中存在的状态紧密相关，工业纯铝中不可避免的杂质元素Ti、V、Cr、Mn等对导电性影响较大，特别是较高含量的杂质元素固溶于铝基体时，会大幅降低铝导体的电导率。固溶原子导致晶格畸变而破坏金属库仑势场的周期性，并成为对导电电子的散射中心，固溶原子摩尔浓度越大，相邻散射中心间的距离越小，电子的平均自由程越小，电导率越低，以Zr为例，少量Zr原子固溶于铝基体中便会显著降低合金的电导率。纯度为99.99%的高纯Al在20℃的电导率高达64.94% IACS，密度为2.7g/cm3，但强度仅为80~100MPa，再结晶温度为150℃左右。添加0.6~0.9wt.%Mg、0.5~0.9 wt.% Si、0.5wt.%Fe、0.1 wt.% Cu、0.1 wt.% Zn的6021合金是常用的高强度电工铝合金，抗拉强度可达到295~325MPa，但是，其20℃时的导电率仅为52.5~55%IACS。
旨在提高铝导体耐热性和强度的微合金化，特别是当合金组分及配比设计不当时，会对导电性能产生非常不利的影响，研发轻质高导耐热铝导线的技术难点是在导电性、耐热性、比强度之间寻求最佳平衡点。通常，导电率和耐热性呈此消彼长的关系，现有公开的技术方案中往往存在着顾此失彼的情况，导电率高的技术方案，耐热性不理想，耐热性好的技术方案，导电率不够理想。公开号为CN102230113A的专利，公开的成分为0.06～0.15 wt.% Zr，0.15～0.30 wt.%Er，0.1～0.2 wt.%Fe，通过Zr、Er、Fe的微合金化，采用连铸连轧工艺，制备出的铝电线，导电率只有59.5～60.5% IACS，短时耐热温度为210℃，长期耐热温度为180℃，抗拉强度为157MPa，没有公开合金的密度参数。公开号为CN103498083A的专利，公开的成分为0.01～0.2 wt.%Er，0～0.3% wt.Zr，0～0.2 wt.%B，从其实施例记载的参数来看，含有Er、Zr、B的实施例的导电率仅为60% IACS，而只含Er、Zr元素中的一种或两种的实施例的导电率只有58% IACS，且没有公开合金密度、强度、耐热性能参数及连铸连轧的工艺参数。
因此，通过优化合金组分及制备工艺，在不降低电导率的前提下，提高铝导线的耐热性和比强度，制备轻质、高导、耐热铝导线是本领域长期以来的追求。
 技术问题
本发明的目的在于克服现有技术之不足而提供一种组分配比合理、合金化元素少、工艺简单且灵活、生产成本低的轻质高导耐热铝导线及制备方法。本发明通过微量添加对导电率损害较小的合金元素，产生净化、变质、细化和弥散强化作用，相对99.99%的高纯铝，在电导率下降很少的前提下，大幅提高导线的耐热性和比强度，从而满足大容量远距离输电线路的轻质、高导、耐热的服役要求。
技术解决方案
本发明一种轻质高导耐热铝导线，包括下述组分按质量百分比组成 ：
B：0.035~0.06 wt.% ；
Zr：0.1~0.2 wt.% ；
Er：0. 2~0.4wt.% （但不包含0.2 wt %）；
Ti、V、Cr、Mn杂质元素总含量小于等于0.01 wt.%，其余为 Al；
其中，Zr、Er按质量比Zr：Er=1：1.5~2.5添加，优选Zr、Er按质量比Zr：Er=1：1.5~2添加。
本发明一种轻质高导耐热铝导线，铸造时，以20-300℃/s的速度冷却至室温，然后在480℃~500℃进行1-10h的高温快速退火。
本发明一种轻质高导耐热铝导线，所述导线具有纳米级的球状Al3（Er，Zr）复合粒子；所述纳米级的球状Al3（Er，Zr）复合粒子为与基体共格的Ll2结构。
本发明一种轻质高导耐热铝导线的制备方法，包括下述步骤 ：
