CN102760508B - High-conductivity creep-resistant aluminium alloy cable conductor containing Hf and Ce and preparation method thereof - Google Patents
High-conductivity creep-resistant aluminium alloy cable conductor containing Hf and Ce and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-conductivity creep-resistant aluminium alloy cable conductor containing Hf and Ce and a preparation method thereof. The aluminium alloy cable conductor disclosed by the invention is composed of the following constituents in percentage by mass: 0.3-1.1% of Fe, 0.1-0.5% of Cu, 0.01-0.2% of Hf, 0.01-0.05% of B, 0.02-0.1%, and the balance of Al. The preparation method comprises the following steps of: proportioning according to the designed alloy constituents, smelting and pouring, homogenizing-annealing and hot-extruding, cold-drawing and annealing to finally obtain the aluminium alloy cable conductor. The aluminium alloy cable conductor prepared by the preparation method disclosed by the invention has an elongation after fracture being greater than 25%, tensile strength being greater than 110 MPa, and conductivity being 61.0-62.5%. By using the conductor manufactured by the preparation method disclosed by the invention, transmission capacity can be increased and electric energy loss can be reduced due to the introduction of other alloy elements; and moreover, many high-temperature stable phases are distributed on the crystal boundaries and in the crystals of alloys, so that the high-temperature performance and the creep-resistant performance of the alloy conductor can be improved, thus guaranteeing the service life and safety of the conductor.
Description
Technical field
The invention discloses a kind of high conductivity creep resistant aluminum alloy cable conductor and preparation method containing Hf and Ce; Belong to aluminum alloy materials technical field.
Background technology
The advantages such as aluminium alloy has that specific strength is high, conductivity is high, plasticity is good, resistance to wear and corrosion resistance and good, therefore in field of power transmission position advantageously.Along with the raising of China's expanding economy and living standards of the people, electricity consumption of resident constantly increases, in wire use procedure, contact point causes internal stress owing to connecting the moment high temperature (150 ℃) producing, there is creep in short-term in wire, the accidents such as the insulant burning under regular creep effect outside the inefficacy of meeting generation conductor material, conductor, therefore interior architecture is subject to growing interest by use safety problem and the increase-volume problem of wire.
Civilian and the wire for building that at present China is used has copper conductor, a small amount of soft state fine aluminium wire, aluminium alloy cable.Copper conductor price is more expensive, is more than 3 times of aluminium.Although soft state fine aluminium wire elongation rate has significantly and improves than hard state, its tensile strength declines to a great extent, and creep resistance is very poor, installs after a period of time, easily causes junction lax, makes joint fails, produces potential safety hazard thus in use procedure.Although the development of aluminium alloy electric cable rapidly, as wire for building, there is variety of issue in existing aluminium alloy electric cable: Al-Mg-Si series alloy wire is due to Mg
2the precipitation strength effect of Si phase, room temperature strength is high, but due to Mg
2si is not high-temperature stable phase, under high temperature loss of strength serious, high temperature resistant property and croop property are poor; Al-Zr series alloy wire has the Al of good heat resistance
3zr phase, so high-temperature behavior and creep-resistant property are good, but conductivity is lower, only there is 58%IACS, reach 60%IACS although add the Al-Zr-Y series alloy wire conductivity of rare earth, compared with the conductivity of the electric work aluminium 61%IACS in steel reinforced aluminium conductor, still have gap.Develop a kind of aluminium alloy cable that had not only there is higher conductivity but also there is good creep-resistant property, to improve power transmission line fail safe, reduce power consumption and energy savings significant.
Summary of the invention
The object of the invention is to overcome the deficiency of prior art and a kind of reasonable mixture ratio of components is provided, fail safe is good, cheap, high conductivity creep resistant aluminum alloy cable conductor and preparation method containing Hf and Rare-Earth Ce that the intensity of the aluminum alloy cable conductor of preparation, conductivity, elongation characteristics are good.
High conductivity creep resistant aluminum alloy cable conductor containing Hf and Ce provided by the invention, by following component, composition by mass percentage:
Fe?0.3%～1.1%，
Cu?0.1%～0.5%，
Hf?0.01%～0.2%，
B?0.01%～0.05%，
Ce 0.02%～0.1%, all the other are Al, each constituent mass percent and be 100%.
