CN103103385A - Al-Fe-Rb-RE aluminium alloy, preparation method thereof and power cable - Google Patents
Al-Fe-Rb-RE aluminium alloy, preparation method thereof and power cable Download PDFInfo
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- CN103103385A CN103103385A CN2012104454540A CN201210445454A CN103103385A CN 103103385 A CN103103385 A CN 103103385A CN 2012104454540 A CN2012104454540 A CN 2012104454540A CN 201210445454 A CN201210445454 A CN 201210445454A CN 103103385 A CN103103385 A CN 103103385A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 41
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- 238000005266 casting Methods 0.000 claims abstract description 38
- 238000009413 insulation Methods 0.000 claims description 74
- 229910052782 aluminium Inorganic materials 0.000 claims description 68
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 65
- 239000004411 aluminium Substances 0.000 claims description 63
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- 238000000034 method Methods 0.000 claims description 26
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- 238000001816 cooling Methods 0.000 claims description 7
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- 239000000463 material Substances 0.000 abstract description 20
- 238000000137 annealing Methods 0.000 abstract description 16
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- 239000000956 alloy Substances 0.000 description 102
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- 238000007670 refining Methods 0.000 description 51
- 238000003756 stirring Methods 0.000 description 43
- 229910052761 rare earth metal Inorganic materials 0.000 description 36
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- 150000001875 compounds Chemical class 0.000 description 26
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- 239000011572 manganese Substances 0.000 description 16
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- 238000007254 oxidation reaction Methods 0.000 description 4
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- 238000007669 thermal treatment Methods 0.000 description 4
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- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
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- 229910052693 Europium Inorganic materials 0.000 description 2
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- 229910052775 Thulium Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- ZZIZZTHXZRDOFM-XFULWGLBSA-N tamsulosin hydrochloride Chemical compound [H+].[Cl-].CCOC1=CC=CC=C1OCCN[C@H](C)CC1=CC=C(OC)C(S(N)(=O)=O)=C1 ZZIZZTHXZRDOFM-XFULWGLBSA-N 0.000 description 2
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- 241001136782 Alca Species 0.000 description 1
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
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- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
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- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
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- Conductive Materials (AREA)
Abstract
The invention provides an Al-Fe-Rb-RE aluminium alloy and a preparation method thereof. The preparation method comprises the following steps of: a) casting an aluminium alloy cast ingot; b) homogenizing the aluminium alloy cast ingot and rolling the homogenized aluminium alloy cast ingot to obtain an aluminium alloy rod material; c) intermittently annealing the aluminium alloy rod material obtained in the step b); and d) aging the aluminium alloy rod material obtained in the step c), thus obtaining the aluminium alloy. The invention also provides a power cable. The aluminium alloy has better overall performances by selecting and controlling the added elements and adopting a reasonable preparation process.
Description
Technical field
The present invention relates to the alloy technology field, relate in particular to Al-Fe-Rb-RE aluminium alloy and preparation method thereof and power cable.
Background technology
Aluminium alloy is a most widely used class non-ferrous metal structured material in industry, is used widely in Aeronautics and Astronautics, automobile, machinofacture, boats and ships and chemical industry.Along with the develop rapidly of science and technology and industrial economy, the demand of aluminium alloy is increasing, and the research of aluminium alloy also thereupon deeply.The widespread use of aluminium alloy has promoted the development of aluminium alloy in power industry, and the Application Areas of aluminium alloy has been expanded again in the development of power industry simultaneously.
Power cable is the resource of carrying and distributing electric energy, and its basic structure is comprised of core, insulation layer, screen layer and protective layer four parts.Wherein, core is the current-carrying part of power cable, is used for transmission of electric energy, and it is the major portion of power cable; Insulation layer will be isolated from each other at electric equipment compartment between core and the earth and out of phase core, guarantees power delivery, and it is indispensable integral part in power cable structure; Protective layer is that the protection power cable is avoided the intrusion of introduced contaminants and moisture, and prevents that external force from directly damaging power cable.Because copper has good electroconductibility, copper is widely used in the core of power cable.But along with the scarcity day by day of copper resource, and the content of aluminium is very abundant, has received investigator's concern with aluminium substitution copper, so aluminium alloy becomes the focus of research as cable conductor.
Aluminium alloy power cable substitutes copper cable becomes a kind of trend gradually, and is widely applied.Aluminum-alloy conductor material of the prior art, comparatively excellent at aspects such as electrical property, corrosion resistance nature and mechanical propertys, but aspect anti-fatigue performance or poor, thereby quality problems easily appear, affect the work-ing life of aluminum alloy materials or bring potential safety hazard, therefore, the aluminium alloy power cable over-all properties is still relatively poor.
Summary of the invention
Aluminium alloy that provides a kind of over-all properties to be used for preferably power cable and preparation method thereof is provided the technical problem that the present invention solves.
In view of this, the invention provides a kind of Al-Fe-Rb-RE aluminium alloy, comprising:
0.01 the Fe of ~ 1.6wt%; 0.001 the Cu of ~ 0.3wt%; 0.001 the Mg of ~ 0.3wt%; 0.001 the Co of ~ 0.3wt%; 0.001 the Be of ~ 0.2wt%; 0.001 the Ca of ~ 0.3wt%; 0.001 the Zn of ~ 0.2wt%; 0.001 the Sr of ~ 0.3wt%; 0.001 the Zr of ~ 0.3wt%; 0.002 the Li of ~ 0.25wt%; 0.001 the Na of ~ 0.2wt%; 0.002 the K of ~ 0.25wt%; 0.001 the Ti of ~ 0.2wt%; 0.001 the V of ~ 0.15wt%; 0.001 the Cr of ~ 0.12wt%; 0.001 the Mn of ~ 0.12wt%; 0.001 the Ni of ~ 0.15wt%; 0.001 the Ga of ~ 0.2wt%; 0.003 the Ge of ~ 0.2wt%; 0.001 the Rb of ~ 0.2wt%; 0.01 the RE of ~ 3.0wt%; Greater than zero and less than or equal to the Si of 0.2wt%; Greater than zero and less than or equal to the B of 0.8wt%; The aluminium of surplus.
Preferably, the Fe that comprises 0.25 ~ 0.6wt%.
Preferably, the RE that comprises 0.1 ~ 0.6wt%.
Preferably, the Rb that comprises 0.005 ~ 0.15wt%.
