WO2017162198A1 - 一种加铁的轻质高导耐热铝导线及其制备工艺 - Google Patents

一种加铁的轻质高导耐热铝导线及其制备工艺 Download PDF

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Publication number
WO2017162198A1
WO2017162198A1 PCT/CN2017/078007 CN2017078007W WO2017162198A1 WO 2017162198 A1 WO2017162198 A1 WO 2017162198A1 CN 2017078007 W CN2017078007 W CN 2017078007W WO 2017162198 A1 WO2017162198 A1 WO 2017162198A1
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iron
aluminum
conductivity
resistant
aluminum wire
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PCT/CN2017/078007
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English (en)
French (fr)
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李红英
宾杰
高兆和
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中南大学
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Priority to US16/082,941 priority Critical patent/US10460849B2/en
Priority to AU2017239455A priority patent/AU2017239455B2/en
Priority to JP2018546582A priority patent/JP6691612B2/ja
Publication of WO2017162198A1 publication Critical patent/WO2017162198A1/zh

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    • 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
    • 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
    • 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
    • H01B1/023—Alloys based on aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0036—Details

Definitions

  • the invention relates to an aluminum wire for wire and cable, in particular to an iron-clad used for an overhead power transmission line
  • the lightweight high-conductivity heat-resistant aluminum wire and the preparation process thereof belong to the technical field of electrical materials.
  • the long-term operating temperature of heat-resistant wires used in urban and rural power transmission and transmission lines in China generally does not exceed 180 °C, and the conductivity is 61% IACS. And below, the line loss is large. According to the requirements of China's national economic development and energy interconnection, high-voltage, large-capacity, and long-distance have become the development direction of transmission lines. In order to save the tight corridor resources, reduce the line construction cost, and reduce the transmission line loss, high requirements are placed on the transmission line, which must have high electrical conductivity, good heat resistance and anti-sag characteristics.
  • Microalloying is an effective way to improve the heat resistance and strength of aluminum conductors, but it has an adverse effect on electrical conductivity.
  • the conductivity of high purity aluminum with a purity of 99.99% at 20 ° C is 64.94%
  • IACS has a density of 2.7 g/cm3, a strength of only 80 to 100 MPa, and a recrystallization temperature of about 150 °C.
  • Alloy elements such as Zn are commonly used high-strength electrical aluminum, and the tensile strength can reach 295 ⁇ 325MPa, but the conductivity at 20°C is only 52.5 ⁇ 55% IACS. Therefore, the development of low-cost wires with high electrical conductivity, good heat resistance and high specific strength has become an urgent technical problem in the industry.
  • Chinese patent CN 102230113A discloses a heat-resistant aluminum alloy conductor material and a preparation process thereof.
  • the aluminum conductor material obtained by zirconium and bait composite microalloying has a conductivity of between 59.5 and 60.5% IACS and a long-term heat resistance temperature of 180. °C, tensile strength is less than 160MPa.
  • Chinese patent CN 102965550A discloses a high-strength and high-conductivity heat-resistant aluminum conductor material and a preparation process thereof, which adopts a composite micro-alloying of zirconium, hafnium and iron, and uses an isothermal precipitation annealing process to obtain a fine granular Al(Tm,Fe) phase and dispersion.
  • the distributed Al3 (Tm, Zr) shell core structure phase greatly improves the heat resistance and strength of the aluminum conductor material.
  • the long-term heat resistance temperature of the prepared aluminum conductor material reaches 210 ° C, and the tensile strength is above 185 MPa, however, The maximum conductivity is only 60.8% IACS.
  • Chinese patent CN 102758107A discloses a high-strength and high-conductivity heat-resistant aluminum alloy wire and a preparation process thereof, and six kinds of alloying elements are added, wherein three kinds of rare earth elements are added, and a higher content of zirconium elements is added, which is 0.15% to 0.60%.
  • the annealing time is up to 30 ⁇ 50 hours, and the prepared aluminum conductor material can withstand heating at 280 °C for 1 hour, but its tensile strength is lower than or equal to 160 MPa, and the electrical conductivity is lower than or equal to 61.8% IACS.
  • the temperature is only 180 °C.
  • the object of the present invention is to overcome the deficiencies of the prior art and provide a lightweight high-conductivity heat-resistant aluminum wire with a reasonable group distribution ratio, a short production process, a simple process, and a low production cost, and a preparation process thereof.
  • the invention produces purification, metamorphism, refinement and dispersion strengthening by adding a small amount of alloying elements which have less damage to electrical conductivity and a reasonable process, and compared with 99.99% of high-purity aluminum, under the premise that the conductivity decreases little.
  • the heat resistance and specific strength of the wire are greatly improved.
  • the present invention utilizes the metamorphism of boron-containing iron phase and the crushing action of extrusion on the coarse iron-containing phase, and exerts a beneficial effect of iron on the comprehensive performance of the aluminum alloy while reducing the cost of controlling iron.
  • the invention relates to an iron-added lightweight high-conductivity heat-resistant aluminum wire comprising the following components, which are composed by mass percentage:
  • the total content of titanium, vanadium, chromium and manganese is less than 0.01 wt.%, and aluminum is the balance;
  • the B content in the alloy component is from 0.045 to 0.095 wt.%, and more preferably the B content is from 0.055 to 0.08 wt.%.
  • the invention relates to an iron-added lightweight high-conductivity heat-resistant aluminum wire which is cooled to room temperature at a rate of 20-300 ° C / s during casting, and then subjected to high-temperature rapid annealing at 480 ° C to 500 ° C for 1-10 h.
  • the invention relates to an iron-added lightweight high-conductivity heat-resistant aluminum wire, wherein the wire has nano-sized spherical Al3(Er, Zr) composite particles;
  • the invention relates to an iron-added lightweight high-conductivity heat-resistant aluminum wire, wherein the nano-sized spherical Al3(Er, Zr) composite particles are Ll2 structures covalent with the matrix.
  • the preparation process of the iron-added lightweight high-conductivity heat-resistant aluminum wire is selected according to the designed alloy group distribution ratio: industrial pure aluminum and aluminum boron, aluminum zirconium, aluminum iron, aluminum-bismuth intermediate alloy, at 740 ⁇ After melting industrial pure aluminum at 780 ° C, the intermediate alloy is added. After the intermediate alloy is completely melted, the melt is kept at 720 ° C to 740 ° C. After stirring, refining, rapid analysis of the components before the furnace, composition adjustment, standing, and slag The rapid cooling casting is performed at 700 to 720 ° C, and then the blank is annealed, extruded, and drawn to obtain an aluminum alloy monofilament.
  • the invention relates to a process for preparing an iron-added lightweight high-conductivity heat-resistant aluminum wire which can be obtained by ordinary casting or semi-continuous casting; or by continuous casting.
  • the invention relates to a process for preparing an iron-added 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 preparation process of an iron-added lightweight high-conductivity heat-resistant aluminum wire, which is cast by water cooling.
  • the invention discloses a preparation process of an iron-added 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 2-10 hours.
  • the invention relates to a preparation process of an iron-added 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 rod.
  • the billet is continuously extruded at a temperature of 300 to 450 °C.
  • the invention relates to a preparation process of an iron-added 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 preparation process of an iron-added 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 actual needs