第一步：将工业纯铝锭加热至 740℃~780℃熔化，按设计的铝导线组分中Zr、Er的质量百分比配取Al-Zr和Al-Er中间合金加入铝熔体中，待中间合金完全熔化并搅拌均匀后，对Zr、Er、Al合金熔体进行炉前快速成分分析，并将合金熔体降至 720℃~730℃保温，同时添加Al-B中间合金进行精炼，然后静置、扒渣、铸造，得到坯料；
第二步：将坯料退火后，进行挤压、拉拨成单丝。
本发明一种轻质高导耐热铝导线的制备方法， 所述Al-B中间合金的添加量由以下两部分确定：第一，按设计组分中B的质量百分比配取的Al-B中间合金；第二，按B的质量为Zr、Er、Al合金熔体中Ti、V、Cr、Mn杂质元素总含量的2-5倍配取的Al-B中间合金。
本发明一种轻质高导耐热铝导线的制备方法，所述铸造方式可根据生产线设备配置情况变换，既可通过普通铸造或半连续铸造获得锭坯，也可通过连续铸造获得杆坯。
本发明一种轻质高导耐热铝导线的制备方法，铸造时，铸锭以20-300℃/s的速度冷却至室温。
本发明一种轻质高导耐热铝导线的制备方法，铸造时采用水冷铸造。
本发明一种轻质高导耐热铝导线的制备方法，所述坯料的退火工艺为：退火温度为480℃~500℃，保温1-10h后随炉冷却。
本发明一种轻质高导耐热铝导线的制备方法，所述挤压方式可根据生产线设备配置情况进行变换，既可采用加热的锭坯进行常规热挤压，也可采用室温杆坯进行连续挤压，所述热挤压温度为300~450℃。
本发明一种轻质高导耐热铝导线的制备方法，热挤压或室温连续挤压的挤压比大于等于80，挤压总变形量大于等于80%。
本发明一种轻质高导耐热铝导线的制备方法，所述拉拔采用挤压杆料进行多道次冷拉拔，可根据实际需要确定拉拔坯料直径，特别是可根据服役强度要求确定所用坯料直径，并通过不同的拉拨变形量来调控单丝的强度。
本发明一种轻质高导耐热铝导线的制备方法，挤压后进行多道次拉拨，道次延伸系数为1.2~1.5，累计总延伸系数为5.5~10.5，可采用普通润滑油或乳浊液进行润滑，乳浊液还可起冷却作用，以使铝丝的温度不超过180℃。
本发明一种轻质高导耐热铝导线的制备方法，所制备的导线，密度小于等于2.71g/cm3，在20℃的电导率大于等于62% IACS，短时耐热温度高达230℃，长期耐热温度高达210℃，抗拉强度大于等于165MPa。
 有益效果
根据金属导电理论，杂质和晶体缺陷对铝的导电性影响很大，杂质含量越少、晶格畸变和晶界等晶体缺陷越少，金属晶体的导电性越好，在工业纯铝的不可避免的杂质中，Ti、V、Cr、Mn对导电性的有害影响较大，特别是当其以固溶形式存在于铝基体时。
本发明B的添加量为按设计的铝导线组分中B的质量百分比（0.035-0.06wt.%）和工业纯铝中Ti、V、Cr、Mn杂质元素总含量的2-5倍确定的B的质量之和，在满足B元素作为精炼剂和变质剂的前提下，B、Zr、Er的协同作用带来了预料不到的技术效果。
本发明的合金熔炼过程中， Al-B中间合金的添加量按两部分确定，合金熔体中B含量远远超过0.06wt.%，其作为精炼剂和变质剂。首先，B作为精炼剂时，与工业纯铝中不可避免的Ti、V等杂质反应，生成比重较大的硼化物，以炉渣的形式被除去（见附图2、附图3），从而大幅提高铝导体的电导率。其次，富余的B作为变质剂，产生变质作用，可以使沿晶界连续分布的富Fe相变为不连续的颗粒状，既可以改善铝导线的导电性能的同时，也可提高其强度和热稳定性，同时，可以降低对原材料工业纯铝锭的纯度要求，从而大幅度降低合金制备成本。发明人发现：如果加入的精炼剂和变质剂的B含量太少，使合金基体中B含量小于0.035%，则会降低材料的电导率，但是，如果加入过量的B作为精炼剂和变质剂（B含量为Ti、V总含量的8倍），则铝中会出现较多粗大的Al、B的化合物，也会明显降低材料的电导率。
