CN102760508A - 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 high conductivity creep resistant aluminium alloy cable conductor and the preparation method of a kind of Hf of containing and Ce; Belong to the aluminum alloy materials technical field.
Background technology
Advantages such as aluminium alloy has that specific strength height, conductivity are high, plasticity is good, resistance to wear and corrosion resistance and good are so have superiority in field of power transmission.Raising along with Chinese economic development and living standards of the people; Electricity consumption of resident constantly increases; In the lead use, contact point causes internal stress, lead that creep in short-term takes place owing to connect the moment high temperature (150 ℃) that produces; The accidents such as insulant burning that conductor material lost efficacy, conductor is outer can take place down in regular creep effect, so interior architecture receives growing interest with the problem safe in utilization and the increase-volume problem of lead.
The lead civilian and for building of China's use at present has copper conductor, a spot of soft attitude fine aluminium lead, aluminium alloy cable.The copper conductor price is more expensive, is more than 3 times of aluminium.Improve though soft attitude fine aluminium wire elongation rate has significantly than hard attitude, its tensile strength declines to a great extent, and creep resistance is very poor, after installation a period of time, causes the junction lax easily, makes joint fails, produces potential safety hazard in use thus.Although the development of aluminium alloy electric cable rapidly, as lead for building, there is variety of issue in existing aluminium alloy electric cable: Al-Mg-Si series alloy lead is because Mg
2The precipitation strength effect of Si phase, room temperature strength is high, but because Mg
2Si is not the high-temperature stable phase, under the high temperature loss of strength serious, high temperature resistant property and croop property are poor; Al-Zr series alloy lead has the Al of good heat resistance
3The Zr phase, so high-temperature behavior and creep-resistant property are good, but conductivity is lower; 58%IACS is only arranged; Reach 60%IACS although add the Al-Zr-Y series alloy lead conductivity of rare earth, compare, still have gap with the conductivity of electric work aluminium 61%IACS in the steel reinforced aluminium conductor.Develop a kind of aluminium alloy cable that had not only had higher conductivity but also had good creep-resistant property, to the fail safe that improves power transmission line, reduce power consumption and energy savings significant.
Summary of the invention
The objective 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, the high conductivity creep resistant aluminium alloy cable conductor and the preparation method that contain Hf and Rare-Earth Ce that intensity, conductivity, the elongation characteristics of the aluminium alloy cable conductor of preparation is good.
The high conductivity creep resistant aluminium alloy cable conductor that contains Hf and Ce provided by the invention, by following component, form 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%, and all the other are Al, each constituent mass percent and be 100%.
The present invention contains the preparation method of the high conductivity creep resistant aluminium alloy cable conductor of Hf and Ce, and concrete steps are following:
The first step: founding
By the aluminium alloy cable conductor set of dispense ratio of design, getting respectively with the commercial-purity aluminium is ferro-aluminum intermediate alloy, aluminum bronze intermediate alloy, aluminium hafnium intermediate alloy, aluminium boron intermediate alloy, the aluminium cerium intermediate alloy of matrix preparation; Be that 99.99% fine aluminium is heated to 750-900 ℃ of fusing with aluminium content earlier, the aluminium liquid after the fusing is 700-750 ℃ of insulation, and adds surface dopant; Then, add said ferro-aluminum intermediate alloy, aluminum bronze intermediate alloy, aluminium hafnium intermediate alloy, aluminium boron intermediate alloy and aluminium cerium intermediate alloy successively, treat that intermediate alloy is all after the fusing; Add refining agent; Stir, skim, 715-725 ℃ is poured in 150-200 ℃ the mould, obtains aluminium ingot;
Second step: homogenizing is handled and hot extrusion
The gained aluminium ingot is heated to 500-550 ℃, after being incubated 10-15 hour homogenizing and handling, is chilled to 380-420 ℃, in the extrusion die of 300-420 ℃ of mould temperature, carry out hot extrusion, obtain extruded stock behind the air cooling with stove; Extrusion speed 5-20m/min, extrusion ratio is 25-64:1;
The 3rd step: cold-drawn and annealing
Said extruded stock is carried out cold drawing, and cold drawing speed is 10-15m/min, and every time deflection is 8.5-20%; After being drawn to the conductor size of design; In 250-350 ℃, insulation 1-2h anneals, and obtains containing the high conductivity creep resistant aluminium alloy cable conductor of Hf and Rare-Earth Ce.