  • the service strength requirements determine the diameter of the blank used and control the strength of the monofilament by different pull deformations.
  • the invention relates to a preparation process of an iron-added lightweight high-conductivity heat-resistant aluminum wire, which is subjected to multi-pass drawing after extrusion, and has a pass extension coefficient of 1.2 to 1.5, and a cumulative total elongation coefficient of 5.5 to 10.5, which can be used in common Lubricating oil or 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 process of an iron-added lightweight high-conductivity heat-resistant aluminum wire, wherein the prepared wire has a density of 2.714 g/cm3 or less and a conductivity of more than 62% at 20 °C.
  • IACS long-term heat-resistant temperature up to 210 ° C
  • the residual rate of strength after annealing at 230 ° C for 1 hour is greater than 91%
  • tensile strength is greater than or equal to 170MPa.
  • the present invention adds a small amount of alloying elements, a low content, a reasonable ratio of aluminum, boron, zirconium, hafnium, iron, and a rapid cooling casting, high temperature short-time annealing of the billet, large deformation
  • the wire density prepared by the invention is close to the density of pure aluminum ( ⁇ 2.715 g/cm3), and the conductivity is kept at 62% IACS.
  • the tensile strength is above 170 MPa
  • the long-term heat-resistant temperature is as high as 210 ° C
  • the short-time heat-resistant temperature is as high as 230 ° C.
  • the invention also has the advantages of short production process, simple process, low requirement and low production cost, and the prepared aluminum alloy wire can meet the requirements of high conductivity, high heat resistance and high specific strength of long-distance and large-capacity transmission lines. .
  • 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 inevitable impurity elements in industrial pure aluminum, titanium, vanadium, chromium, manganese, silicon, iron, etc. have a great influence on the conductivity, especially when the higher content of impurity elements is dissolved in the aluminum matrix, the conductance of the aluminum conductor is greatly reduced. rate.
  • the solid solution atoms cause lattice distortion and destroy the periodicity of the pure metal Coulomb potential field, and become the scattering center of the conductive electrons.
  • a small amount of zirconium dissolved in the aluminum matrix can significantly reduce the conductivity of the alloy.
  • Iron is usually defined as a harmful impurity element of aluminum alloy and should be removed. This is because iron tends to be in the grain boundary during the casting process. Precipitating the skeletal phase of the continuous network, when the iron content is high, a lamellar or needle-like iron phase will appear. It has a very adverse effect on the strength and toughness of the alloy. These continuous networked iron-containing phases are difficult to eliminate by heat treatment and also adversely affect the processing properties of the alloy. By adding a modifier and adopting appropriate smelting, casting, and plastic deformation processes, the morphology and distribution of the iron-containing phase can be changed, and the iron-containing phase can be distributed in the aluminum matrix in fine particles, which can effectively hinder dislocation and grain boundary movement. The effect of the alloy is that it has high strength and heat resistance and has little effect on the electrical conductivity.
  • the invention adds a higher content of boron (>0.04 Wt.%), mainly used as a metamorphism, in addition to the refining action of the purification matrix.
  • the refining action of boron of the invention is mainly reflected in the reaction with impurity elements such as titanium, vanadium, chromium, manganese, etc., and the compound with a larger specific gravity is deposited in the bottom of the furnace to be discharged into the slag, thereby effectively purifying the alloy matrix.
  • the metamorphism of boron of the invention is mainly reflected in improving the morphology and distribution of the iron-containing phase, which not only improves the comprehensive performance of the alloy, but also reduces the requirements for the purity of the raw materials and the cost of controlling the iron, which is multiplied.
  • the inventors have found that insufficient or excessive boron content does not achieve the goal of effectively improving electrical conductivity.
  • the boron content is 0.035 At wt.%, as shown in Fig. 3(a) and Fig. 3(b), the aluminum-iron phase is continuously distributed in the form of bones at the grain boundary or the lamellar eutectic structure, and the conductivity of the corresponding wire is only 59.5% IACS.
  • the addition of zirconium element content of the invention is relatively small, which weakens the adverse effect of zirconium on the electrical conductivity of the alloy.
  • the rapid solidification of the melt can inhibit the formation of coarse primary Al3Zr particles, and the zirconium is mainly solidified by metastable supersaturation. The state exists, and a large number of fine Al3Zr particles dispersed in the matrix and coherent with the matrix are precipitated in the subsequent annealing process, thereby greatly improving the heat resistance and strength of the alloy.
  • the ruthenium element added by the invention may produce three functions, one is degassing and impurity removal refining, the electrical conductivity of the alloy is improved by reducing the hydrogen content and the impurity content in the melt, and the second is to refine the grains and dendrites.
  • the structure is used to improve the toughness of the slab.
  • the third is to form a fine Al3 (Zr, La) composite phase during annealing, which acts to hinder the growth of grain boundaries and subgrain boundaries and dislocation migration, thereby strengthening the alloy and improving its heat resistance. performance.
  • 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, and the precondition of the prepared wire in ensuring high conductivity. Under, it has better heat resistance and specific strength.
  • the rapid cooling casting of the invention has certain effects of inhibiting the formation of coarse aluminum-zirconium and aluminum-iron primary phases, so that the slab has a higher supersaturated solid solubility, and provides a driving force for the precipitation of fine dispersed second phase particles in the subsequent annealing process.
  • the high temperature short-time annealing of the slab of the invention mainly discharges fine zirconium-containing second phase particles such as Al3Zr, and the secondary function is to appropriately eliminate the composition segregation, tissue segregation and casting stress of the blank, thereby improving the foundry structure and processing.
  • Performance in addition, the annealing time of the invention is shorter than that of the aluminum alloy, and the annealing time of the patented invention is short, and has the advantages of energy saving and consumption reduction.
  • the invention adopts extrusion to carry out plastic deformation, has the advantages of flexible production and simple process, and can be used for one-time extrusion of the ingot into a wire rod, or continuous extrusion of the continuous production of the blank into a smaller diameter coiled wire blank.
  • 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 utilizes a reasonable ratio of aluminum, boron, zirconium, hafnium and iron elements, and utilizes rapid cooling casting, high-temperature short-time annealing of the slab, and large-deformation extrusion to synergistically produce purification and deterioration. Refinement and strengthening and toughening.
  • the invention has short production process, simple and flexible process and low requirement, and the number of alloying elements added is small and the content is low, the amount of expensive rare earth elements is saved, the impurity content of the raw materials and the quality of the slab are not strictly required, and the energy consumption is not high. Therefore, it also has the advantage of lower production costs.
  • the prepared wire has a conductivity of 62% or more at 20 ° C IACS, long-term heat-resistant temperature up to 210 ° C, short-term heat-resistant temperature up to 230 ° C, tensile strength above 170MPa, density ( ⁇ 2.714g / cm3) and pure aluminum density of 2.7g / cm3 is relatively close ( ⁇ 2.714g / Cm3), can meet the requirements of long-distance, large-capacity transmission lines, its high conductivity can increase the transmission line capacity and reduce the transmission line loss, and its good heat resistance can improve the safety and stability of the line and its service life.