Er元素倾向于吸附在α-Al晶核上，生成Al3Er阻碍α-Al枝晶成长，达到细化二次枝晶组织的效果，初生的Al3Er被推挤到晶界，在熔体最后完全凝固时形成含α-Al相和Al3Er相的共晶化合物。作为稀土元素，Er也可与Fe等杂质元素形成化合物，产生净化和变质作用。附图6为对比例2中的第二相粒子及能谱分析结果，对比例2未添加B，图6(b)显示晶内可能形成了Al3Er和(Al,Fe)的混合相，或(Al,Fe,Er)三元化合物，没有B的作用，Er元素更倾向于与杂质元素形成化合物或者形成Al3X相。本发明的优势是利用B和Zr 、Er的协同作用，由B来产生除杂和变质作用，抑制含Er杂质相的形成，并通过铸造过程的快速冷却抑制粗大的初生相形成，使Zr和Er主要以亚稳定的过饱和固溶态存在，从而促使后续退火过程析出大量与基体共格的Al3(Er,Zr)复合粒子，如附图5所示。本发明Al3(Er,Zr)三元相析出的原理是：退火过程中，扩散速率较快的Er在基体中率先形成粒子，为Zr的脱溶析出提供形核质点，促进Al-Zr固溶体的分解，扩散速率较慢的Zr聚集在Al3Er粒子的外层，形成与基体共格的、L12结构的、纳米级的球状Al3(Er,Zr)复合粒子。本发明析出纳米尺度的Al3(Er,Zr)复合粒子有如下优势：一方面，降低Zr和Er在铝基体中的固溶程度，提高铝导线的电导率，另一方面，弥散分布的与晶体共格的纳米尺度的Al3(Er,Zr)复合粒子，对位错、亚晶、晶界产生钉扎作用，具有明显的强化作用及抑制再结晶作用，能有效提高铝导体的强度和耐热性。
本发明采用铸造、退火、挤压、拉拨的制备工艺，能够区别其他铝导线的连铸连轧工艺，具有生产流程短、工艺控制简单灵活的优势，制备的导线在保证较高导电率的前提下，具有较好的耐热性和比强度。本发明的快速冷却铸造有一定抑制粗大初生相形成的作用，使铸坯具有较高过饱和固溶度，为后续退火工序析出细小弥散分布的第二相粒子提供驱动力。本发明的铸坯高温短时退火，其主要作用是析出大量弥散分布的第二相粒子，尤其是析出很多与晶体共格的纳米尺度的Al3(Er,Zr)复合粒子，其次要作用是适当消除坯料的成分偏析、组织偏析及铸造应力，从而改善铸造组织和加工性能，此外，相对铝合金的均匀化退火时间及已公开专利的退火时间，本发明的退火时间较短，具有节能降耗优势。本发明采用挤压进行塑性变形，具有生产灵活、工艺控制简单的优势，既可采用锭坯一次挤压成线杆，也可采用连续铸造的杆坯连续挤压成较小直径的线坯，相比轧制变形，具有更大的变形程度和更强烈的三向压应力状态，可大大改善铸造组织和提高后续加工性能。本发明采用挤压杆料进行多道次冷拉拔获得铝合金单丝，可根据实际需要确定杆料直径，特别是可根据服役强度要求确定所用杆料直径，并通过不同拉拨变形量来调控单丝的强度。
综上所述，本发明基于Al、B、Zr、Er元素的合理配比和含B精炼剂的适量加入，通过快速冷却铸造、铸坯的高温短时退火、大变形量的挤压，使B产生净化、变质及协同Zr、Er的复合微合金化作用，制备出的导线在20℃的电导率大于等于62% IACS，长期耐热温度高达210℃，短时耐热温度高达230℃，抗拉强度大于等于165MPa，密度（≤2.71g/cm3）与纯铝的密度2.7g/cm3比较接近，可提高输电线路容量和降低输送线损，具有良好的抗弧垂特性和耐热性能，可增加输电线路塔杆的间距和提高远距离、大容量输电线路的安全稳定性和服役寿命。本发明生产流程短、工艺控制简单灵活且要求较低，加入的合金化元素数目少、含量低，节省了昂贵稀土元素的用量，对原材料杂质含量和铸坯质量没有严格要求，能源消耗也不高，因此，还具有生产成本较低的优势。
 附图说明
附图 1(a) 为实施例 1 的铸态金相组织，
附图1(b)为实施例2的铸态金相组织，
附图1(c)为实施例3的铸态金相组织；
附图2为本发明实施例2熔炼炉渣的微观组织照片，
附图3为附图2中质点的能谱分析结果；