The invention provides a kind of preparation method of Al-Fe-Rb-RE aluminium alloy, comprise the following steps:
a) aluminium alloy cast ingot of the following composition of casting: the Fe of 0.01 ~ 1.6wt%, 0.001 the Cu of ~ 0.3wt%, 0.001 the Mg of ~ 0.3wt%, 0.001 the Co of ~ 0.3wt%, 0.001 the Be of ~ 0.2wt%, 0.001 the Ca of ~ 0.3wt%, 0.001 the Zn of ~ 0.2wt%, 0.001 the Sr of ~ 0.3wt%, 0.002 the Li of ~ 0.25wt%, 0.001 the Zr of ~ 0.3wt%, 0.001 the Na of ~ 0.2wt%, 0.002 the K of ~ 0.25wt%, 0.001 the Ti of ~ 0.2wt%, 0.001 the V of ~ 0.15wt%, 0.001 the Cr of ~ 0.12wt%, 0.001 the Mn of ~ 0.12wt%, 0.001 the Ni of ~ 0.15wt%, 0.001 the Ga of ~ 0.2wt%, 0.003 the Ge of ~ 0.2wt%, 0.001 the Rb of ~ 0.2wt%, 0.01 the RE of ~ 3.0wt%, greater than zero and less than or equal to the Si of 0.2wt%, greater than zero and less than or equal to the B of 0.8wt% and the aluminium of surplus,
B) described aluminium alloy cast ingot is carried out homogenizing and process, the aluminium alloy cast ingot after homogenizing is processed is rolled, and obtains the aluminium alloy pole stock;
C) the aluminium alloy pole stock that step b) is obtained carries out the intermittent type anneal;
D) the aluminium alloy pole stock that step c) is obtained carries out ageing treatment, obtains aluminium alloy.
Preferably, the temperature that described homogenizing is processed is 450 ~ 550 ℃, and the time that described homogenizing is processed is 6 ~ 16h, and the heat-up rate that described homogenizing is processed is 3 ~ 8 ℃/min.
Preferably, described step c) is specially:
The aluminium alloy pole stock that step b) is obtained is heated to 280 ~ 350 ℃, lowers the temperature after insulation 2 ~ 8h, and temperature is down to 150 ~ 200 ℃, and is cooling after insulation 2 ~ 4h.
Preferably, described ageing treatment is to carry out in 5 ~ 15KV/cm uniform electric field in strength of electric field.
Preferably, the temperature of described ageing treatment is 250 ~ 320 ℃, and the time of described ageing treatment is 4 ~ 20h.
The present invention also provides a kind of power cable, comprises core, insulation layer, screen layer and protective layer, and described core is the described aluminium alloy of such scheme or the prepared aluminium alloy of such scheme.
The invention provides a kind of Al-Fe-Rb-RE aluminium alloy, the present invention has added micro-iron take aluminium as base, and aluminium can form Al with iron
3Fe, the Al that separates out
3The Fe dispersed granules has suppressed the creep strain of alloy, and part Fe also forms the AlFeRE compound with RE and separates out, and precipitated phase AlFeRE can strengthen the anti-fatigue performance of alloy and the resistance toheat of hot operation, and the rare earth compound precipitated phase can also improve yield strength intensity; The copper that adds forms the θ phase with aluminium, and θ plays solution strengthening and dispersion-strengthened action mutually, has improved tensile strength and the yield strength of aluminium alloy; Vanadium in alloy melt with the elements such as Fe, Cu, RE form al-based compounds be distributed in aluminium base in, have the High-Temperature Strengthening effect, improve the thermotolerance of aluminium alloy; Nickel can form AlNi2, Al in melt
3The High-Temperature Strengthening phases such as Ni are disperse phase and are distributed in the matrix crystal boundary, put forward heavy alloyed room temperature strength and hot strength; Germanium can form Al in melt
9Ge
7, Al
6Ge
5, Al
5Ge
2, Al
3Ge
4Deng alloy cpd, form the High-Temperature Strengthening phase, improve the thermally-stabilised and high-temperature creep resistance of alloy operation; Rubidium can form Al in melt
7Rb
9, Al
5Rb
3, AlRb
2, AlRb
4Deng metallic compound, put forward heavy alloyed tensile strength; Rare earth element can be concentrated to be distributed on crystal boundary as surface active element, reduces pulling force between phase and phase, thereby makes grain refining.The present invention is conducive to the raising of aluminium alloy over-all properties by the selection of alloy element and the control of content.
The present invention also provides a kind of preparation method of Al-Fe-Rb-RE aluminium alloy, at first carries out homogenizing by ingot casting and processes, and homogenizing is processed ingot casting is heated evenly, and the weave construction of optimized alloy; Then the aluminium alloy cast ingot of homogenizing being processed is rolled into pole stock and carries out the intermittent type anneal, eliminate the internal stress that produces in mechanical processing process and to the damage of microtexture, optimize crystalline structure, recover the electrical property of wire rod, optimize mechanical property, make tensile property, flexility and the anti-fatigue performance of material keep coupling preferably; Again the aluminium alloy pole stock after anneal is carried out ageing treatment in uniform electric field, can make the performance of whole material reach even distribution by ageing treatment, the properties overall target reaches all good couplings.The present invention is by the optimization to the aluminium alloy preparation method, tensile property, flexility, electrical property, corrosion resistance nature and the anti-fatigue performance aspect maintenance of material are mated preferably, and the performance that makes whole material reaches even distribution, thereby obtains over-all properties aluminium alloy preferably.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just as further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
The embodiment of the invention discloses a kind of Al-Fe-Rb-RE aluminium alloy, comprising:
0.01 the Fe of ~ 1.6wt%; 0.001 the Cu of ~ 0.3wt%; 0.001 the Mg of ~ 0.3wt%; 0.001 the Co of ~ 0.3wt%; 0.001 the Be of ~ 0.2wt%; 0.001 the Ca of ~ 0.3wt%; 0.001 the Zn of ~ 0.2wt%; 0.001 the Sr of ~ 0.3wt%; 0.001 the Zr of ~ 0.3wt%; 0.002 the Li of ~ 0.25wt%; 0.001 the Na of ~ 0.2wt%; 0.002 the K of ~ 0.25wt%; 0.001 the Ti of ~ 0.2wt%; 0.001 the V of ~ 0.15wt%; 0.001 the Cr of ~ 0.12wt%; 0.001 the Mn of ~ 0.12wt%; 0.001 the Ni of ~ 0.15wt%; 0.001 the Ga of ~ 0.2wt%; 0.003 the Ge of ~ 0.2wt%; 0.001 the Rb of ~ 0.2wt%; 0.01 the RE of ~ 3.0wt%; Greater than zero and less than or equal to the Si of 0.2wt%; Greater than zero and less than or equal to the B of 0.8wt%; The aluminium of surplus.