  • the high specific strength can increase the anti-sag characteristics of the wire and increase the distance between the towers of the transmission line, which has significant economic benefits and energy saving and environmental protection significance.
  • Figure 1 is a microstructure of the slag of Example 1;
  • Figure 2 is a graph showing the results of energy spectrum analysis of the particles in Figure 1.
  • Figure 3 (a) is a SEM photograph of the alloy of Comparative Example 1;
  • Figure 3 (b) is the result of energy spectrum analysis of the second phase in Figure 3 (a);
  • Figure 3 (c) is a SEM photograph of the alloy of Example 1;
  • Figure 3 (d) is the result of the energy spectrum analysis of the second phase in Figure 3 (c);
  • Figure 3 (e) is a SEM photograph of the alloy of Example 3;
  • Figure 3 (f) is the energy spectrum analysis result of the second phase in Figure 3 (e);
  • Figure 3 (g) is a SEM photograph of the alloy of Comparative Example 2;
  • Figure 3 (h) is the result of the energy spectrum analysis of the second phase in Figure 3 (g).
  • Figure 4 (a) is a metallographic photograph of the as-cast microstructure of the alloy of Example 1;
  • Figure 4 (b) is a metallographic photograph of the as-cast microstructure of the alloy of Example 3.
  • Figure 5 (a) is a TEM photograph of the alloy of Example 3, wherein there is a second phase pinning dislocation
  • Figure 5 (b) is a TEM photograph of the alloy of Example 3 with a second phase pinned grain boundary.
  • FIG. 9 are performance test reports of the ⁇ 4 aluminum wire prepared in Example 3 of the present invention.
  • the second phase of white in Figure 1 is an aluminum-iron phase, and there is also a darker, brighter white particle in the matrix (as indicated by the arrow).
  • the energy spectrum analysis in Figure 2 indicates that the particle is aluminum and boron.
  • the phase of titanium and vanadium indicates that an impurity element such as titanium or vanadium can react with boron to form a compound, which is removed in the form of slag during smelting, thereby improving the electrical conductivity of the alloy.
  • the aluminum-iron phase in the alloy mainly exists in a continuous skeleton, and there is a lamellar eutectic structure; as shown in Fig. 3(c) and Fig. 3(d), the boron content is 0.04.
  • the aluminum-iron phase is discontinuous in the form of short strips or dots, as indicated by the arrow in Fig. 3(c); as can be seen from Fig. 3(e) and Fig. 3(f), the amount of boron added is increased.
  • the aluminum-iron phase in the alloy mainly exists in discontinuous strips or spots; as can be seen from Fig. 3(g) and Fig. 3(h), when the boron content is 0.12 At wt.%, a large amount of coarse aluminum boron phase appears in the alloy.
  • Figure 4(a) and Figure 4(b) As shown in the photograph of the as-cast structure, the content of the lanthanum element added in the first embodiment is small, the grain size of the alloy is coarse, and there are many coarse dendritic structures. The content of the lanthanum element added in the embodiment 3 is relatively large, and the grain shape is equiaxed. And the grains are significantly refined.
  • the aluminum wire prepared by the invention has a conductivity of 62% at 20 ° C. IACS, short-term heat-resistant temperature reached 230 ° C (230 ° C insulation 1h tensile strength residual rate of 91%), tensile strength of 170MPa, can be a strong support for the advancement and superiority of the present invention.
  • the melt temperature is lowered to 740 ° C for heat preservation, and then subjected to stirring, refining, rapid analysis of the components before the furnace, composition adjustment, standing, slag slag, and supersaturated solid solution aluminum alloy obtained by rapid cooling casting.
  • Slab. The billet was annealed at 480 °C for 10 h, then cooled with the furnace, and then hot extruded at 400 ° C. The extrusion ratio was 89.7 and the extrusion deformation was 98.7%.
  • the round aluminum rod of ⁇ 9.5 was obtained and obtained by multi-pass drawing. ⁇ 4.0mm aluminum alloy monofilament. The performance test of the monofilament was carried out, and the results are shown in Table 1.
  • the melt temperature is lowered to 740 ° C for heat preservation, and after stirring, refining, rapid analysis of the components before the furnace, composition adjustment, standing, slag slag, and then obtaining a supersaturated solid solution aluminum alloy by rapid cooling casting.
  • Slab. The billet was annealed at 480 °C for 10 h, then cooled with the furnace, and then hot extruded at 400 ° C. The extrusion ratio was 89.7 and the extrusion deformation was 98.7%.
  • the round aluminum rod of ⁇ 9.5 was obtained and obtained by multi-pass drawing. ⁇ 4.0mm aluminum alloy monofilament. The performance of the monofilament was tested. As shown in Table 2, the electrical conductivity, the tensile strength and the heat resistance were improved with respect to Comparative Example 1.
  • the melt temperature is lowered to 740 ° C for heat preservation, and after stirring, refining, rapid analysis of the components before the furnace, composition adjustment, standing, slag slag, and then obtaining a supersaturated solid solution aluminum alloy by rapid cooling casting.
  • Slab. The billet was annealed at 490 °C for 8 h, then cooled with the furnace, and then hot extruded at 400 ° C. The extrusion ratio was 89.7 and the extrusion deformation was 98.7%.
  • the round aluminum rod of ⁇ 9.5 was obtained and the multi-pass was drawn.
  • An aluminum alloy monofilament of ⁇ 4.0 mm was obtained. The performance test of the monofilament was carried out, and the results are shown in Table 3.
  • the melt temperature is lowered to 740 ° C for heat preservation, and after stirring, refining, rapid analysis of the components before the furnace, composition adjustment, standing, slag slag, and then obtaining a supersaturated solid solution aluminum alloy by rapid cooling casting.
  • Ingot blank The billet was annealed at 500 °C for 2 h, then cooled with the furnace, and then hot extruded at 400 ° C. The extrusion ratio was 89.7 and the extrusion deformation was 98.7%.
  • the round aluminum rod of ⁇ 9.5 was obtained and the multi-pass was drawn.
  • An aluminum alloy monofilament of ⁇ 4.0 mm was obtained. The performance test of the monofilament was carried out, and the results are shown in Table 5.
  • the boron content of Comparative Example 1 was 0.035 wt. %, as can be seen from Fig. 3 (a), Fig. 3 (b), the second phase in the alloy is mainly in the form of continuous bone, the corresponding conductivity is 59.5% IACS, and the boron content of Example 1 is 0.04wt. %, as can be seen from Fig. 3(c) and Fig. 3(d), part of the second phase in the alloy exhibits a discontinuous short strip or dot (as indicated by the arrow in the figure), and the corresponding conductivity is 62.1.
  • %IACS shows that only when the amount of boron added reaches a certain value, it will have a significant effect on improving the conductivity.
  • Example 3 The boron content of Example 3 was 0.095. Wt.%, as can be seen from Figure 3 (g) and Figure 3 (h), the aluminum-iron phase in the alloy is mainly in the form of discontinuous strips or spots, the corresponding conductivity is 62% IACS, the proportion 2 boron content reached 0.12 Wt.%, as can be seen from Fig. 3(g) and Fig. 3(h), more coarse aluminum boron phase is formed in the alloy, and the corresponding conductivity is 60.2% IACS, indicating that the addition amount of boron is too high. The conductivity is reduced.
  • the density of the aluminum alloy wire obtained by the three embodiments of the present invention is less than or equal to 2.714 g/cm 3
  • the electrical conductivity is 62% IACS at a normal temperature of 20 ° C
  • the short-time heat resistance temperature is up to 230 ° C ( 230 ° C).
  • the residual rate of strength after annealing for 1 hour is more than 90%
  • the long-term heat resistance temperature is as high as 210 °C (the residual rate of strength after annealing at 210 °C for 400 hours is more than 90%).
  • Comparative Example 1 The other components were the same as in Example 1, except that less boron was added, and Comparative Example 2 was the same as Example 3 except that the boron content was higher, but two comparative examples were conducted.
  • the rate is lower than 61% IACS, and the residual rate of the strength of annealing 1 at 230 °C for 1 hour is only 86.5%, and the residual rate of strength after annealing at 210 °C for 400 hours is only 87.1%.