The present invention contains the preparation method of the high conductivity creep resistant aluminium alloy cable conductor of Hf and Ce, and said ferro-aluminum intermediate alloy iron content mass fraction is 7% ~ 15%; Aluminum bronze intermediate alloy cupric mass fraction is 42% ~ 56%; It is 1.2% ~ 3.0% that aluminium hafnium intermediate alloy contains the hafnium mass fraction; Aluminium boron intermediate alloy boracic mass fraction is 2% ~ 3%; It is 6% ~ 9% that aluminium cerium intermediate alloy contains the cerium mass fraction.
The present invention contains the preparation method of the high conductivity creep resistant aluminium alloy cable conductor of Hf and Ce, and said surface dopant is selected from least a in sodium chloride, potassium chloride, calcirm-fluoride, the sodium carbonate, addition be after the said fusing aluminium liquid quality 0.5 ~ 0.8%.
The present invention contains the preparation method of the high conductivity creep resistant aluminium alloy cable conductor of Hf and Ce, and said refining agent is a carbon trichloride.
The present invention contains the preparation method of the high conductivity creep resistant aluminium alloy cable conductor of Hf and Ce, and said founding is carried out in furnace cupola.
The present invention contains the preparation method of the high conductivity creep resistant aluminium alloy cable conductor of Hf and Ce, before the casting, at said mould external coating oxide powder and zinc.
The present invention contains the preparation method of the high conductivity creep resistant aluminium alloy cable conductor of Hf and Ce, and said homogenizing is handled and in air furnace, carried out.
The present invention contains the preparation method of the high conductivity creep resistant aluminium alloy cable conductor of Hf and Ce, and said hot extrusion is carried out on the 500t extruder.
The present invention contains the preparation method of the high conductivity creep resistant aluminium alloy cable conductor of Hf and Ce, and said annealing is carried out in box type furnace.
Among this preparation method, adopt coverture to cover, can avoid the reaction of airborne moisture and aluminium liquid to generate hydrogen, avoid ingot casting to produce the cavity, and impel the hydrogen in the aluminium liquid to overflow smoothly, simultaneously, effectively remove oxide inclusion; The boron that adopts carbon trichloride to carry out in refining and the alloy compositions carries out removal of impurities; Through the stirring method processing of rolling; Make oxidation impurities swim in liquid surface, can control in the high conductivity creep resistant aluminium alloy cable conductor component that contains Hf and Ce content of impurities such as Mg, Zn, Si smaller or equal to 0.1%, thus; Can improve alloy purity, improve the electric property of lead.Before the cast,, can prevent that melt is air-breathing at mould external coating oxide powder and zinc; Adopt the moulding process of hot extrusion and cold drawing and adopt annealing in process, can guarantee that the primary phase on the crystal boundary is evenly distributed, reach the effect of crystal grain thinning simultaneously; The alloy interior tissue is evenly distributed, the 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 defective is brought conductivity, improves the alloy conductivity.Hot extrusion and cold-drawing process are than casting and rolling process and Kang Fang extrusion process, and crystallite dimension is little, because distortion is even, defective is few, so conductivity is high simultaneously.Owing to reply and recrystallization to a certain degree, conductivity gets a promotion in the annealing in process process.
Inventor's research shows, when iron and copper content are low, guaranteeing that its conductivity simultaneously, can better improve its tensile strength.The aluminium alloy cable conductor that contains small amounts of iron and copper simultaneously is not only cheap, and plasticity and yield strength all approach copper conductor, and the alloy lead wire conductivity after the annealed processing is also higher.Rare earth element and magnesium-yttrium-transition metal are because its unique chemical characteristic more and more shows its application prospect in aluminium alloy cable conductor in addition.