According to the present invention, iron is as the feature microalloy element, because aluminium can form Al3Fe with iron, and the Al that separates out
3The Fe diffusing particle has suppressed the creep strain of alloy, and improves the stability that connects.Fe can improve aluminium base tensile strength, yield strength and resistance toheat, can also put forward heavy alloyed plasticity simultaneously.In the preparation process of aluminium alloy, in alloy, part Fe separates out with the form of Al3Fe, and part Fe and RE form the AlFeRE compound and separate out, and after the high temperature anneal, the solid solution of Fe in aluminium base is less, and the impact of the electrical property of Fe alloy is very little; The anti-fatigue performance of enhancing alloy and the resistance toheat of hot operation but these disperse educts are on good terms, and the rare earth compound precipitated phase can also improve yield strength intensity.In alloy, the content of Fe is below 0.01wt%, very little to aluminium base performance change, do not have effect, but the content of Fe can not be too high, if surpass 1.6wt%, the weakening of aluminium base electrical property is comparatively obvious, and influential for the use meeting that is used for electric wire and cable conductor, cable accessory and appliance field aspect, it is better that therefore total body burden is controlled the following effect of 1.6wt%.The content of described Fe is 0.01 ~ 1.6wt%, is preferably 0.20 ~ 1.0wt%, more preferably 0.25 ~ 0.6wt%, more preferably 0.30 ~ 0.45wt%.
Copper is the basic strengthening element in aluminium alloy, and it and aluminium form θ (Al
2Cu) phase, and θ has the effect of solution strengthening and dispersion-strengthened mutually, can effectively improve tensile strength and the yield strength of aluminium alloy.If it is not obvious that the content of copper less than 0.001wt%, improves the mechanical property of aluminium alloy, if content surpasses 0.3wt%, reduce specific conductivity.In addition, Cu can also improve the aluminum alloy heat performance.The content of described Cu is 0.001 ~ 0.3wt%, is preferably 0.008 ~ 0.28wt%, 0.01 ~ 0.25wt% more preferably, and more preferably 0.05 ~ 0.20wt%, most preferably be 0.10 ~ 0.15wt%.
The present invention has also added the larger magnesium elements of atomic radius in aluminium alloy, magnesium can make lattice produce distortion, causes solution hardening; Magnesium can also improve erosion resistance and the resistance toheat of aluminium alloy simultaneously.But the content of magnesium should not surpass 0.3wt%, and too Gao Zehui causes the reduction of the too much increase of resistance and resistance toheat.The content of described magnesium is 0.001 ~ 0.3wt%, is preferably 0.005 ~ 0.25wt%, and more preferably 0.01 ~ 0.20wt%, most preferably be 0.05 ~ 0.15wt%.
According to the present invention, select the high reactivity element cobalt as the alloying trace additives, cobalt can form AlCo, Al in alloy
3Co
2, AlCo
2Etc. multiple dispersivity High-Temperature Strengthening phase; When coexisting, it and iron forms Al in the interdendritic
4(CoFe) etc. complicated strengthening phase, hinder dislocation, stop grain sliding, effectively improved antifatigue and creep-resistant property under Alloy At Room Temperature and high temperature, thereby improve the thermotolerance of aluminium alloy.The content of described cobalt is 0.001 ~ 0.3wt%, is preferably 0.003 ~ 0.28wt%, and more preferably 0.005 ~ 0.25wt%, most preferably be 0.01 ~ 0.20wt%, most preferably is 0.055 ~ 0.18wt%.
Beryllium (Be) forms α, β dispersivity High-Temperature Strengthening phase in alloy, can prevent oxidation, the scaling loss and air-breathing of alloying element, puies forward the density of heavy alloyed smelting quality and surface film oxide.Be can also make impurity iron become a shape by needle-like, sand mold casting and model recoil in the time of can preventing from pouring into a mould.Because Be has high affinity to oxygen and nitrogen, so it is efficiently when melt is degassed, thereby it is better to access surface smoothness, and intensity is higher, and the improved premium casting of ductility.On the other hand, add Be can make the Fe intermetallic crystal of fragility be transformed into little equiaxed crystal by large needle-like shape and stratiform shape in alloy, improve intensity and the ductility of alloy, and can allow that higher Fe content is arranged in aluminium alloy.Be can also improve the mobility of aluminium alloy, the mobility of melt is increased, and can put forward heavy alloyed tensile strength and yield strength.According to the present invention, the content of described Be is 0.001 ~ 0.2wt%, is preferably 0.005 ~ 0.18wt%, more preferably 0.10 ~ 0.15wt%.
Calcium (Ca) element adds element as the feature of complex compound, forms Al in alloy melt
4Ca, Al
2Ca
3, AlCa
2Deng metallic compound, high-temperature behavior that can reinforced aluminium alloy strengthens resistance toheat and the anti-fatigue performance of aluminium alloy, and it can not cause on the electrical property of aluminium alloy too large impact below 0.3wt%.The content of described calcium is 0.001 ~ 0.3wt%, is preferably 0.004 ~ 0.28wt%, and more preferably 0.011 ~ 0.25wt%, most preferably be 0.05 ~ 0.20wt%, most preferably is 0.08 ~ 0.15wt%, most preferably is 0.10 ~ 0.12wt%.
The present invention has added micro-zinc in aluminium alloy, zinc forms REAl with Al in melt
2Zn
3, Fe
3Al
2The various metals compounds such as Zn can play the tensile property of improving aluminium alloy, and to a certain degree can effectively improve the high-temp anti-corrosion performance of aluminium alloy, can also improve the wear resisting property of aluminium alloy.The content of described zinc is 0.001 ~ 0.2wt%, is preferably 0.005 ~ 0.18wt%, 0.01 ~ 0.15wt% more preferably, and more preferably 0.05 ~ 0.12wt%, most preferably be 0.08 ~ 0.10wt%.
Strontium (Sr) element adds element as the feature of complex compound, can form Al in melt
7Sr
8, Al
4Sr
3, AlSr
2And AlSr
3Etc. multiple alloying element, can play the High-Temperature Strengthening effect, improve high temperature creep property.Secondly, Sr adds in aluminium alloy, can prevent aluminium alloy high temperature cracking when casting, occurs unnecessary impact in avoiding casting, and reduces process costs, improves the disposable power that is processed into.The content of described strontium is 0.001 ~ 0.3wt%, is preferably 0.005 ~ 0.28wt%, 0.01 ~ 0.26wt% more preferably, and 0.06 ~ 0.24wt% more preferably, more preferably 0.10 ~ 0.20wt%, most preferably be 0.12 ~ 0.15wt%.
Zirconium (Zr) element adds element as the feature of complex compound, and it is by forming tiny dispersion-strengthened phase in alloy, and the strengthening effect that reaches a high temperature improves the thermostability of aluminium alloy under hot operation; On the other hand, Zr and Fe, Cu and Al form complicated alloy cpd, can improve the anti-fatigue performance of aluminium alloy.The content of described zirconium is 0.001 ~ 0.3wt%, is preferably 0.005 ~ 0.25wt%, 0.01 ~ 0.20wt% more preferably, and more preferably 0.05 ~ 0.15wt%, most preferably be 0.10 ~ 0.12wt%.