附图4(a)为对比例2合金的金相组织照片，
附图4(b)为实施例2合金的金相组织照片，
附图4(c)为对比例1合金的金相组织照片；
附图5(a)为实施例2合金的低倍率TEM照片，
附图5(b)为实施例2合金的高倍率TEM照片，
附图5(c)为实施例2合金中Al3(Er,Zr)复合粒子的高分辨TEM形貌；
附图6(a) 为对比例2合金退火态合金的微观组织形貌，
附图6(b)为附图6(a)中标识处A点析出相能谱分析结果，
附图6(c)为附图6(a)中标识处B点析出相能谱分析结果，
附图6(d)为附图6(a)中标识处C点析出相能谱分析结果；
附图7~附图10为实施例2所制备的Φ4铝导线的性能检测报告。
由图1(a)、图1 (b)、图1 (c)可以看出，Zr、Er元素的联合添加具有明显的晶粒细化效果，并且Zr、Er元素的含量越大，晶粒细化效果越明显。
由图2、图3 所示实施例2炉渣的微观组织形貌及能谱分析结果可以看出：存在不同于白色AlFe相的另一种相，该相呈现出四周较暗中间亮白的特点，能谱分析结果显示，该相为含Al、B、Ti、V的相，说明杂质Ti、V确实与B形成了化合物而进入炉渣，这是使得合金电导率提高的重要原因之一。
由图4(a)可以看出，不用B作精炼剂时，晶界分布着较多连续的杂质相；由图4(b)可以看出，采用合适质量比例的硼精炼剂后，基体中出现了较多的点状相，晶界的连续相也转变为不连续的条状及点状；由图4(c)可以看出，采用过量的B作为精炼剂后，基体中出现了较多粗大的第二相，能谱分析结果表明为Al、B的化合物。结合对比例2中的材料导电率较低的事实，说明添加过量的B对材料的电导率有负面影响。
在图5(a)所示析出相周围可以观察到清晰的Ashby-Brown应力衬度，析出相仍与基体保持良好的共格性，图5(b)所示析出相的外壳和内核表现出了明显的衬度差异，图5(c)所示区域可分为基体、析出相的壳、析出相的核3个部分，析出相的壳的选区电子衍射斑点对应L12结构，析出相外壳对应的衍射强度比内核要强，确定为一种内部富含Er、外部壳富含Zr的Al3(Er1-xZrx) 复合相。图5(a)、图5(b)、图5(c)证明本发明合金退火过程中析出了大量与基体共格的纳米尺度的Al3(Er，Zr) 复合相粒子，从而保障了电导率和耐热性及强度的协调发展
图6(a)-(d)为对比例2中的第二相粒子及能谱分析结果，图6(b)显示晶内A点可能是Al3Er和(Al,Fe)的混合相，也可能是(Al,Fe,Er)三元化合物，图6(c)显示晶界B点颗粒相为Al3Er相，图6(d)显示晶界C点针状相为Al3Fe相。对比例2未添加B， Er元素更倾向于与杂质元素形成化合物或者形成Al3X相，证明B元素有促进Al3(Er1-xZrx)三元复合相析出的作用。
附图7~附图10可知，本发明实施例2所制备的铝导线在20℃的电导率达到了62% IACS，短期耐热温度达到230℃(230℃保温1h抗拉强度残留率高达92%，抗拉强度为165MPa，可作为本发明导线性能优越性的有力支撑材料。
 本发明的实施方式
实施例1
以纯度大于 99.7％的工业纯铝锭、Al-11.34％Zr 中间合金和Al-4.7％ Er 中间合金为原料，先将工业纯铝在760℃熔化后，加入Al-Zr、Al-Er中间合金，待中间合金完全熔化并搅拌均匀后，对Zr、Er、Al合金熔体进行炉前快速成分分析，并将合金熔体降至730℃保温，再按合金熔体中杂质元素Ti、V总含量的2倍及合金中B的质量百分比，加入Al-2.5％ B 中间合金进行精炼，使各元素的质量百分比为 ：B为0.035wt.%，Zr为 0.1 wt.％，Er为 0.21 wt.％，Ti、V、Cr、Mn等杂质元素总和为 0.001wt.％，Al为余量。然后依次进行搅拌、静置、扒渣，水冷铸造。坏料在480℃保温10h随炉冷却，随后在420℃进行热挤压，挤压比为89.7，挤压变形量为98.7%，得到Φ9.5的圆铝杆，经5道次拉拔成Φ4.0mm的铝导线。对铝导线进行导电率、抗拉强度、耐热性能、密度测试，结果如表 1 所示。