A series of variation takes place in the element that adds in preparation process and heat treatment process, thereby the tissue and the performance of aluminium alloy cable conductor exerted an influence.The solid solubility of iron in aluminium is very little, small amounts of iron in aluminium mainly with Al
3The form of Fe intermetallic compound exists.Al
3Fe generates in the process of melting, and the presentation layer sheet is distributed in the crystal boundary place, and the grain growth in the alloy graining process is had inhibition, so can crystal grain thinning.The solid solubility of copper in aluminium is bigger, and little copper can be solid-solubilized in the aluminium separately and aluminium when existing uniformly.When iron and copper joined in the aluminium simultaneously, the part copper element generated Al with aluminium element and ferro element through eutectic reaction in casting process
7Cu
2The Fe phase is the synusia shape on crystal boundary.Because the solid solution of copper is bigger to the influence of alloy conductivity, when copper is participated in into phase time, can reduce the adverse effect of solid solution attitude copper to conductivity.In hot extrusion process, the facies evolution of synusia shape is the phase of two kinds of forms: a kind of spherical phase that is of a size of about 0.2～0.5um, another kind is tiny nanoscale disperse phase.Spherical mainly concentrating on mutually on the crystal boundary can be hindered the 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 the wire drawing, the tissue of alloy lead wire obtains obvious refinement, and crystal particle scale is 200nm ~ 500nm, and strength ratio extruding attitude alloy structure doubles, and spherical phase and disperse phase are formed and form does not change.After the annealing in process through different temperatures and different time, the work-hardening effect that wire drawing produces improves, and the inner dislocation density of alloy lead wire reduces, and the intensity decreases of lead, plasticity rise.In annealing process, be accompanied by the variation of Al-Fe-Cu phase, be mainly reflected in the Cu element and at high temperature be dissolved in the aluminum substrate, along with the rising of annealing temperature, the middle mutually Fe constituent content of Al-Fe-Cu increases, the Cu constituent content reduces.The Cu element be solid-solubilized in the conductivity that has reduced alloy lead wire to a certain extent, and because the return action that produces in the annealing process raises conductivity, total bulk conductivity rises.The copper of solid solution attitude is useful to the intensity of lead, has reduced the material softening effect that annealing causes to a certain extent.
The solid solubility of Hf in aluminium mainly is 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 very little
3The Hf phase, this does not decompose mutually in follow-up processing and heat treatment process, at high temperature has thermal stability, improves the high-temperature behavior and the creep-resistant property of alloy.Simultaneously because Hf has lower diffusion velocity, the Al of formation in aluminium
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 the aluminium alloy cable conductor can crystal grain thinning and the impurity of removing in the aluminium alloy, can reduce the dendrite interval of aluminium alloy cable conductor, refined cast structure.Owing to the free energy of reaction of two kinds of elements and impurity element formation compound is low, so can form compounds, eliminate the caused distortion of lattice of objectionable impurities solid solution, thereby reduce adverse effect the lead conductivity with various impurity elements.The Ce element also can form Al
3The Ce phase, the distribution disperse has improved intensity on the basis that does not reduce conductivity.
Because the Al of crystal boundary and intracrystalline
7Cu
2Fe, Al
3Fe and Al
3Hf has reduced crystallite dimension to the inhibition of crystal boundary, and these precipitated phases have high-temperature stability simultaneously, in the high temperature use, do not decompose, and the creep-resistant property of lead is improved, and long-term the use is difficult for losing efficacy, and guarantees the security performance of conductor material.
The advantage that the present invention has is sketched in following:
On preparation technology, hot extrusion and cold-drawing process are than casting and rolling process and Kang Fang extrusion process, and crystallite dimension is little, and the refined crystalline strengthening effect is obvious; Because distortion is even, defective is few, so conductivity is high simultaneously.
Say that from heat treating regime homogenizing is handled the Hf element is separated out, owing to reply and recrystallization to a certain degree, conductivity gets a promotion in the annealing in process process.