Silicon (Si) can promote Al
3Zr separates out, and improves tensile strength; Si can also form the Mg-Si metallic compound with Mg, improves the thermal characteristics of aluminium alloy.But the content of Si should not surpass 0.2%, otherwise can cause electrical property obviously to descend, and cast bar easily produces defective, phenomenon of rupture easily occurs in rolling and strand process processed.The content of described silicon less than or equal to 0.2wt%, is preferably 0.001 ~ 0.18wt% greater than zero, and more preferably 0.05 ~ 0.15wt%, most preferably be 0.08 ~ 0.12wt%.
The present invention with boron (B) add aluminium base in, can crystal grain thinning, form tiny disperse educt phase, owing to there being a large amount of this disperse phase in alloy, growing up of crystal grain also hindered, thereby can significantly improve recrystallization temperature, extend recrystallize incubation period, reduce recrystallize speed.On the other hand, boron can also improve intensity and the extension property of aluminium alloy, and makes alloy have fatigue resistance preferably.B can also form complex compound with Zr and Al, puies forward heavy alloyed thermal characteristics.The content of described boron be greater than zero less than or equal to 0.8wt%, be preferably 0.001 ~ 0.70wt%, 0.01 ~ 0.65wt% more preferably, 0.10 ~ 0.5wt% more preferably, more preferably 0.25 ~ 0.45wt%, most preferably be 0.30 ~ 0.40wt%.
According to the present invention, added elemental lithium in aluminium alloy, lithium (Li) element adds element as the feature of complex compound, forms Al in alloy melt
2Li
3, AlLi
2And AlLi
5Etc. dispersivity High-Temperature Strengthening phase, thus hardness, corrosion resistance nature and the toughness of raising aluminium alloy.The content of described lithium is 0.002 ~ 0.25wt%, is preferably 0.005 ~ 0.20wt%, and more preferably 0.01 ~ 0.15wt%, most preferably be 0.05 ~ 0.10wt%.
Sodium (Na) element adds element as the feature of complex compound, forms Al in alloy melt
2Na
3, AlNa
2, AlNa
5Deng the complex alloys compound, form the complex alloys compound with Fe, Mg, RE simultaneously in melt, above-mentioned alloy cpd disperse is distributed in alloy, can crystal grain thinning, thereby raising intensity of aluminum alloy, improve the anti-fatigue performance of aluminium alloy and increase the plasticity of aluminium alloy, strengthen the workability of aluminium alloy.The content of described sodium is 0.001 ~ 0.2wt%, is preferably 0.003 ~ 0.18wt%, 0.005 ~ 0.15wt% more preferably, and more preferably 0.01 ~ 0.13wt%, most preferably be 0.05 ~ 0.10wt%.
Potassium (K) element forms Al as the trace additives of aluminium alloy in alloy melt
5K
7, Al
3K
4, Al
2K
3, AlK
2Deng the complex alloys compound, described alloy cpd has the High-Temperature Strengthening effect, can improve thermotolerance and the workability of aluminium alloy, strengthens the plasticity of aluminium alloy.The content of described potassium is 0.002 ~ 0.25wt%, is preferably 0.005 ~ 0.23wt%, 0.01 ~ 0.20wt% more preferably, and more preferably 0.05 ~ 0.18wt%, most preferably be 0.10 ~ 0.15wt%.
Titanium (Ti) element is as the trace additives of complex compound, form aluminium base complex compound with multiple elements such as Fe, Mg, Cu, RE in alloy melt, effective crystallization of refinement, improve the crystalline structure structure, and separate out the composite alloy compound on aluminium base crystal boundary, reduce other trace element to the abated effect of aluminium alloy electric performance, and the creep-resistant property of raising aluminium alloy improves the castability of alloy.The content of described titanium is 0.001 ~ 0.2wt%, is preferably 0.003 ~ 0.18wt%, 0.005 ~ 0.15wt% more preferably, and more preferably 0.01 ~ 0.13wt%, most preferably be 0.05 ~ 0.10wt%.
Vanadium (V) element is as the trace additives of complex compound, in alloy melt with the elements such as Fe, Cu, RE form aluminium base complex compound be distributed in aluminium base in, the effect with High-Temperature Strengthening can improve the thermotolerance of aluminium alloy.The content of described vanadium is 0.001 ~ 0.15wt%, is preferably 0.005 ~ 0.13wt%, and more preferably 0.01 ~ 0.10wt%, most preferably be 0.03 ~ 0.07wt%.
Chromium (Cr) forms β-GrAl7, η-Gr in alloy
27 kinds of dispersivity High-Temperature Strengthening phases such as Al have refinement cast structure, the ability of heat resistanceheat resistant crackle when the material crystallization; Chromium can also improve the wear resistance of aluminium alloy.The content of described chromium is 0.001 ~ 0.12wt%, is preferably 0.003 ~ 0.10wt%, more preferably 0.01 ~ 0.08wt%.
The MnAl that manganese (Mn) element and the effect of matrix element aluminium obtain
4Have identical current potential with fine aluminium, can effectively improve erosion resistance and the weldability of alloy; Manganese as the High-Temperature Strengthening phase, has the raising recrystallization temperature simultaneously, suppresses the effect of recrystallize alligatoring, can realize the solution strengthening of alloy, the additional reinforcement and the raising resistance toheat.The content of described manganese is 0.001 ~ 0.12wt%, is preferably 0.003 ~ 0.10wt%, and more preferably 0.005 ~ 0.08wt%, most preferably be 0.01 ~ 0.05wt%.
Nickel (Ni) element adds element as the feature of complex alloys, can form AlNi in melt
2, Al
3The High-Temperature Strengthening phases such as Ni are disperse phase and are distributed in the matrix crystal boundary, put forward heavy alloyed room temperature intensity and hot strength and volume, dimensional stability, and have the tendency that the compound that makes Fe becomes bulk, namely reduce Fe to the impact of aluminium base electrical property.The content of described nickel is 0.001 ~ 0.15wt%, is preferably 0.003 ~ 0.10wt%, and more preferably 0.01 ~ 0.08wt%, most preferably be 0.03 ~ 0.05wt%.
Gallium (Ga) element adds element as the feature of complex alloys, has to improve the problem of oxidation of aluminium alloy in melting, casting, welding, rolling, forging and pressing and extruding heat-processed.The content of described gallium is 0.001 ~ 0.2wt%, is preferably 0.003 ~ 0.18wt%, 0.008 ~ 0.15wt% more preferably, and more preferably 0.01 ~ 0.12wt%, most preferably be 0.05 ~ 0.08wt%.
Germanium (Ge) adds element as the feature of complex alloys, can form Al in melt
9Ge
7, Al
6Ge
5, Al
5Ge
2, Al
3Ge
4Etc. multiple alloy cpd, form the High-Temperature Strengthening phase, improve the thermally-stabilised and high-temperature creep resistance of alloy operation.The content of described germanium is 0.003 ~ 0.2wt%, is preferably 0.005 ~ 0.18wt%, and more preferably 0.01 ~ 0.15wt%, most preferably be 0.05 ~ 0.10wt%.