The present invention is containing the preparation method of the high conductivity creep resistant aluminum alloy cable conductor of Hf and Ce, and concrete steps are as follows:
The first step: founding
By the aluminum alloy cable conductor component proportion of design, get respectively ferro-aluminum intermediate alloy, aluminum bronze intermediate alloy, aluminium hafnium intermediate alloy, aluminium boron intermediate alloy, the aluminium cerium intermediate alloy prepared take commercial-purity aluminium as matrix; The fine aluminium that is first 99.99% by aluminium content is heated to 750-900 ℃ of fusing, aluminium liquid after fusing is 700-750 ℃ of insulation, and add surface dopant, then, add successively described ferro-aluminum intermediate alloy, aluminum bronze intermediate alloy, aluminium hafnium intermediate alloy, aluminium boron intermediate alloy and aluminium cerium intermediate alloy, after intermediate alloy all melts, add refining agent, stir, skim, 715-725 ℃ is poured in the mould of 150-200 ℃, obtains aluminium ingot;
Second step: homogenizing is processed and hot extrusion
Gained aluminium ingot is heated to 500-550 ℃, is incubated after homogenizing processing in 10-15 hour, be chilled to 380-420 ℃ with stove, in the extrusion die of 300-420 ℃ of mould temperature, carry out hot extrusion, after air cooling, obtain extruded stock; Extrusion speed 5-20m/min, extrusion ratio is 25-64:1;
The 3rd step: cold-drawn and annealing
Described extruded stock is carried out to cold drawing, and cold drawing speed is 10-15m/min, and every time deflection is 8.5-20%, be drawn to after the conductor size of design, in 250-350 ℃, insulation 1-2h annealing, obtains the high conductivity creep resistant aluminum alloy cable conductor containing Hf and Rare-Earth Ce.
The present invention is containing the preparation method of the high conductivity creep resistant aluminum alloy cable conductor of Hf and Ce, and described ferro-aluminum intermediate alloy iron content mass fraction is 7% ~ 15%; Aluminum bronze intermediate alloy is 42% ~ 56% containing Copper mass fraction; Aluminium hafnium intermediate alloy is 1.2% ~ 3.0% containing hafnium mass fraction; Aluminium boron intermediate alloy boracic mass fraction is 2% ~ 3%; Aluminium cerium intermediate alloy is 6% ~ 9% containing cerium mass fraction.
The present invention is containing the preparation method of the high conductivity creep resistant aluminum alloy cable conductor of Hf and Ce, and described surface dopant is selected from least one in sodium chloride, potassium chloride, calcirm-fluoride, sodium carbonate, and addition is 0.5 ~ 0.8% of aluminium liquid quality after described fusing.
The present invention is containing the preparation method of the high conductivity creep resistant aluminum alloy cable conductor of Hf and Ce, and described refining agent is carbon trichloride.
The present invention is containing the preparation method of the high conductivity creep resistant aluminum alloy cable conductor of Hf and Ce, and described founding is carried out in furnace cupola.
The present invention is containing the preparation method of the high conductivity creep resistant aluminum alloy cable conductor of Hf and Ce, before casting, at described mould external coating oxide powder and zinc.
The present invention is containing the preparation method of the high conductivity creep resistant aluminum alloy cable conductor of Hf and Ce, and described homogenizing is processed and carried out in air furnace.
The present invention is containing the preparation method of the high conductivity creep resistant aluminum alloy cable conductor of Hf and Ce, and described hot extrusion is carried out on 500t extruder.
The present invention is containing the preparation method of the high conductivity creep resistant aluminum alloy cable conductor of Hf and Ce, and described annealing is carried out in box type furnace.