表 1
实施例 编号 密度g/cm3 导电率/IACS 抗拉强度/MPa 230℃/1h退火强度残存率 210℃/400h退火强度残存率
1# 2.708 62.0 165 90.1% 90.8%
实施例2
以纯度大于 99.7％的工业纯铝锭、Al-11.34％Zr和Al-4.7％ Er 中间合金为原料，将工业纯铝在760℃熔化后，加入Al-Zr、Al-Er中间合金，待中间合金完全熔化并搅拌后，对Zr、Er、Al合金熔体进行炉前快速成分分析，并将合金熔体降至730℃保温，再按合金熔体中杂质元素Ti、V总含量的3.5倍及合金中B的质量百分比，加入Al-2.5％ B 中间合金进行精炼，使各元素的质量百分比为 ：B为0.05 wt.%，Zr为 0.1wt.％，Er为 0.21wt.％，Ti、V、Cr、Mn等杂质元素总和为 0.001wt.％，Al为余量。然后依次进行搅拌、静置、扒渣，水冷铸造。坏料在490℃保温8h随炉冷却，随后在420℃进行热挤压，挤压比为89.7，挤压变形量为98.7%，得到Φ9.5的圆铝杆，经5道次拉拔成Φ4.0mm的铝导线。对铝导线进行导电率、抗拉强度、耐热性能、密度测试，结果如表2 所示。
表2
实施例 编号 密度g/cm3 导电率/IACS 抗拉强度/MPa 230℃/1h退火强度残存率 210℃/400h退火强度残存率
2# 2.707 62.0 165 92.0 % 93.8%
实施例3
以纯度大于99.7％的工业纯铝锭、Al-11.34％Zr 中间合金和Al-4.7％ Er 中间合金为原料，将工业纯铝在760℃熔化后，加入Al-Zr、Al-Er中间合金，待中间合金完全熔化并搅拌后，对Zr、Er、Al合金熔体进行炉前快速成分分析，并将合金熔体降至730℃保温，再按合金熔体中杂质元素Ti、V总含量的5倍及合金中B的质量百分比，加入Al-2.5％ B 中间合金精炼后，各元素的质量百分比为 ：B为0.06 wt.%，Zr为 0.2 wt.％，Er为 0.4wt.％，Ti、V、Cr、Mn等杂质元素总和为 0.001 wt.％，Al为余量。然后依次进行搅拌、静置、扒渣，水冷铸造。坯料在500℃保温1h随炉冷却，随后在420℃进行热挤压，挤压比为89.7，挤压变形量为98.7%，得到Φ9.5的圆铝杆，经5道次拉拔成Φ4.0mm的铝导线。对铝导线进行导电率、抗拉强度、耐热性能、密度测试，结果如表3 所示。
表3
实施例 编号 密度g/cm3 导电率/IACS 抗拉强度/MPa 230℃/1h退火强度残存率 210℃/400h退火强度残存率
3# 2.71 62.1 170 90.7% 91.9%
对比例1
以纯度大于99.7％的工业纯铝锭、Al-11.34％Zr 中间合金和Al-4.7％ Er 中间合金为原料，将工业纯铝在760℃熔化后，加入Al-Zr、Al-Er中间合金，待中间合金完全熔化并搅拌后，对Zr、Er、Al合金熔体进行炉前快速成分分析，并将合金熔体降至730℃保温，再按合金熔体中杂质元素Ti、V总含量的8倍及合金中B的质量百分比，加入Al-2.5％ B 中间合金精炼后，各元素的质量百分比为 ：B为0.10wt.%，Zr为 0.1wt.％，Er为 0.21wt.％，Ti、V、Cr、Mn等杂质元素总和为 0.001wt.％，Al为余量。然后依次进行搅拌、静置、扒渣，水冷铸造。坯料在490℃保温8h后随炉冷却，随后在420℃进行热挤压，挤压比为89.7，挤压变形量为98.7%，得到Φ9.5的圆铝杆，经多道次拉拔成Φ4.0mm的铝导线。对铝导线进行导电率、抗拉强度、耐热性能、密度测试，结果如表4所示。