Rubidium (Rb) adds element as the feature of complex alloys, can form Al in melt
7Rb
9, Al
5Rb
3, AlRb
2, AlRb
4Deng metallic compound, improve the tensile strength of aluminium alloy, particularly improve the yield strength of aluminium alloy.The content of described rubidium is 0.001 ~ 0.2wt%, is preferably 0.003 ~ 0.18wt%, 0.005 ~ 0.15wt% more preferably, and 0.005 ~ 0.15wt% more preferably, more preferably 0.01 ~ 0.10wt%, most preferably be 0.03 ~ 0.08wt%.
The present invention has added rare earth element in aluminium alloy, described rare earth element can be put forward heavy alloyed electroconductibility, due to rare earth element energy crystal grain thinning, and form stable compound and separate out from crystal with elements such as Fe, Cu in alloy, reduce electrolytical liquidus temperature, ion movement velocity under the effect of electric field is accelerated, reduced concentration overpotential, thereby make the resistivity decreased of aluminium alloy.On the other hand, rare earth element is larger than aluminium with the avidity of the elements such as hydrogen, oxygen, nitrogen, form multiple compounds, thereby rare earth is degasification in alloy, denitrogenation, slag making, neutralization trace low melting point impurity and the clearing machine that changes impurity state, can play refining effect preferably, make alloy become purer, thereby resistivity is greatly improved, electric conductivity can reach 60%IACS.On the other hand, rare earth element can form the dense oxidation film structure, plays fabulous effect for carrying heavy alloyed oxidisability and electrochemical corrosion resistant, has improved the work-ing life of aluminium alloy.In addition, rare earth is surface active element, can concentrate to be distributed on the crystal boundary face, reduces pulling force between phase and phase, and the merit that forms the critical size nucleus is reduced, and nuclei of crystallization quantity increases, thereby makes grain refining.Secondly, after ageing treatment in melting, high temperature annealing and uniform electric field, Fe forms complicated ferro-aluminum rare earth metal with RE in Al, improved the antifatigue limit and the yield strength of alloy, increases alloy result of use and work-ing life in actual applications.
Described rare earth elements RE is one or more in lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc) and yttrium (Y), is preferably one or more in Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tm and Lu.Wherein, rare earth Pm forms Al in alloy
11Pm
3~ AlPm
2Deng 6 kinds of active metallic compounds; Rare-earth Sm forms Al in alloy
11Sm
4, Al
3Sm, Al
2Sm, AlSm, AlSm
3The isoreactivity metallic compound; Rare earth Eu forms EuAl in alloy
4, EuAl
2, EuAl isoreactivity metallic compound; Rare-earth Gd forms Al in alloy
4Gd ~ Al
17Gd
2Deng 7 kinds of infusibility metallic compounds; Rare earth Tb forms Al in alloy
3Tb, Al
2Tb, AlTb, AlTb
2, AlTb
3Deng the infusibility active metallic compound; Rare earth Dy forms Al in alloy
5Dy ~ Al
17Dy
2Deng 8 kinds of infusibility active metallic compounds; Rare earth Ho forms Al in alloy
5Ho
3, Al
3Ho, AlHo
2, AlHo
3Deng the infusibility active metallic compound; Rare earth Tm forms Al in alloy
3Tm
2, Al
3Tm, AlTm, AlTm
3Deng the infusibility active metallic compound; Rare earth Lu forms Al in alloy
7Lu
3, Al
5Lu
3, Al
2Lu
3, AlLu
2, the infusibility active metallic compound such as AlLu3.Above-mentioned dystectic active metallic compound disperse is distributed in intergranular and the interdendritic that is netted or skeleton shape, and with the matrix mortise, played and strengthened and the effect of stable crystal boundary.Simultaneously, also can in and the elements such as element of Fe, Cu in molten metal, forms dystectic compound or they is evenly distributed in the whole crystalline structure in interdendritic, eliminated dendritic structure, with the over-all properties of raising alloy material.The content of described rare earth element is 0.01 ~ 3.0wt%, is preferably 0.03 ~ 2.5wt%, and more preferably 0.05 ~ 1.5wt%, most preferably be 0.1 ~ 0.6wt%.
According to the present invention, for the base aluminum in aluminium alloy, can adopt the fine aluminium of industrial Al99.70, make the aluminium alloy that the present invention prepares have the advantages such as raw material supply abundance, cost is low, buying is convenient; Simultaneously aluminium base refined aluminium or high-purity grade of aluminium of can also adopting is as matrix alloy, and this is aluminium base has higher quality than conventional aluminium sill, and the product that is processed into has more advantage at electrical property and mechanical properties.
The invention provides a kind of Al-Fe-Rb-RE aluminium alloy, described aluminium alloy has added micro-iron take aluminium as base, and aluminium can form Al with iron
3Fe, the Al that separates out
3The Fe dispersed granules has suppressed the creep strain of alloy, and part Fe also forms the AlFeRE compound with RE and separates out, and precipitated phase AlFeRE can strengthen the anti-fatigue performance of alloy and the resistance toheat of hot operation, and the rare earth compound precipitated phase can also improve yield strength intensity; Copper forms the θ phase with aluminium, has played effect preferably for the tensile strength and the yield strength that improve aluminium alloy; Vanadium in alloy melt with the elements such as Fe, Cu, RE form al-based compounds be distributed in aluminium base in, have the High-Temperature Strengthening effect, improve the thermotolerance of aluminium alloy; Germanium can form Al in melt
9Ge
7, Al
6Ge
5, Al
5Ge
2, Al
3Ge
4Deng alloy cpd, form the High-Temperature Strengthening phase, improve the thermally-stabilised and high-temperature creep resistance of alloy operation; Rubidium can form Al in melt
7Rb
9, Al
5Rb
3, AlRb
2, AlRb
4Deng metallic compound, put forward heavy alloyed tensile strength; Rare earth element is surface active element, can concentrate to be distributed on the crystal boundary face, reduces pulling force between phase and phase, thereby makes grain refining.The present invention is by adding Determination of multiple metal elements and to the control of constituent content, being conducive to the raising of aluminium alloy over-all properties.