In this preparation method, adopt coverture to cover, can avoid airborne moisture to react with aluminium liquid and generate hydrogen, avoid ingot casting to produce cavity, and impel the hydrogen in aluminium liquid to overflow smoothly, meanwhile, effectively remove oxide inclusion; The boron that adopts carbon trichloride to carry out in refining and alloy compositions carries out removal of impurities, by the method processing of rolling of stirring, make oxidation impurities swim in liquid surface, can control containing content of impurities such as Mg, Zn, Si in the high conductivity creep resistant aluminum alloy cable conductor component of Hf and Ce and be less than or equal to 0.1%, thus, can improve alloy purity, improve the electric property of wire.Before cast, at mould external coating oxide powder and zinc, can prevent that melt is air-breathing; Adopt the moulding process of hot extrusion and cold drawing and adopt annealing in process, can guarantee that the primary phase on crystal boundary is evenly distributed, reach the effect of crystal grain thinning simultaneously, can make alloy interior tissue be evenly distributed, precipitated phase small and dispersed, high deflection makes crystal grain obtain refinement simultaneously, make alloy proof strength in high conductivity, last annealing in process is replied tissue, eliminates the adverse effect that defect is brought conductivity, improves alloy conductivity.Hot extrusion and cold-drawing process are than casting and rolling process and Kang Fang extrusion process, and crystallite dimension is little, and because distortion is even, defect is few, therefore conductivity is high simultaneously.In annealing in process process, due to reply and recrystallization to a certain degree, conductivity gets a promotion.
Inventor's research shows, when iron and copper content are when lower, guaranteeing that its conductivity simultaneously, can better improve its tensile strength.The aluminum alloy cable conductor that simultaneously contains a small amount of iron and copper is not only cheap, and plasticity and yield strength are all close to copper conductor, and annealed alloy lead wire conductivity after treatment is also higher.Rare earth element and magnesium-yttrium-transition metal, due to its unique chemical characteristic, more and more show its application prospect in aluminum alloy cable conductor in addition.
There is a series of variation in the element adding, thereby tissue and performance to aluminum alloy cable conductor exert an influence in preparation process and heat treatment process.The solid solubility of iron in aluminium is very little, a small amount of iron in aluminium mainly with Al
3the form of Fe intermetallic compound exists.Al
3fe generates in the process of melting, and presentation layer sheet is distributed in grain boundaries, and the grain growth in alloy process of setting has inhibition, therefore can crystal grain thinning.The solid solubility of copper in aluminium is larger, when a small amount of copper separately and aluminium exists, can be solid-solubilized in uniformly in aluminium.In the time that iron and copper join in aluminium simultaneously, part copper element generates Al with aluminium element and ferro element by eutectic reaction in casting process
7cu
2fe phase is lamellar on crystal boundary.Because the impact of the solid solution alloy conductivity of copper is larger, when copper participates in into phase time, can reduce the adverse effect of solid solution state copper to conductivity.In hot extrusion process, the facies evolution of lamellar is the phase of two kinds of forms: a kind of spherical phase that is of a size of 0.2～0.5um left and right, another kind is tiny nanoscale disperse phase.Spherical mainly concentrating on mutually on crystal boundary, can hinder dynamic recrystallization and the growth process of hot extrusion process, reduces the size of crystal grain, improves intensity, the moulding and creep-resistant property of alloy lead wire; Disperse phase is distributed in crystal grain inside, can hinder the motion of dislocation, improves the intensity of alloy lead wire.After wire drawing, the tissue of alloy lead wire obtains obvious refinement, and crystal particle scale is 200nm ~ 500nm, and strength ratio As-extruded alloy structure doubles, and spherical phase and disperse phase composition and form do not change.After the annealing in process through different temperatures and different time, the work-hardening effect that wire drawing produces improves, and the dislocation density of alloy lead wire inside reduces, and the intensity of wire declines, plasticity rises.In annealing process, be accompanied by the variation of Al-Fe-Cu phase, be mainly reflected in Cu element and be at high temperature dissolved in aluminum substrate, along with the rising of annealing temperature, Al-Fe-Cu mutually middle Fe constituent content increase, Cu constituent content reduces.Cu element be solid-solubilized in the conductivity that has reduced to a certain extent alloy lead wire, and raise because the return action producing in annealing process makes conductivity, total bulk conductivity rises.The copper of solid solution state is useful to the intensity of wire, has reduced to a certain extent the material softening effect that annealing causes.