Abstract

一种加铁的轻质高导耐热铝导线及其制备工艺。该铝导线主要由铝、硼、锆、铁、镧和不可避免的杂质元素组成，其制备流程是：将工业纯铝熔化，然后向熔体中加入硼、锆、铁、镧的中间合金，经搅拌、精炼、炉前成分快速分析、成分调整、静置、扒渣、快速冷却铸造获得铝合金坯料，再进行铸坯退火、挤压、拉拔获得铝合金单丝。所获导线密度小于等于2.714g/cm3，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170MPa。

Description

一种加铁的轻质高导耐热铝导线及其制备工艺 技术领域
本发明涉及一种电线电缆用铝导线，具体是指一种架空供电输变线路所使用的 加铁的 轻质高导耐热铝导线及其制备工艺，属于电工材料技术领域。
背景技术
目前，我国城乡供电输变线路所使用的耐热导线，长期运行温度一般不超过 180 ℃，电导率在 61%IACS 及以下，线损较大。根据我国国民经济发展及能源互联的要求，高压化、大容量化、远距离化成为输电线路的发展方向。 为了节约紧张的走廊资源、减少线路建设成本、降低输送线损，对输电导线提出了很高的要求，既要有高电导率，又要有良好的耐热性能和抗弧垂特性。
通常，电导率与耐热性及强度存在此消彼长的关系，微合金化是提高铝导体耐热性和强度的有效途径，但是，会对导电性能产生不利的影响。纯度为99.99%的高纯铝在20℃的电导率为64.94% IACS，密度为2.7g/cm3，强度仅为80~100MPa，再结晶温度为150℃左右。6021合金添加了0.6~0.9wt.%Mg、0.5~0.9 wt.% Si、0.5wt.%Fe、0.1 wt.% Cu、0.1 wt.% Zn等合金元素，是常用的高强度电工铝，抗拉强度可达到295~325MPa，但是，其20℃时的导电率仅为52.5~55%IACS。因此，开发具有高导电率、良好耐热性能、比强度高的低成本导线，成为业内亟需解决的技术难题。
中国专利CN 102230113A公开了一种耐热铝合金导体材料及其制备工艺，采用锆、饵复合微合金化，获得的铝导体材料，其电导率介于59.5~60.5%IACS之间，长期耐热温度为180℃，抗拉强度低于160MPa。中国专利CN 102965550A公开了一种高强高导耐热铝导体材料及其制备工艺，采用锆、铥、铁复合微合金化，运用等温析出退火工艺，得到了细小颗粒状的Al(Tm,Fe)相和弥散分布的Al3(Tm,Zr)壳核结构相，大幅提高了铝导体材料的耐热性和强度，制备的铝导体材料的长期耐热温度达到了210℃，抗拉强度在185MPa以上，但是，导电率最大值只有60.8%IACS。中国专利CN 102758107A公开了一种高强高导耐热铝合金导线及其制备工艺，加入了6种合金元素，其中稀土元素有3种之多，加入了较高含量的锆元素，为0.15%~0.60%，其退火时间长达30~50小时，制备的铝导体材料经得起280℃加热1小时考核运行，但是，其抗拉强度低于等于160MPa，电导率低于等于61.8%IACS，长时耐热温度只有180℃。
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、生产流程短、工艺简单、生产成本低的轻质高导耐热铝导线及制备工艺。本发明通过微量添加对导电率损害较小的合金元素及合理的工艺，产生净化、变质、细化和弥散强化作用，相对于99.99%的高纯铝，在电导率下降很少的前提下，大幅提高了导线的耐热性和比强度。此外，本发明利用硼对含铁相的变质作用和挤压对粗大含铁相的破碎作用，在降低控铁成本的同时发挥了铁对铝合金综合性能的有益作用。
技术解决方案
本发明一种加铁的轻质高导耐热铝导线，包括下述组分，按质量百分比组成：
B 0.04~0.10wt.%，
Zr 0.10~0.15wt.%，
Fe 0.10~0.20wt.%，
La 0.05~0.30wt.%，
不可避免钛、钒、铬、锰的含量总和小于0.01wt.％，铝为余量；
优选合金组分中B含量为0.045~0.095wt.%，更优选的B含量为0.055~0.08wt.%。
本发明一种加铁的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。
本发明一种加铁的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；
本发明一种加铁的轻质高导耐热铝导线，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。
本发明一种加铁的轻质高导耐热铝导线的制备工艺，是按设计的合金组分配比分别选取工业纯铝及铝硼、铝锆、铝铁、铝镧中间合金，在740~780℃熔化工业纯铝后，加入中间合金，待中间合金完全熔化后，让熔体在720℃~740℃保温，经搅拌、精炼、炉前成分快速分析、成分调整、静置、扒渣后，在700~720℃进行快速冷却铸造，然后对坯料进行退火、挤压、拉拔，获得铝合金单丝。
本发明一种加铁的轻质高导耐热铝导线的制备工艺，所述铸造可通过普通铸造或半连续铸造获得锭坯；或通过连续铸造获得杆坯。
本发明一种加铁的轻质高导耐热铝导线的制备工艺，铸造时，铸锭以20-300℃/s的速度冷却至室温。
本发明一种加铁的轻质高导耐热铝导线的制备工艺，铸造时采用水冷铸造。
本发明一种加铁的轻质高导耐热铝导线的制备工艺，所述坯料的退火工艺为：退火温度为480℃~500℃，保温2-10h后随炉冷却。
本发明一种加铁的轻质高导耐热铝导线的制备工艺，所述挤压方式可根据生产线设备配置进行变换，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，所述挤压温度为300~450℃。
本发明一种加铁的轻质高导耐热铝导线的制备工艺，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%。
本发明一种加铁的轻质高导耐热铝导线的制备工艺，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。
本发明一种加铁的轻质高导耐热铝导线的制备工艺，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℃。
本发明一种加铁的轻质高导耐热铝导线的制备工艺，所制备的导线，密度小于等于2.714g/cm3，在20℃的电导率大于62% IACS，长期耐热温度高达210℃，230℃退火1小时后的强度残存率大于91%，抗拉强度大于等于170MPa。
综上所述，本发明加入的合金化元素数目少、含量低，通过铝、硼、锆、镧、铁元素的合理配比，以及利用快速冷却铸造、铸坯的高温短时退火、大变形程度的挤压，协同产生净化、变质、细化及强化作用，特别是铸坯退火析出的弥散强化相对提高导线的耐热性具有很好的效果。本发明制备出的导线密度与纯铝的密度比较接近（<2.715g/cm3），电导率保持在62%IACS 以上，抗拉强度在170MPa以上，长期耐热温度高达210℃，短时耐热温度高达230℃。本发明还具有生产流程短、工艺简单且要求较低、生产成本较低的优势，制备出的铝合金导线能够满足远距离、大容量输电线路的高导、高耐热、高比强度的要求。
 有益效果