The present invention also provides a kind of preparation method of Al-Fe-Rb-RE aluminium alloy, comprises the following steps:
a) raw material of following composition is cast, obtain aluminium alloy cast ingot: the Fe of 0.01 ~ 1.6wt%, 0.001 the Cu of ~ 0.3wt%, 0.001 the Mg of ~ 0.3wt%, 0.001 the Co of ~ 0.3wt%, 0.001 the Be of ~ 0.2wt%, 0.001 the Ca of ~ 0.3wt%, 0.001 the Zn of ~ 0.2wt%, 0.001 the Sr of ~ 0.3wt%, 0.001 the Zr of ~ 0.3wt%, 0.002 the Li of ~ 0.25wt%, 0.001 the Na of ~ 0.2wt%, 0.002 the K of ~ 0.25wt%, 0.001 the Ti of ~ 0.2wt%, 0.001 the V of ~ 0.15wt%, 0.001 the Cr of ~ 0.12wt%, 0.001 the Mn of ~ 0.12wt%, 0.001 the Ni of ~ 0.15wt%, 0.001 the Ga of ~ 0.2wt%, 0.003 the Ge of ~ 0.2wt%, 0.001 the Rb of ~ 0.2wt%, 0.01 the RE of ~ 3.0wt%, greater than zero and less than or equal to the Si of 0.2wt%, greater than zero and less than or equal to the B of 0.8wt% and the aluminium of surplus,
B) described aluminium alloy cast ingot is carried out homogenizing and process, the aluminium alloy cast ingot after homogenizing is processed is rolled, and obtains the aluminium alloy pole stock;
C) the aluminium alloy pole stock that step b) is obtained carries out the intermittent type anneal;
D) the aluminium alloy pole stock that step c) is obtained carries out ageing treatment, obtains aluminium alloy.
according to the present invention, step a) is casting process, obtain aluminium alloy cast ingot, for various elements are fully melted, evenly distribute, as preferred version, above-mentioned casting technique specifically comprises: aluminium ingot is dropped in smelting furnace, be heated to 720 ~ 800 ℃ and insulation in closed environment, add again Fe after the aluminium ingot fusing, Cu, Mg, Co, Be, Ca, Zn, Sr, Zr, Si, B, Li, Na, K, Ti, V, Cr, Mn, Ni, Ga, Ge and Rb or Al-Fe, Al-Cu, Al-Mg, Al-Co, Al-Be, Al-Ca, Al-Zn, Al-Sr, Al-Zr, Al-Si, Al-B, Al-Li, Al-Na, Al-K, Al-Ti, Al-V, Al-Cr, Al-Mn, Al-Ni, Al-Ga, Al-Ge and Al-Rb master alloy, after stirring, add rare earth elements RE, obtain alloy melt, described alloy melt is added refining agent, carry out furnace refining, insulation 20 ~ 40min obtains aluminium alloy, described aluminium alloy through degasification, slagging-off, is entered casting machine and casts, obtain aluminium alloy cast ingot.Because aluminium is difficult for scaling loss, and add-on is more, therefore first aluminium is added smelting furnace, then adds other metallic element.Alloying element of the present invention preferably adopts said sequence to add, and loss does not occur after making various element meltings, and various elements can fully melt simultaneously, evenly distributes.
The treatment stage that step b) being homogenizing, the temperature that described homogenizing is processed is preferably 450 ~ 550 ℃, and more preferably 480 ℃ ~ 520 ℃, the time that described homogenizing is processed is preferably 2 ~ 8h, more preferably 3 ~ 6h.Aluminium alloy cast ingot is carried out homogenizing process, can guarantee ingot casting in the process of rolling pole stock, its intensity and ductility have coupling preferably, thereby avoid adopting traditional way to cause the destruction of material microstructure and further affect processing characteristics.In order to guarantee that ingot casting is heated evenly, the weave construction of optimized alloy, avoid alloy in the course of processing owing to heating up or the too fast generation that causes the internal structure defective of lowering the temperature, the heat-up rate that described homogenizing is processed is preferably 3 ~ 8 ℃/min, more preferably 5 ℃/min.After aluminium alloy cast ingot is carried out the homogenizing processing, that aluminium alloy cast ingot is rolling, obtain the aluminium alloy pole stock.
Subsequently the aluminium alloy pole stock is heat-treated, at first the aluminium alloy pole stock is carried out the anneal at intermittence in annealing furnace.Described intermittence, anneal was specially: described aluminium alloy pole stock is heated to 280 ~ 350 ℃, lowers the temperature after insulation 2 ~ 8h, temperature is down to 150 ~ 200 ℃, and is cooling after insulation 2 ~ 4h.At high temperature oxidation occurs and cause material to weaken at electrical property and surface corrosion-resistant erosion aspect of performance for fear of aluminum alloy materials, described anneal is preferably carried out under inert atmosphere.The present invention adopts intermittent type substep anneal, and cooling down progressively, this kind processing mode can be eliminated the internal stress that produces in mechanical processing process and to the damage of microtexture, optimize crystalline structure, recover the electrical property of wire rod, optimize mechanical property, tensile property, flexility and the anti-fatigue performance aspect maintenance of material are mated preferably.
After the aluminium alloy pole stock is carried out anneal, the aluminium alloy pole stock after anneal is carried out ageing treatment.Described ageing treatment is preferably to carry out in 5 ~ 15KV/cm uniform electric field in strength of electric field.The temperature of described ageing treatment is preferably 250 ~ 320 ℃, and more preferably 280 ~ 300 ℃, the time of described ageing treatment is preferably 4 ~ 20h, and more preferably 8 ~ 15h, most preferably be 10 ~ 13h.Carry out ageing treatment on the basis of anneal technology, can further make up heat conduction inequality in the anneal process, cause the characteristics of the inside and outside performance profile inequality of material or local defect.Can make the performance of whole material reach even distribution by ageing treatment, the properties overall target reaches all good couplings.So anneal and ageing treatment, both effective combinations have been played vital effect for the optimization of material monolithic performance, and Neither of the two can be dispensed.The present invention preferably carries out ageing treatment in high-intensity uniform electric field, first aspect has changed arrangement, coupling and the migration of atom, and second aspect has improved the solid solution degree of alloying element, has brought out the homogeneous nucleation of T1 phase, has improved the yield strength of alloy; After the sample that homogenizing is processed carried out ageing treatment, the precipitated phase even dispersion distributed, and the mechanical property of alloy improves greatly; The third aspect, what changed the fine crystals tissue separates out form and quantity, makes the orientations such as form, size, distribution occur in the material solid-state phase changes to be controlled, thereby controls the tissue of material, finally obtains good mechanical property and electric property.
The present invention also provides a kind of preparation method of aluminium alloy, at first carrying out homogenizing by ingot casting processes, then the aluminium alloy cast ingot of homogenizing being processed is rolled into pole stock and puts into annealing furnace again, carry out anneal, carry out again ageing treatment in uniform electric field, tensile property, flexility, electrical property, corrosion resistance nature and the anti-fatigue performance aspect maintenance of material are mated preferably, and make the performance of whole material reach even distribution, thereby obtain over-all properties aluminium alloy preferably.Aluminum alloy materials of the present invention is by adding multiple alloying element and adopting heat treatment technics, improved greatly the resistance toheat of fine aluminium, make this aluminum alloy materials long-time running temperature at 235 ℃, creep is less, tensile strength keeps 91% survival rate, ensured that mechanical property changes less under hot operation, anti-fatigue performance has also obtained good raising simultaneously, the number of times of bending repeatedly of aluminium alloy reaches 37 times, can avoid like this loss in various degree that occurs in installation process as conductor thread core; And make the snappiness of alloy fairly good by heat treatment technics, cable is installed bending radius at 4.5 times more than the outside diameter of cable, greatly improved the ductility of aluminium alloy, unit elongation surpasses 32%, the damage phenomenon can easily not appear due to the pulling force effect, and processing characteristics is very good, is applicable to be drawn into the monofilament that filament diameter differs in size more than 0.1mm.