表4
实施例 编号 密度g/cm3 导电率/IACS 抗拉强度/MPa 230℃/1h退火强度残存率 210℃/400h退火强度残存率
1# 2.708 60.7 170 87.5 88.9%
对比例2
按照工业纯铝、Zr 0.2％，Er 0.4％进行配料，其原料为纯度大于 99.7％的工业纯铝锭、Al-11.34％Zr中间合金、Al-4.7％ Er中间合金。将工业纯铝在760℃熔化后，加入Al-Zr、Al-Er中间合金，待中间合金完全熔化并搅拌后，对Zr、Er、Al合金熔体进行炉前快速成分分析，并将合金熔体降至730℃保温，依次进行搅拌、静置、扒渣，水冷铸造。铸锭在500℃保温1h随炉冷却，随后在420℃进行热挤压，挤压比为89.7，挤压变形量为98.7%，得到Φ9.5的圆铝杆，经5道次拉拔成Φ4.0mm的铝导线。对铝导线进行导电率、抗拉强度、耐热性能、密度测试，结果如表 5所示。
表 5
实施例 编号 密度g/cm3 导电率/IACS 抗拉强度/MPa 230℃/1h退火强度残存率 210℃/400h退火强度残存率
2# 2.713 58.2 190 86.3% 87.6%
本发明3个实施例得到的铝合金导线，密度均小于等于2.71g/cm3，在20℃常温下导电率大于等于62% IACS，短时耐热温度达到230℃，长期耐热温度达到210℃。对比例1加入了过量的B，其他组分和实施例1和实施例2相同，退火工艺与实施例2相同，对比例2除了未加入B元素外，其他组分与实施例3相同，2个对比例的电导率均低于61%IACS，在230℃退火1小时的强度残存率均低于90%，在230℃退火400小时的强度残存率也低于90%。从以上实施例与对比例所得到的性能参数可知：作为精炼剂和变质剂的B，如果加入含量太少，导致合金基体中B含量小于0.035wt.%，或者加入量过多，如加入Ti、V总含量8倍的B，均会降低导线的导电性能和耐热性能。

Claims (15)

  1. 一种轻质高导耐热铝导线，包括下述组分按质量百分比组成：
    B：0.035～0.06wt.％；
    Zr：0.1～0.2wt.％；
    Er：0.2～0.4wt.％(但不包含0.2wt％)；
    Ti、V、Cr、Mn杂质元素总含量小于等于0.01wt.％，其余为Al；
    其中，Zr、Er按质量比Zr：Er＝1：1.5～2.5添加；
  2. 根据权利要求1所述的一种轻质高导耐热铝导线，其特征在于：铸造时，以20-300℃/s的速度冷却至室温，然后在480℃~500℃进行1-10h的高温退火。
  3. 根据权利要求1所述的一种轻质高导耐热铝导线，其特征在于：所述导线具有纳米级的球状Al3（Er，Zr）复合粒子。
  4. 根据权利要求3所述的一种轻质高导耐热铝导线，其特征在于：所述纳米级的球状Al3（Er，Zr）复合粒子为与基体共格的Ll2结构。
  5. 根据权利要求1所述的轻质高导耐热铝导线，其特征在于，导线密度小于等于2.71g/cm3，在20℃的电导率大于62％IACS，短期耐热温度高达230℃，长期耐热温度高达210℃，抗拉强度大于等于165MPa。
  6. 如权利要求1所述的一种轻质高导耐热铝导线的制备方法，包括下述步骤：
    第一步：取工业纯铝锭加热至740℃～780℃熔化后，按设计的铝导线组分中Zr、Er的质量百分比，配取Al-Zr、Al-Er中间合金加入铝熔体中，待中间合金完全熔化并搅拌均匀后，对Zr、Er、Al合金熔体进行炉前快速成分分析，同时添加Al-B中间合金进行精炼、铸造，得到铝合金坯料；
    第二步：将坯料退火后，进行挤压、拉拨成单丝。