The solid solubility of Hf in aluminium, very little, is mainly in homogenizing or ag(e)ing process, to generate the thermally-stabilised phase Al that a kind of small and dispersed distributes in aluminium alloy
3hf phase, in follow-up processing and heat treatment process, this does not decompose mutually, at high temperature has thermal stability, carries heavy alloyed high-temperature behavior and creep-resistant property.Simultaneously because Hf has lower diffusion velocity in aluminium, the Al of formation
3hf is difficult for growing up mutually, makes its strengthening effect and heat-resisting effect more obvious.Rare-Earth Ce and B element join in aluminum alloy cable conductor can crystal grain thinning and remove the impurity in aluminium alloy, can reduce the dendrite interval of aluminum alloy cable conductor, refined cast structure.Because the free energy of reaction of two kinds of elements and impurity element formation compound is low, so can form compounds with various impurity elements, eliminate the caused distortion of lattice of objectionable impurities solid solution, thereby reduce the adverse effect to wire conductivity.Ce element also can form Al
3ce phase, distribution disperse has improved intensity on the basis that does not reduce conductivity.
Due to the Al of crystal boundary and intracrystalline
7cu
2fe, Al
3fe and Al
3the inhibition of Hf to crystal boundary, has reduced crystallite dimension, and these precipitated phases have high-temperature stability simultaneously, in applied at elevated temperature process, do not decompose, and the creep-resistant property of wire is improved, and long-term use is difficult for losing efficacy, and guarantees the security performance of conductor material.
The advantage that the present invention has sketch under:
Preparation technology, hot extrusion and cold-drawing process are than casting and rolling process and Kang Fang extrusion process, and crystallite dimension is little, refined crystalline strengthening successful; Because distortion is even, defect is few, therefore conductivity is high simultaneously.
From heat treating regime, homogenizing processing is separated out Hf element, and in annealing in process process, due to reply and recrystallization to a certain degree, conductivity gets a promotion.
From adding element, by adding Fe and Cu element, make to generate on intracrystalline and crystal boundary heat-staple Al
3fe and Al
7cu
2fe phase, thermal endurance and the creep-resistant property of raising wire; By adding Hf element, generate Al
3hf phase, disperse is distributed in matrix, and does not grow up in applied at elevated temperature process, has improved the applied at elevated temperature performance of aluminium alloy cable.Being added with of Rare-Earth Ce is beneficial to purification impurity, thereby improves the conductivity of aluminium alloy cable.Wire elongation after fracture prepared by the present invention exceedes 25%, and tensile strength exceedes 110MPa, and conductivity is 60.5%～62.5%.
In a word, the inventive method is simple, easy to operate, compound interpolation multiple element impels the numerous thermal stability phases of the inner generation of alloy, improve electric property and the high-temperature behavior of aluminium alloy cable by improving the tissue of aluminium alloy, among intensity, conductivity, percentage elongation, find a good balance, reduced power consumption, improved the usage safety performance of cable, be a kind of very promising novel aluminum alloy cable simultaneously.
Accompanying drawing explanation
The transmission electron microscope tissue of the aluminum alloy cable conductor cold drawing state longitudinal section that accompanying drawing 1 makes for the embodiment of the present invention 3.
The transmission electron microscope tissue of the aluminum alloy cable conductor annealing finished product state that accompanying drawing 2 makes for the embodiment of the present invention 3.
As seen from Figure 1, the grain size after cold drawing is 200-500nm, and cold drawing has good refining effect to tissue, and the nascent ferro-aluminum phase simultaneously distributing on crystal boundary, inherits in the tissue after annealing, and carries heavy alloyed creep-resistant property.
As seen from Figure 2, the phase of two types of distributing in the tissue of annealed state, a kind of is that micron order is distributed in the Al on crystal boundary
3fe phase, is to produce at fusion process, forms spherical or long bar-shaped form in extrusion process; Another kind is the nano level Al of intracrystalline
3hf phase is separated out in the process of homogenizing, in follow-up heat treatment and the course of processing, remains unchanged.Two kinds of phases are all thermally-stabilised phases, useful to the creep-resistant property of material.
Embodiment
Embodiment 1:
In furnace cupola, drop into mass fraction and be 99.99% fine aluminium, be fused into aluminium water and 700 ℃ of insulations at 750 ℃, add sodium chloride as coverture, drop into successively aluminium-iron intermediate alloy, Solder for Al-Cu Joint Welding intermediate alloy, aluminium-hafnium intermediate alloy, aluminium-boron intermediate alloy and aluminium-cerium intermediate alloy, be made into aluminum alloy melt, add carbon trichloride as refining agent, stir, skim, be poured in the mould of 150 ℃ at 715 ℃, each constituent content is (mass fraction): Fe 1.1%, Cu 0.1%, Ce 0.02%, Hf 0.01%, B 0.01%, all the other are Al.After 500 ℃/15h homogenizing is processed, be chilled to 380 ℃ with stove, in the extrusion die of 300 ℃ of mould temperature, push, extrusion speed is 5m/min, extrusion ratio is 25:1, carries out drawing with the speed of 10m/min, in 250 ℃ of insulation 2h annealing, the air cooling of coming out of the stove.