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。工业纯铝中不可避免的杂质元素钛、钒、铬、锰、硅、铁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纯金属库仑势场的周期性，并成为对导电电子的散射中心，少量固溶于铝基体中的锆元素便会显著降低合金的导电性能，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。因此，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。
通常把铁元素定义为铝合金的有害杂质元素，应加以去除。这是因为铁在铸造过程中倾向于在 晶界 析出连续网状分布的骨骼相，当铁含量较高时会出现层片状或针状含铁相 ， 对合金的强度及韧性产生极为不利的影响，这些连续网状的含铁相难以通过热处理消除，同时还会对合金的加工性能产生不利影响。通过加入变质剂和采用适当的熔炼、铸造、塑性变形工艺可以改变含铁相的形态和分布，使含铁相以细小颗粒状分布于铝基体中，可以起到有效阻碍位错和晶界移动的作用，从而使合金具有较高的强度和耐热性，且对导电性能影响不大。
本发明添加较高含量的硼（＞0.04 wt.%），除起净化基体的精炼作用外，主要用作变质作用。本发明硼的精炼作用主要体现在与钛、钒、铬、锰等杂质元素反应，生成比重较大的化合物沉入炉底变成炉渣被排出，从而有效净化合金基体。本发明硼的变质作用主要体现在改善含铁相的形态及分布状况，既可提高合金的综合性能，还可降低对原料纯度的要求及控铁成本，可谓一举多得。发明人发现：硼含量不足或过量均达不到有效提高导电性能的目标。当硼含量为0.035 wt.%时，如图3(a)和图3(b)所示，铝铁相基本以骨骼状连续分布在晶界或形成层片状共晶组织，对应导线的电导率只有59.5%IACS；当硼含量为0.04 wt.%时，如图3（c）和图3(d)所示，合金中出现少量不连续的短条状或点状铝铁相，但仍有较多铝铁相以连续网状存在；当硼含量增加到0.1wt.%时，有效抑制了网状及层片状铝铁相的形成，如图3(e) 和图3(f)所示，铝铁相主要以不连续的条状或点状存在，从而使铝导线的导电性能、强度和热稳定性得到不同程度的改善；当硼含量为0.12 wt.%时，如图3(g)和图3 (h)所示，合金中出现了很多粗大的铝硼相，对应导线的电导率只有60.2%IACS。
相比专利CN 102758107A，本发明添加的锆元素含量相对较小，弱化了锆对合金导电性能的不利影响，同时，熔体的快速凝固可抑制粗大初生Al3Zr粒子形成，使锆主要以亚稳定的过饱和固溶态存在，并在后续退火过程中析出大量细小弥散分布且与基体共格的Al3Zr粒子，从而大大提升合金的耐热性和强度。
本发明添加的镧元素可能产生3个作用，一是除气、除杂的精炼作用，通过降低熔体中的氢含量和杂质含量来提升合金的导电性能，二是通过细化晶粒和枝晶组织来提高铸坯的强韧性，三是退火时形成细小的Al3(Zr,La)复合相，起阻碍晶界和亚晶界长大及位错迁移的作用，从而强化合金并提高其耐热性能。
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铝锆、铝铁初生相形成的作用，使铸坯具有较高过饱和固溶度，为后续退火过程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，主要作用是析出细小弥散分布的Al3Zr等含锆第二相粒子，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成卷线坯，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，特别是对晶界处的粗大脆性铝铁相有一定的破碎作用。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，本发明通过铝、硼、锆、镧、铁元素的合理配比，并利用快速冷却铸造、铸坯的高温短时退火、大变形量的挤压，协同产生净化、变质、细化及强韧化作用。本发明生产流程短、工艺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。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℃，抗拉强度在170MPa以上，密度（≤2.714g/cm3）与纯铝的密度2.7g/cm3比较接近（≤2.714g/cm3），能够满足远距离、大容量输电线路的要求，其高电导率可使输电线路容量提高和输送线损降低，其良好的耐热性可使线路的安全稳定性和服役寿命提高，其高比强度可使导线的抗弧垂特性提高和输电线路塔杆间距增加，具有显著的经济效益和节能环保意义。
 附图说明
附图1为实施例1炉渣的微观组织形貌；
附图2为附图1中质点的能谱分析结果。
附图3(a)为对比例1合金的SEM照片；
附图3 (b) 为附图3(a)中第二相的能谱分析结果；
附图3(c)为实施例1合金的SEM照片；
附图3 (d) 为附图3(c)中第二相的能谱分析结果；
附图3(e)为实施例3合金的SEM照片；
附图3 (f) 为附图3(e)中第二相的能谱分析结果；
附图3(g)为对比例2合金的SEM照片；
附图3 (h) 为附图3(g)中第二相的能谱分析结果。
附图4(a)为实施例1合金铸态组织的金相照片；
附图4(b)为实施例3合金铸态组织的金相照片。
附图5(a)为实施例3合金TEM照片，其中有第二相钉扎位错；
附图5(b)为实施例3合金TEM照片，其中有第二相钉扎晶界。
附图6~附图9为本发明实施例3所制备的Φ4铝导线的性能检测报告。
图1中白色的第二相为铝铁相，同时基体中还存在一种四周较暗、中间亮白的粒子（如箭头所示），图2的能谱分析表明该粒子为含铝、硼、钛、钒的相，说明钛、钒等杂质元素可以与硼元素反应形成化合物，在熔炼时以炉渣的形式排除，因而提高了合金的电导率。
由图3(a)和图3(b)可以看出，当硼含量为0.035 wt.%，合金中的铝铁相主要以连续骨骼状存在，并且存在层片状共晶组织；由图3(c)和图3(d)可以看出，硼含量为0.04 wt.%时，铝铁相部分呈不连续的短条状或点状，如图3(c)箭头所指；由图3(e)和图3(f)可以看出，硼添加量增加到0.1 wt.%时，合金中的铝铁相主要以不连续的条状或点状形式存在；由图3(g)和图3(h)可以看出，当硼含量为0.12 wt.%时，合金中出现了大量粗大铝硼相。
由图4(a)和图4(b) 所示铸态组织照片可知，实施例1加入的镧元素含量较少，合金晶粒较粗大，存在较多粗大枝晶组织，实施例3加入的镧元素含量较多，晶粒形状等轴化，且晶粒得到明显细化。
由图5(a)可以看出，合金基体中析出了大量弥散分布的第二相钉扎位错，由图5(b)可以看出，第二相钉扎、阻碍晶界移动。
由图6~图9可知，本发明所制备的铝导线在20℃的电导率达到了62% IACS，短期耐热温度达到230℃(230℃保温1h抗拉强度残留率达到91%)，抗拉强度为170MPa，可作为本发明先进性、优越性的有力支撑证明。
 本发明的实施方式
对比例1