the present invention also provides a kind of power cable, described power cable comprises core, insulation layer, screen layer and protective layer, described core is aluminium alloy, described aluminium alloy contains the Fe of 0.01 ~ 1.6wt%, 0.001 the Cu of ~ 0.3wt%, 0.001 the Mg of ~ 0.3wt%, 0.001 the Co of ~ 0.3wt%, 0.001 the Be of ~ 0.2wt%, 0.001 the Ca of ~ 0.3wt%, 0.001 the Zn of ~ 0.2wt%, 0.001 the Sr of ~ 0.3wt%, 0.001 the Zr of ~ 0.3wt%, 0.002 the Li of ~ 0.25wt%, 0.001 the Na of ~ 0.2wt%, 0.002 the K of ~ 0.25wt%, 0.001 the Ti of ~ 0.2wt%, 0.001 the V of ~ 0.15wt%, 0.001 the Cr of ~ 0.12wt%, 0.001 the Mn of ~ 0.12wt%, 0.001 the Ni of ~ 0.15wt%, 0.001 the Ga of ~ 0.2wt%, 0.003 the Ge of ~ 0.2wt%, 0.001 the Rb of ~ 0.2wt%, 0.01 the RE of ~ 3.0wt%, greater than zero Si less than or equal to 0.2wt%, greater than zero less than or equal to the B of 0.8wt% and the aluminium of surplus, the preparation method of described aluminium alloy is by the method preparation according to such scheme.Preparation method the present invention of described power cable does not have special restriction, for mode well known to those skilled in the art gets final product.
With the core of the aluminium alloy in such scheme of the present invention as power cable, can make power cable have over-all properties preferably, experimental result shows: the aluminium alloy electric conductivity of the present invention's preparation is greater than 60%, tensile strength is greater than 129MPa, elongation at break is greater than 32%, and the long-time running heat resisting temperature can reach 235 ℃, and after heat-resisting test run(s), the intensity survival rate can reach 91%, 90 degree repeatedly bend number of times and reach 37 times, and the mass loss of 400h corrosion resistance nature is less than 0.9g/m
2Hr, minimum bending radius is greater than 5 times of outside diameters of cable, and the monofilament minimum diameter is greater than 0.1m.
In order further to understand the present invention, below in conjunction with embodiment, aluminium alloy provided by the invention and preparation method thereof is elaborated, protection scope of the present invention is not limited by the following examples.
Embodiment 1
(1) aluminium ingot is dropped in smelting furnace, heating makes it fusing and insulation under 720 ℃, and melting process is completed in sealed environment; First add Fe, Cu, Mg, Co, Be, Ca, Zn, Sr, Zr, Si, B, Li, Na, K, Ti, V, Cr, Mn, Ni, Ga, Ge and Rb pure metal, add again rare earth RE to stir 20min until stir standing insulation 30min after stirring; Then above-mentioned alloy melt is carried out furnace refining; Add refining agent in alloy melt, and stir, more standing insulation 30min, the melt refining operates in sealed environment; Slag hitting after refining, standing, temperature adjustment to 650 ℃, aluminium alloy are toppled over and are come out of the stove, then after degasification, slagging-off are processed, enter casting machine and cast, and obtain aluminium alloy cast ingot, and ingot casting becomes to be respectively in table 1;
(2) speed that the aluminium alloy cast ingot that step (1) is obtained carries out 5 ℃/min heats up, and temperature to 450 ℃ is rolled into pole stock after insulation 6h;
(3) pole stock that step (2) is obtained carries out anneal under inert atmosphere, be heated to 280 ℃ of insulation 2h, then annealing temperature is down to 150 ℃ of insulation 3h, is cooled to room temperature;
(4) pole stock that step (3) is obtained carries out ageing treatment in strength of electric field is the uniform electric field of 5kV/cm, aging temp is 250 ℃, and aging time is 4h, obtains aluminium alloy.
The aluminium alloy of preparation is according to the method described above carried out performance test, and result is referring to table 2.
Embodiment 2
(1) aluminium ingot is dropped in smelting furnace, heating makes it fusing and insulation under 740 ℃, and melting process is completed in sealed environment; First add Fe, Cu, Mg, Co, Be, Ca, Zn, Sr, Zr, Si, B, Li, Na, K, Ti, V, Cr, Mn, Ni, Ga, Ge and Rb pure metal, add again rare earth RE to stir 20min until stir standing insulation 30min after stirring; Then above-mentioned alloy melt is carried out furnace refining; Add refining agent in alloy melt, and stir, more standing insulation 30min, the melt refining operates in sealed environment; Slag hitting after refining, standing, temperature adjustment to 720 ℃, aluminium alloy are toppled over and are come out of the stove, then after degasification, slagging-off are processed, enter casting machine and cast, and obtain aluminium alloy cast ingot, and ingot casting becomes to be respectively in table 1;
(2) speed that the aluminium alloy cast ingot that step (1) is obtained carries out 3 ℃/min heats up, and temperature to 550 ℃ is rolled into pole stock after insulation 16h;
(3) pole stock that step (2) is obtained carries out anneal under inert atmosphere, be heated to 360 ℃ of insulation 8h, then annealing temperature is down to 200 ℃ of insulation 2h, is cooled to room temperature;
(4) pole stock that step (3) is obtained carries out ageing treatment in strength of electric field is the uniform electric field of 15kV/cm, aging temp is 320 ℃, and aging time is 20h, obtains aluminium alloy.
The aluminium alloy of preparation is according to the method described above carried out performance test, and result is referring to table 2.
Embodiment 3
(1) aluminium ingot is dropped in smelting furnace, heating makes it fusing and insulation under 760 ℃, and melting process is completed in sealed environment; First add Al-Fe, Al-Cu, Al-Mg, Al-Co, Al-Be, Al-Ca, Al-Zn, Zn-Sr, Al-Zr, Al-Si, Al-B, Al-Li, Al-Na, Al-K, Al-Ti, Al-V, Al-Cr, Al-Mn, Al-Ni, Al-Ga, Al-Ge and Al-Rb master alloy, add again rare earth RE to stir 20min until stir standing insulation 30min after stirring; Then above-mentioned alloy melt is carried out furnace refining; Add refining agent in alloy melt, and stir, more standing insulation 30min, the melt refining operates in sealed environment; Slag hitting after refining, standing, temperature adjustment to 680 ℃, aluminium alloy are toppled over and are come out of the stove, then after degasification, slagging-off are processed, enter casting machine and cast, and obtain aluminium alloy cast ingot, and ingot casting becomes to be respectively in table 1;
(2) speed that the aluminium alloy cast ingot that step (1) is obtained carries out 8 ℃/min heats up, and temperature to 500 ℃ is rolled into pole stock after insulation 10h;
(3) pole stock that step (2) is obtained carries out anneal under inert atmosphere, be heated to 300 ℃ of insulation 4h, then annealing temperature is down to 160 ℃ of insulation 3h, is cooled to room temperature;
(4) pole stock that step (3) is obtained carries out ageing treatment in strength of electric field is the uniform electric field of 10kV/cm, aging temp is 260 ℃, and aging time is 10h, obtains aluminium alloy.