  7. 根据权利要求6所述的一种轻质高导耐热铝导线的制备方法，其特征在于：Al-B中间合金的添加量由以下两部分确定：第一，按设计组分中B的质量百分比配取的Al-B中间合金；第二，按B的质量为Zr、Er、Al合金熔体中Ti、V、Cr、Mn杂质元素总含量的2-5倍配取的Al-B中间合金。
  8. 根据权利要求6所述的一种轻质高导耐热铝导线的制备方法，其特征在于：铸造采用普通铸造或半连续铸造方式获得锭坯；或采用连续铸造方式获得杆坯。
  9. 根据权利要求8所述的一种轻质高导耐热铝导线的制备方法，其特征在于：铸造时，铸锭以20-300℃/s的速度冷却至室温。
  10. 根据权利要求9所述的一种轻质高导耐热铝导线的制备方法，其特征在于：铸造时采用水冷铸造。
  11. 根据权利要求8所述的一种轻质高导耐热铝导线的制备方法，其特征在于：锭坯或杆坯的退火温度为480℃～500℃，保温1-10h后随炉冷却。
  12. 根据权利要求8所述的一种轻质高导耐热铝导线的制备方法，其特征在于：锭坯进行热挤压，热挤压温度为300～450℃；杆坯进行室温连续挤压。
  13. 根据权利要求12所述的一种轻质高导耐热铝导线的制备方法，其特征在于：热挤压或室温连续挤压的挤压比大于等于80，挤压变形量大于等于80％。
  14. 根据权利要求6-13任意一项所述的一种轻质高导耐热铝导线的制备方法，其特征在于：挤压后进行多道次拉拨，道次延伸系数为1.2～1.5，累计总延伸系数为5.5～10.5，拉拨时，采用普通润滑油或乳浊液进行润滑、冷却，控制铝丝的温度小于等于180℃。
  15. 根据权利要求14所述的一种轻质高导耐热铝导线的制备方法，其特征在于：所制备的导线，密度小于等于2.71g/cm3，在20℃的电导率大于62％IACS，短期耐热温度高达230℃，长期耐热温度高达210℃，抗拉强度大于等于165MPa。
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Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105734353B (zh) * 2016-03-25 2017-06-23 中南大学 一种轻质高导耐热铝导线及其制备方法
CN107587004B (zh) * 2017-08-30 2019-03-29 中南大学 一种Al-Ni-Cu-Fe-Yb-Sc合金导体材料及其制备方法
CN108220716B (zh) * 2018-01-22 2020-08-07 合肥工业大学 一种具有优异冲压成形性能的Al-Mg-Si-Cu-Zr-Er合金及其制备方法
CN109338166A (zh) * 2018-09-25 2019-02-15 全球能源互联网研究院有限公司 一种Al-Er-B耐热合金单丝及其制备方法
CN109468478A (zh) * 2018-12-18 2019-03-15 云南云铝涌鑫铝业有限公司 一种铝锭的制备方法
CN110042276A (zh) * 2019-04-24 2019-07-23 安徽省金兰金盈铝业有限公司 一种交通用轻量化铝合金新材料的加工工艺
CN114381634B (zh) * 2021-12-11 2022-07-29 江西理工大学 具有双球壳结构析出相耐热铝锆合金电缆材料及其制备方法
CN115608961A (zh) * 2022-10-31 2023-01-17 河南科技大学 一种轻质高强高导铜铝复合材料及其制备方法
CN116872577B (zh) * 2023-07-10 2025-07-08 上海交通大学 一种导电用强界面结合铜铝复合材料及其制备方法
CN117568663A (zh) * 2023-11-13 2024-02-20 中南大学 含高密度纳米粒子的高韧耐热铝导体材料及制备方法