以纯度大于99.7％的工业纯铝锭、Al-2.5％B中间合金、Al-11.34％Zr中间合金、Al-31.48％La中间合金、Al-9.33％Fe中间合金为原料，先将工业纯铝在760℃熔化，然后加入铝硼、铝锆、铝镧、铝铁中间合金，使各元素的质量百分比为：硼为0.035 wt.％，锆为0.10 wt.％，镧为0.09 wt.％，铁为0.10 wt.％。待中间合金完全熔化后，将熔体温度降至740℃保温，然后经搅拌、精炼、炉前成分快速分析、成分调整、静置、扒渣，通过快速冷却铸造获得过饱和固溶的铝合金铸坯。坯料在480℃退火10h后随炉冷却，再在400℃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，经多道次拉拔获得Φ4.0mm的铝合金单丝。对单丝进行性能测试，结果如表1所示。
表1 对比例1铝单丝的综合性能指标
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（%）
2.710 59.5 165 86.5 87.1
实施例1
以纯度大于99.7％的工业纯铝锭、Al-2.5％B中间合金、Al-11.34％Zr中间合金、Al-31.48％La中间合金、Al-9.33％Fe中间合金为原料，先将工业纯铝在760℃熔化，然后加入铝硼、铝锆、铝镧、铝铁中间合金，使各元素的质量百分比为：硼为0.04 wt.％，锆为0.10 wt.％，镧为0.09 wt.％，铁为0.10 wt.％。待中间合金完全熔化后，将熔体温度降至740℃保温，经搅拌、精炼、炉前成分快速分析、成分调整、静置、扒渣，再通过快速冷却铸造获得过饱和固溶的铝合金铸坯。坯料在480℃退火10h后随炉冷却，再在400℃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，经多道次拉拔获得Φ4.0mm的铝合金单丝。对单丝进行性能测试，结果如表2所示，相对于对比例1，导电率、抗拉强度和耐热性均得到提升。
表2 实施例1铝单丝的综合性能指标
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（%）
2.713 62.1 170 90.5 91.1
实施例2
以纯度大于99.7％的工业纯铝锭、Al-2.5％B中间合金、Al-11.34％Zr中间合金、Al-31.48％La中间合金、Al-9.33％Fe中间合金为原料，先将工业纯铝在760℃熔化，然后加入铝硼、铝锆、铝镧、铝铁中间合金，使各元素的质量百分比为：硼为0.07 wt.％，锆为0.15 wt.％，镧为0.19 wt.％，铁为0.20 wt.％。待中间合金完全熔化后，将熔体温度降至740℃保温，经搅拌、精炼、炉前成分快速分析、成分调整、静置、扒渣，再通过快速冷却铸造获得过饱和固溶的铝合金铸坯。坯料在490℃退火8h后随炉冷却，再在400℃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，并经多道次拉拔获得Φ4.0mm的铝合金单丝。对单丝进行性能测试，结果如表3所示。
表3 实施例2铝单丝的综合性能指标
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（%）
2.711 62.5 175 90.8 91.7
实施例3
以纯度大于 99.7 ％的工业纯铝锭、 Al-2.5 ％ B 中间合金、 Al-11.34 ％ Zr 中间合金、 Al-31.48 ％ La 中间合金、 Al-9.33 ％ Fe 中间合金为原料，先将工业纯铝在 760 ℃熔化，然后加入铝硼、铝锆、铝镧、铝铁中间合金，使各元素的质量百分比为：硼为 0.095 wt. ％，锆为 0.15 wt. ％，镧为 0.29 wt. ％，铁为 0.20 wt. ％。待中间合金完全熔化后，将熔体温度降至 740 ℃保温，经搅拌、精炼、炉前成分快速分析、成分调整、静置、扒渣，再利用快速冷却铸造获得过饱和固溶的铝合金铸坯。坯料在 500 ℃退火 2h 后随炉冷却，再 在 400 ℃ 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，并经多道次拉拔 获得 Φ4.0mm 的铝合金单丝。对单丝进行性能测试，结果如表 4 所示。
表4 实施例3铝单丝的综合性能指标
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（%）
2.714 62 170 91 92.3
对比例2
以纯度大于99.7％的工业纯铝锭、Al-2.5％B中间合金、Al-11.34％Zr中间合金、Al-31.48％La中间合金、Al-9.33％Fe中间合金为原料，以纯度大于99.7％的工业纯铝锭、Al-2.5％B中间合金、Al-11.34％Zr中间合金、Al-31.48％La中间合金、Al-9.33％Fe中间合金为原料，先将工业纯铝在780℃熔化，然后加入铝硼、铝锆、铝镧、铝铁中间合金，使各元素的质量百分比为：硼为0.12 wt.％，锆为0.15 wt.％，镧为0.29 wt.％，铁为0.20 wt.％。待中间合金完全熔化后，将熔体温度降至740℃保温，经搅拌、精炼、炉前成分快速分析、成分调整、静置、扒渣，再通过快速冷却铸造获得过饱和固溶的铝合金锭坯。坯料在500℃退火2h后随炉冷却，再在400℃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，并经多道次拉拔获得Φ4.0mm的铝合金单丝。对单丝进行性能测试，结果如表5所示。
表5 对比例2铝单丝的综合性能指标
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（%）
2.715 60.2 175 90.1 90.9
对比例1的硼含量为0.035 wt. %，由附图3(a)、图3(b)可以看出，合金中的第二相主要以连续骨骼状存在，相应电导率为59.5%IACS，实施例1的硼含量为0.04wt.%，由附图3(c)、图3(d)可以看出，合金中的部分第二相呈现不连续的短条状或点状（如图中箭头所示），相应电导率为62.1%IACS，表明只有当硼的加入量达到一定值后，才会对提高电导率产生明显作用。实施例3的硼含量为0.095 wt.%，由附图3(g)和图3(h)可以看出，合金中的铝铁相主要以不连续的条状或点状形式存在，相应电导率为62%IACS，对比例2的硼含量达到0.12 wt.%，由附图3(g)和图3(h)可以看出，合金中生成了较多粗大的铝硼相，相应电导率为60.2%IACS，表明硼的加入量过高反而使电导率降低。
综上所述，本发明 3 个实施例得到的铝合金导线密度均小于等于 2.714g/cm3 ，在 20 ℃常温下导电率大于等于 62% IACS ，短时耐热温度高达 230 ℃（ 230 ℃退火 1 小时的强度残存率大于 90% ），长期耐热温度高达 210 ℃（ 210 ℃退火 400 小时的强度残存率大于 90% ）。对比例 1 除了加入的硼元素较少外，其他组分与实施例 1 相同，对比例 2 除了加入的硼含量较高外，其他组分与实施例 3 相同，但是， 2 个对比例的电导率均低于 61%IACS ，且对比例 1 在 230 ℃退火 1 小时的强度残存率仅为 86.5% ，在 210 ℃退火 400 小时的强度残存率仅为 87.1% 。