Embodiment 2:
In furnace cupola, drop into mass fraction and be 99.99% fine aluminium, be fused into aluminium water and 750 ℃ of insulations at 900 ℃, add sodium chloride, potassium chloride, calcirm-fluoride, the salt-mixture (mass ratio is 30:30:25:15) of sodium carbonate is as coverture, drop into successively aluminium-iron intermediate alloy, Solder for Al-Cu Joint Welding intermediate alloy, aluminium-hafnium intermediate alloy, aluminium-boron intermediate alloy and aluminium-cerium intermediate alloy, be made into aluminum alloy melt, add carbon trichloride as refining agent, stir, skim, be poured in the mould of 200 ℃ at 725 ℃, each constituent content is (mass fraction): Fe 0.3%, Cu 0.5%, Ce 0.1%, B 0.05%, Hf 0.2%, all the other are Al.After 550 ℃/10h homogenizing is processed, be chilled to 420 ℃ with stove, in the extrusion die of 420 ℃ of mould temperature, push, extrusion speed is 20m/min, extrusion ratio is 64:1, carries out drawing with the speed of 15m/min, in 350 ℃ of insulation 1h annealing, the air cooling of coming out of the stove.
Embodiment 3:
In furnace cupola, drop into mass fraction and be 99.99% fine aluminium, be fused into aluminium water and 730 ℃ of insulations at 850 ℃, add the salt-mixture (mass ratio is 1:1) of sodium chloride and potassium chloride as coverture, drop into successively aluminium-iron intermediate alloy, Solder for Al-Cu Joint Welding intermediate alloy, aluminium-hafnium intermediate alloy, aluminium-boron intermediate alloy and aluminium-cerium intermediate alloy, be made into aluminum alloy melt, add carbon trichloride as refining agent, stir, skim, be poured in the mould of 180 ℃ at 720 ℃, each constituent content is (mass fraction): Fe 0.75%, Cu 0.25%, Ce 0.05%, B 0.03%, Hf 0.1%, all the other are Al.After 530 ℃/12h homogenizing is processed, be chilled to 400 ℃ with stove, in the extrusion die of 400 ℃ of mould temperature, push, extrusion speed is 15m/min, extrusion ratio is 36:1, carries out drawing with the speed of 12m/min, in 320 ℃ of insulation 1.5h annealing, the air cooling of coming out of the stove.
The product property index of embodiment 1,2,3 preparation is as table 1:
Table 1
Can be found out by the performance index in upper table embodiment and each comparative example, the disclosed high conductivity creep resistant aluminum alloy cable conductor containing Hf and Ce of this patent has higher conductivity, intensity and elongation, has higher the tensile strength survival rate of heating and slower steady state creep speed when long in short-term simultaneously.Fe and Cu impel on crystal boundary and produce precipitated phase, make wire have good creep-resistant property, and the interpolation of Hf has further improved the creep-resistant property of wire, thereby the effect that purifies alloy and improve conductivity has been played in the interpolation of Ce and B.Use coverture and use carbon trichloride refining, controlling alloy impurity content, improving wire electric property; Use homogenizing annealing, hot extrusion, cold drawing, annealing in process technological means, make that alloy structure is even, crystal grain is tiny, precipitated phase small and dispersed, alloy defect reduce, and effectively improves electric property, mechanical property and the creep-resistant property of wire.