CN117587299A (zh) * 2023-11-21 2024-02-23 国网智能电网研究院有限公司 一种高强高导耐热铝合金节能线材及其制备方法和应用
CN121380687B (zh) * 2025-12-24 2026-03-24 中南大学 一种含双相纳米结构的耐热铝稀土合金导线及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102021443A (zh) * 2010-10-15 2011-04-20 北京工业大学 Al-Er-Zr合金及其时效强化工艺
CN103627935A (zh) * 2013-12-09 2014-03-12 国家电网公司 一种非热处理型耐热铝合金单丝及其制备方法
WO2015138748A1 (en) * 2014-03-12 2015-09-17 NanoAL LLC Aluminum superalloys for use in high temperature applications
CN105063433A (zh) * 2015-08-17 2015-11-18 国网智能电网研究院 一种高导耐热铝合金单丝及其制备方法
CN105734353A (zh) * 2016-03-25 2016-07-06 中南大学 一种轻质高导耐热铝导线及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08144003A (ja) * 1994-11-16 1996-06-04 Mitsubishi Alum Co Ltd 耐熱性に優れた高強度アルミニウム合金
CN102230113B (zh) * 2011-07-18 2013-06-26 中南大学 一种耐热铝合金导体材料及其制备方法
CN103498083B (zh) * 2013-10-10 2016-04-20 郑州大学 一种耐热导电铝合金

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102021443A (zh) * 2010-10-15 2011-04-20 北京工业大学 Al-Er-Zr合金及其时效强化工艺
CN103627935A (zh) * 2013-12-09 2014-03-12 国家电网公司 一种非热处理型耐热铝合金单丝及其制备方法
WO2015138748A1 (en) * 2014-03-12 2015-09-17 NanoAL LLC Aluminum superalloys for use in high temperature applications
CN105063433A (zh) * 2015-08-17 2015-11-18 国网智能电网研究院 一种高导耐热铝合金单丝及其制备方法
CN105734353A (zh) * 2016-03-25 2016-07-06 中南大学 一种轻质高导耐热铝导线及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BIN JIE: "Effect of Zr, Er Composite Microalloying on Microstructure and properties of Industrial Pure Aluminium", MASTER'S DISSERTATION OF CENTRAL SOUTH UNIVERSITY, 30 June 2012 (2012-06-30), pages 12 - 13 & 38 *

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