Claims (15)

  1. 一种加铁的轻质高导耐热铝导线，包括下述组分，按质量百分比组成：
    B 0.04~0.10wt.%，
    Zr 0.10~0.15wt.%，
    Fe 0.10~0.20wt.%，
    La 0.05~0.30wt.%，
    不可避免钛、钒、铬、锰的含量总和小于0.01wt.％，铝为余量。
  2. 根据权利要求1所述的一种加铁的轻质高导耐热铝导线，包括下述组分，按质量百分比组成：
    B 0.045~0.095wt.%，
    Zr 0.10~0.15wt.%，
    Fe 0.10~0.20wt.%，
    La 0.05~0.30wt.%，
    不可避免钛、钒、铬、锰的含量总和小于 0.01wt. ％，铝为余量。
  3. 据权利要求1或2所述的一种加铁的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。
  4. 根据权利要求1或2所述的一种加铁的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。
  5. 根据权利要求4所述的一种加铁的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。
  6. 根据权利要求1或2所述的一种加铁的轻质高导耐热铝导线，其特征还在于，导线密度小于等于2.714g/cm3，在20℃的电导率大于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170MPa。
  7. 一种加铁的轻质高导耐热铝导线的制备工艺，是按设计的材料组分配比分别选取工业纯铝及铝硼、铝锆、铝铁、铝镧中间合金，在740~780℃熔化工业纯铝，然后加入中间合金，经精炼和快速冷却铸造得到铸坯，再对坯料进行退火、挤压、拉拔，获得铝合金单丝。
  8. 根据权利要求7所述的一种加铁的轻质高导耐热铝导线的制备工艺，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7所述的一种加铁的轻质高导耐热铝导线的制备工艺，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所述的一种加铁的轻质高导耐热铝导线的制备工艺，其特征在于：铸造时采用水冷铸造。
  11. 根据权利要求8所述的一种加铁的轻质高导耐热铝导线的制备工艺，其特征在于：锭坯或杆坯的退火温度为480℃~500℃，保温2-10h后随炉冷却。
  12. 据权利要求8所述的一种加铁的轻质高导耐热铝导线的制备工艺，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所述的一种加铁的轻质高导耐热铝导线的制备工艺，其特征在于：热挤压或室温连续挤压的挤压比大于等于80，挤压总变形量大于等于80%。
  14. 根据权利要求6-13任意一项所述的一种加铁的轻质高导耐热铝导线的制备工艺，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所述的一种加铁的轻质高导耐热铝导线的制备工艺，其特征在于：所制备的导线，密度小于等于2.714g/cm3，在20℃的电导率大于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170MPa。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110819853A (zh) * 2019-10-30 2020-02-21 全球能源互联网研究院有限公司 一种高导电率软铝单丝及其制备方法