Claims (9)
1. the preparation method who contains the high conductivity creep resistant aluminum alloy cable conductor of Hf and Ce, comprises the steps:
The first step: founding
By the aluminum alloy cable conductor component proportion of design, get respectively ferro-aluminum intermediate alloy, aluminum bronze intermediate alloy, aluminium hafnium intermediate alloy, aluminium boron intermediate alloy, the aluminium cerium intermediate alloy prepared take commercial-purity aluminium as matrix; The fine aluminium that is first 99.99% by aluminium content is heated to 750-900 ℃ of fusing, aluminium liquid after fusing is 700-750 ℃ of insulation, and add surface dopant, then, add successively described ferro-aluminum intermediate alloy, aluminum bronze intermediate alloy, aluminium hafnium intermediate alloy, aluminium boron intermediate alloy and aluminium cerium intermediate alloy, after intermediate alloy all melts, add refining agent, stir, skim, 715-725 ℃ is poured in the mould of 150-200 ℃, obtains aluminium ingot; Cable conductor, by following component, composition by mass percentage:
Fe?0.3%～1.1%，
Cu?0.1%～0.5%，
Hf?0.01%～0.2%，
B?0.01%～０.05%，
Ce 0.02%～0.1%, all the other are Al, each constituent mass percent and be 100%;
Second step: homogenizing is processed and hot extrusion
Gained aluminium ingot is heated to 500-550 ℃, is incubated after homogenizing processing in 10-15 hour, be chilled to 380-420 ℃ with stove, in the extrusion die of 300-420 ℃ of mould temperature, carry out hot extrusion, after air cooling, obtain extruded stock; Extrusion speed 5-20m/min, extrusion ratio is 25-64:1;
The 3rd step: cold-drawn and annealing
Described extruded stock is carried out to cold drawing, and cold drawing speed is 10-15m/min, and every time deflection is 8.5-20%, be drawn to after the conductor size of design, in 250-350 ℃, insulation 1-2h annealing, obtains the high conductivity creep resistant aluminum alloy cable conductor containing Hf and Rare-Earth Ce.
2. the preparation method of the high conductivity creep resistant aluminum alloy cable conductor containing Hf and Ce according to claim 1, is characterized in that: described ferro-aluminum intermediate alloy iron content mass fraction is 7% ~ 15%; Aluminum bronze intermediate alloy is 42% ~ 56% containing Copper mass fraction; Aluminium hafnium intermediate alloy is 1.2% ~ 3.0% containing hafnium mass fraction; Aluminium boron intermediate alloy boracic mass fraction is 2% ~ 3%; Aluminium cerium intermediate alloy is 6% ~ 9% containing cerium mass fraction.
3. the preparation method of the high conductivity creep resistant aluminum alloy cable conductor containing Hf and Ce according to claim 2, it is characterized in that: described surface dopant is selected from least one in sodium chloride, potassium chloride, calcirm-fluoride, sodium carbonate, addition is 0.5 ~ 0.8% of aluminium liquid quality after described fusing.
4. the preparation method of the high conductivity creep resistant aluminum alloy cable conductor containing Hf and Ce according to claim 3, is characterized in that: described refining agent is carbon trichloride.
5. the preparation method of the high conductivity creep resistant aluminum alloy cable conductor containing Hf and Ce according to claim 4, is characterized in that: described founding is carried out in furnace cupola.
6. the preparation method of the high conductivity creep resistant aluminum alloy cable conductor containing Hf and Ce according to claim 5, is characterized in that: before casting, at described mould external coating oxide powder and zinc.
7. the preparation method of the high conductivity creep resistant aluminum alloy cable conductor containing Hf and Ce according to claim 6, is characterized in that: described homogenizing is processed and carried out in air furnace.
8. the preparation method of the high conductivity creep resistant aluminum alloy cable conductor containing Hf and Ce according to claim 7, is characterized in that: described hot extrusion is carried out on 500t extruder.
9. the preparation method of the high conductivity creep resistant aluminum alloy cable conductor containing Hf and Ce according to claim 8, is characterized in that: described annealing is carried out in box type furnace.
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| CN107557618B (en) * | 2017-08-30 | 2020-03-31 | 中南大学 | Low-resistance temperature-sensitive high-conductivity heat-resistant aluminum alloy and preparation process and application thereof |
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| CN110923529A (en) * | 2019-11-29 | 2020-03-27 | 安徽峰创云通数据科技有限公司 | Al-Cu-Sr-RE-Ge aluminum alloy wire for power cable and preparation method thereof |
| CN114758839B (en) * | 2022-04-16 | 2024-03-26 | 昆明理工大学 | preparation method of high-performance aluminum-zirconium alloy conducting rod |
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