From adding element,, make and generate heat-staple Al on intracrystalline and the crystal boundary through adding Fe and Cu element
3Fe and Al
7Cu
2The Fe phase, the thermal endurance and the creep-resistant property of raising lead; Through adding the Hf element, generate Al
3The Hf phase, disperse is distributed in the matrix, and in the high temperature use, does not grow up, and has improved the high temperature serviceability of aluminium alloy cable.Being added with of Rare-Earth Ce is beneficial to purification impurity, thereby improves the conductivity of aluminium alloy cable.The lead elongation after fracture of the present invention's preparation surpasses 25%, and tensile strength surpasses 110MPa, and conductivity is 60.5%～62.5%.
In a word, the inventive method is simple, and is easy to operate; The multiple element of compound interpolation impels the numerous thermal stability phases of the inner generation of alloy; Improve the electric property and the high-temperature behavior of aluminium alloy cable through the tissue that improves aluminium alloy, among intensity, conductivity, percentage elongation, find a balance preferably, reduced power consumption; Having improved the usage safety performance of cable simultaneously, is a kind of very promising novel aluminum alloy cable.
Description of drawings
The transmission electron microscope tissue of the aluminium alloy cable conductor cold drawing attitude longitudinal section that accompanying drawing 1 makes for the embodiment of the invention 3.
The transmission electron microscope tissue of the aluminium alloy cable conductor annealing finished product attitude that accompanying drawing 2 makes for the embodiment of the invention 3.
Can be found out that by Fig. 1 the grain size after the cold drawing is 200-500nm, cold drawing has good refining effect to tissue, and the primary aluminium iron phase that distributes on the crystal boundary is simultaneously inherited in the annealing tissue afterwards, improves the creep-resistant property of alloy.
Can find out by Fig. 2, two types the phase of distributing in the tissue of annealed state, a kind of is that micron order is distributed in the Al on the crystal boundary
3The Fe phase is to produce at fusion process, in extrusion process, forms spherical or long bar-shaped form; Another kind is the nano level Al of intracrystalline
3The Hf phase is separated out in the process of homogenizing, in the follow-up heat treatment and the course of processing, remains unchanged.Two kinds of phases all are thermally-stabilised phases, and are useful to the creep-resistant property of material.
Embodiment
Embodiment 1:
The input mass fraction is 99.99% fine aluminium in furnace cupola, is fused into aluminium water and 700 ℃ of insulations, adds sodium chloride as coverture at 750 ℃; Drop into 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 successively, be made into aluminum alloy melt, add carbon trichloride as refining agent; Stir, skim, be poured in 150 ℃ the mould at 715 ℃, each constituent content is (mass fraction): Fe 1.1%; Cu 0.1%, and Ce 0.02%, and Hf 0.01%; B 0.01%, and all the other are Al.After the processing of 500 ℃/15h homogenizing, 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, the salt-mixture (mass ratio is 30:30:25:15) that adds sodium chloride, potassium chloride, calcirm-fluoride, sodium carbonate is as coverture at 900 ℃; Drop into 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 successively, be made into aluminum alloy melt, add carbon trichloride as refining agent; Stir, skim, be poured in 200 ℃ the mould at 725 ℃, each constituent content is (mass fraction): Fe 0.3%; Cu 0.5%, and Ce 0.1%, and B 0.05%; Hf 0.2%, and all the other are Al.After the processing of 550 ℃/10h homogenizing, 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, the salt-mixture (mass ratio is 1:1) that adds sodium chloride and potassium chloride is as coverture at 850 ℃; Drop into 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 successively, be made into aluminum alloy melt, add carbon trichloride as refining agent; Stir, skim, be poured in 180 ℃ the mould at 720 ℃, each constituent content is (mass fraction): Fe 0.75%; Cu 0.25%, and Ce 0.05%, and B 0.03%; Hf 0.1%, and all the other are Al.After the processing of 530 ℃/12h homogenizing, 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 such as the table 1 of embodiment 1,2,3 preparations:
Table 1
Can find out with the performance index in each Comparative Examples by last table embodiment; The high conductivity creep resistant aluminium alloy cable conductor of disclosed Hf of containing of this patent and Ce 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 and produce precipitated phase on the crystal boundary, make lead have creep-resistant property preferably, and the interpolation of Hf has further improved the creep-resistant property of lead, thereby the effect that alloy improves conductivity that purifies has been played in the interpolation of Ce and B.Use coverture and use the carbon trichloride refining, control alloy impurity content improves the lead 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 lead.