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105821253B (zh) 2016-03-25 2017-06-23 中南大学 一种加铁的轻质高导耐热铝导线及其制备工艺
CN106119619A (zh) * 2016-08-31 2016-11-16 贵州电网有限责任公司电力科学研究院 一种稀土掺杂高导耐热铝合金导电杆及其制备方法
CN107419141B (zh) * 2017-08-07 2019-03-26 中南大学 一种Al-Si-Fe-RE-B合金导体材料及制备方法
CN109468498B (zh) * 2019-01-03 2020-10-30 包头铝业有限公司 一种用于生产倍容导线的耐热铝合金杆材及其制备方法
CN111041282A (zh) * 2019-11-28 2020-04-21 国网辽宁省电力有限公司沈阳供电公司 架空导线用软铝单丝及其制备方法
CN112159915A (zh) * 2020-09-27 2021-01-01 酒泉钢铁(集团)有限责任公司 一种应用铜辊套铸轧制备1070铝合金带坯的方法
CN113096854A (zh) * 2021-03-11 2021-07-09 湖北洪乐电缆股份有限公司 一种高延伸高导电铝合金软线及其加工工艺
CN113327715B (zh) * 2021-05-26 2022-05-17 深圳市黑金工业制造有限公司 一种铝合金超导电电缆及其制备方法
CN113903499B (zh) * 2021-08-20 2022-06-28 绍兴电力设备有限公司 一种钢芯高导电率铝绞线及其加工方法
CN113684388B (zh) * 2021-08-27 2022-04-26 江苏中天科技股份有限公司 一种高导电率软铝单丝及其制备方法
CN113981278B (zh) * 2021-10-13 2022-05-06 深圳市鑫申新材料科技有限公司 一种高导电耐热压力铸造铝合金
CN114000014B (zh) * 2021-11-03 2022-05-13 大连理工大学 一种稀土La强化的铝基复合材料导线及其制造方法
CN114480921A (zh) * 2022-01-07 2022-05-13 国网辽宁省电力有限公司营口供电公司 一种架空导线用耐热铝合金单丝材料及其制备方法
CN114657403B (zh) * 2022-03-25 2023-03-21 中南大学 一种高导耐热耐损伤铝合金导体材料的制备方法
CN115074582B (zh) * 2022-06-20 2023-07-18 中南大学 一种具有双峰晶粒组织的亚共晶Al-Ce合金的制备方法
CN115522085A (zh) * 2022-09-01 2022-12-27 国网江苏省电力有限公司 一种高导电率耐热硬铝线及制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1292508A (en) * 1969-10-24 1972-10-11 Sumitomo Electric Industries Improved heat resistant alloys for electrical conductors
DE2435456A1 (de) * 1973-07-23 1975-02-20 Held M Leiter aus einer aluminiumlegierung
US4182640A (en) * 1973-05-17 1980-01-08 Sumitomo Electric Industries, Ltd. Aluminum alloy electric conductor wire
CN102760508A (zh) * 2012-07-18 2012-10-31 中南大学 含Hf和Ce的高电导率抗蠕变铝合金电缆导体及制备方法
CN102978458A (zh) * 2012-11-09 2013-03-20 安徽欣意电缆有限公司 Al-Fe-Si-B-RE铝合金及其制备方法和电力电缆
CN105821253A (zh) * 2016-03-25 2016-08-03 中南大学 一种加铁的轻质高导耐热铝导线及其制备工艺

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3807969A (en) * 1970-07-13 1974-04-30 Southwire Co Aluminum alloy electrical conductor
US3807016A (en) * 1970-07-13 1974-04-30 Southwire Co Aluminum base alloy electrical conductor
US4082573A (en) * 1974-01-02 1978-04-04 Southwire Company High tensile strength aluminum alloy conductor and method of manufacture
US5512241A (en) * 1988-08-18 1996-04-30 Martin Marietta Corporation Al-Cu-Li weld filler alloy, process for the preparation thereof and process for welding therewith
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
US20020162607A1 (en) * 2000-11-30 2002-11-07 Chadwick Kenneth E. Creep resistant cable wire
US7615127B2 (en) * 2003-05-13 2009-11-10 Alcan International, Ltd. Process of producing overhead transmission conductor
JP4927366B2 (ja) * 2005-02-08 2012-05-09 古河電気工業株式会社 アルミニウム導電線
US8461485B2 (en) * 2006-12-29 2013-06-11 Kobe Steel, Ltd. Solid wire
JP4646998B2 (ja) * 2008-08-11 2011-03-09 住友電気工業株式会社 アルミニウム合金線
CN102013283A (zh) * 2010-12-04 2011-04-13 江苏南瑞淮胜电缆有限公司 一种超耐热高强度钢芯铝合金导线及其制造方法
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
CN102758107B (zh) 2012-06-11 2015-01-21 上海交通大学 高强高导耐热铝合金导线及其制备方法
CN102965550B (zh) 2012-12-06 2014-08-06 中南大学 一种高强高导耐热铝导体材料及其制备方法
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
EP3108025B1 (en) * 2014-03-12 2019-05-08 NanoAL LLC Aluminum superalloys for use in high temperature applications
EP3150732B1 (en) * 2014-05-26 2021-08-18 Furukawa Electric Co. Ltd. Aluminum alloy conductor wire, aluminum alloy twisted wire, sheathed electrical cable, wire harness, and method for manufacturing aluminum alloy conductor wire

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1292508A (en) * 1969-10-24 1972-10-11 Sumitomo Electric Industries Improved heat resistant alloys for electrical conductors
US4182640A (en) * 1973-05-17 1980-01-08 Sumitomo Electric Industries, Ltd. Aluminum alloy electric conductor wire
DE2435456A1 (de) * 1973-07-23 1975-02-20 Held M Leiter aus einer aluminiumlegierung
CN102760508A (zh) * 2012-07-18 2012-10-31 中南大学 含Hf和Ce的高电导率抗蠕变铝合金电缆导体及制备方法
CN102978458A (zh) * 2012-11-09 2013-03-20 安徽欣意电缆有限公司 Al-Fe-Si-B-RE铝合金及其制备方法和电力电缆
CN105821253A (zh) * 2016-03-25 2016-08-03 中南大学 一种加铁的轻质高导耐热铝导线及其制备工艺

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110819853A (zh) * 2019-10-30 2020-02-21 全球能源互联网研究院有限公司 一种高导电率软铝单丝及其制备方法

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