Claims (10)
1. the high conductivity creep resistant aluminium alloy cable conductor that contains Hf and Ce, by following component, form 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%, and all the other are Al, each constituent mass percent and be 100%.
2. contain the preparation method of the high conductivity creep resistant aluminium alloy cable conductor of Hf and Ce, comprise the steps:
The first step: founding
By the aluminium alloy cable conductor set of dispense ratio of design, getting respectively with the commercial-purity aluminium is ferro-aluminum intermediate alloy, aluminum bronze intermediate alloy, aluminium hafnium intermediate alloy, aluminium boron intermediate alloy, the aluminium cerium intermediate alloy of matrix preparation; Be that 99.99% fine aluminium is heated to 750-900 ℃ of fusing with aluminium content earlier, the aluminium liquid after the fusing is 700-750 ℃ of insulation, and adds surface dopant; Then, add said ferro-aluminum intermediate alloy, aluminum bronze intermediate alloy, aluminium hafnium intermediate alloy, aluminium boron intermediate alloy and aluminium cerium intermediate alloy successively, treat that intermediate alloy is all after the fusing; Add refining agent; Stir, skim, 715-725 ℃ is poured in 150-200 ℃ the mould, obtains aluminium ingot;
Second step: homogenizing is handled and hot extrusion
The gained aluminium ingot is heated to 500-550 ℃, after being incubated 10-15 hour homogenizing and handling, is chilled to 380-420 ℃, in the extrusion die of 300-420 ℃ of mould temperature, carry out hot extrusion, obtain extruded stock behind the air cooling with stove; Extrusion speed 5-20m/min, extrusion ratio is 25-64:1;
The 3rd step: cold-drawn and annealing
Said extruded stock is carried out cold drawing, and cold drawing speed is 10-15m/min, and every time deflection is 8.5-20%; After being drawn to the conductor size of design; In 250-350 ℃, insulation 1-2h anneals, and obtains containing the high conductivity creep resistant aluminium alloy cable conductor of Hf and Rare-Earth Ce.
3. the preparation method who contains the high conductivity creep resistant aluminium alloy cable conductor of Hf and Ce according to claim 2, it is characterized in that: said ferro-aluminum intermediate alloy iron content mass fraction is 7% ~ 15%; Aluminum bronze intermediate alloy cupric mass fraction is 42% ~ 56%; It is 1.2% ~ 3.0% that aluminium hafnium intermediate alloy contains the hafnium mass fraction; Aluminium boron intermediate alloy boracic mass fraction is 2% ~ 3%; It is 6% ~ 9% that aluminium cerium intermediate alloy contains the cerium mass fraction.
4. the preparation method who contains the high conductivity creep resistant aluminium alloy cable conductor of Hf and Ce according to claim 3; It is characterized in that: said surface dopant is selected from least a in sodium chloride, potassium chloride, calcirm-fluoride, the sodium carbonate, addition be after the said fusing aluminium liquid quality 0.5 ~ 0.8%.
5. the preparation method who contains the high conductivity creep resistant aluminium alloy cable conductor of Hf and Ce according to claim 4, it is characterized in that: said refining agent is a carbon trichloride.
6. the preparation method who contains the high conductivity creep resistant aluminium alloy cable conductor of Hf and Ce according to claim 5, it is characterized in that: said founding is carried out in furnace cupola.
7. the preparation method who contains the high conductivity creep resistant aluminium alloy cable conductor of Hf and Ce according to claim 6 is characterized in that: before the casting, at said mould external coating oxide powder and zinc.
8. the preparation method who contains the high conductivity creep resistant aluminium alloy cable conductor of Hf and Ce according to claim 7 is characterized in that: said homogenizing is handled and in air furnace, is carried out.
9. the preparation method who contains the high conductivity creep resistant aluminium alloy cable conductor of Hf and Ce according to claim 8 is characterized in that:, said hot extrusion is carried out on the 500t extruder.
10. the preparation method who contains the high conductivity creep resistant aluminium alloy cable conductor of Hf and Ce according to claim 9, it is characterized in that: said annealing is carried out in box type furnace.
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