The aluminium alloy of preparation is according to the method described above carried out performance test, and result is referring to table 2.
Embodiment 4
(1) aluminium ingot is dropped in smelting furnace, heating makes it fusing and insulation under 780 ℃, and melting process is completed in sealed environment; First add Al-Fe, Al-Cu, Al-Mg, Al-Co, Al-Be, Al-Ca, Al-Zn, Zn-Sr, Al-Zr, Al-Si, Al-B, Al-Li, Al-Na, Al-K, Al-Ti, Al-V, Al-Cr, Al-Mn, Al-Ni, Al-Ga, Al-Ge and Al-Rb master alloy, add again rare earth RE to stir 20min until stir standing insulation 30min after stirring; Then above-mentioned alloy melt is carried out furnace refining; Add refining agent in alloy melt, and stir, more standing insulation 30min, the melt refining operates in sealed environment; Slag hitting after refining, standing, temperature adjustment to 750 ℃, aluminium alloy are toppled over and are come out of the stove, then after degasification, slagging-off are processed, enter casting machine and cast, and obtain aluminium alloy cast ingot, and ingot casting becomes to be respectively in table 1;
(2) speed that the aluminium alloy cast ingot that step (1) is obtained carries out 5 ℃/min heats up, and temperature to 480 ℃ is rolled into pole stock after insulation 8h;
(3) pole stock that step (2) is obtained carries out anneal under inert atmosphere, be heated to 350 ℃ of insulation 4h, then annealing temperature is down to 170 ℃ of insulation 3h, is cooled to room temperature;
(4) pole stock that step (3) is obtained carries out ageing treatment in strength of electric field is the uniform electric field of 12kV/cm, aging temp is 260 ℃, and aging time is 14h, obtains aluminium alloy.
The aluminium alloy of preparation is according to the method described above carried out performance test, and result is referring to table 2.
Embodiment 5
(1) aluminium ingot is dropped in smelting furnace, heating makes it fusing and insulation under 800 ℃, and melting process is completed in sealed environment; First add Fe, Cu, Mg, Co, Be, Ca, Zn, Sr, Zr, Si, B, Li, Na, K, Ti, V, Cr, Mn, Ni, Ga, Ge and Rb pure metal, add again rare earth RE to stir 20min until stir standing insulation 30min after stirring; Then above-mentioned alloy melt is carried out furnace refining; Add refining agent in alloy melt, and stir, more standing insulation 30min, the melt refining operates in sealed environment; Slag hitting after refining, standing, temperature adjustment to 700 ℃, aluminium alloy are toppled over and are come out of the stove, then after degasification, slagging-off are processed, enter casting machine and cast, and obtain aluminium alloy cast ingot, and ingot casting becomes to be respectively in table 1;
(2) speed that the aluminium alloy cast ingot that step (1) is obtained carries out 6 ℃/min heats up, and temperature to 490 ℃ is rolled into pole stock after insulation 18h;
(3) pole stock that step (2) is obtained carries out anneal under inert atmosphere, be heated to 320 ℃ of insulation 6h, then annealing temperature is down to 190 ℃ of insulation 3h, is cooled to room temperature;
(4) pole stock that step (3) is obtained carries out ageing treatment in strength of electric field is the uniform electric field of 12kV/cm, aging temp is 310 ℃, and aging time is 16h, obtains aluminium alloy.
The aluminium alloy of preparation is according to the method described above carried out performance test, and result is referring to table 2.
Embodiment 6
(1) aluminium ingot is dropped in smelting furnace, heating makes it fusing and insulation under 730 ℃, and melting process is completed in sealed environment; First add Fe, Cu, Mg, Co, Be, Ca, Zn, Sr, Zr, Si, B, Li, Na, K, Ti, V, Cr, Mn, Ni, Ga, Ge and Rb pure metal, add again rare earth RE to stir 20min until stir standing insulation 30min after stirring; Then above-mentioned alloy melt is carried out furnace refining; Add refining agent in alloy melt, and stir, more standing insulation 30min, the melt refining operates in sealed environment; Slag hitting after refining, standing, temperature adjustment to 800 ℃, aluminium alloy are toppled over and are come out of the stove, then after degasification, slagging-off are processed, enter casting machine and cast, and obtain aluminium alloy cast ingot, and ingot casting becomes to be respectively in table 1;
(2) speed that the aluminium alloy cast ingot that step (1) is obtained carries out 7 ℃/min heats up, and temperature to 460 ℃ is rolled into pole stock after insulation 14h;
(3) pole stock that step (2) is obtained carries out anneal under inert atmosphere, be heated to 350 ℃ of insulation 7h, then annealing temperature is down to 190 ℃ of insulation 4h, is cooled to room temperature;
(4) pole stock that step (3) is obtained carries out ageing treatment in strength of electric field is the uniform electric field of 11kV/cm, aging temp is 305 ℃, and aging time is 18h, obtains aluminium alloy.
The aluminium alloy of preparation is according to the method described above carried out performance test, and result is referring to table 2.
Embodiment 7
(1) aluminium ingot is dropped in smelting furnace, heating makes it fusing and insulation under 750 ℃, and melting process is completed in sealed environment; First add Al-Fe, Al-Cu, Al-Mg, Al-Co, Al-Be, Al-Ca, Al-Zn, Zn-Sr, Al-Zr, Al-Si, Al-B, Al-Li, Al-Na, Al-K, Al-Ti, Al-V, Al-Cr, Al-Mn, Al-Ni, Al-Ga, Al-Ge and Al-Rb master alloy, add again rare earth RE to stir 20min until stir standing insulation 30min after stirring; Then above-mentioned alloy melt is carried out furnace refining; Add refining agent in alloy melt, and stir, more standing insulation 30min, the melt refining operates in sealed environment; Slag hitting after refining, standing, temperature adjustment to 720 ℃, aluminium alloy are toppled over and are come out of the stove, then after degasification, slagging-off are processed, enter casting machine and cast, and obtain aluminium alloy cast ingot, and ingot casting becomes to be respectively in table 1;
(2) speed that the aluminium alloy cast ingot that step (1) is obtained carries out 4 ℃/min heats up, and temperature to 470 ℃ is rolled into pole stock after insulation 12h;
(3) pole stock that step (2) is obtained carries out anneal under inert atmosphere, be heated to 340 ℃ of insulation 5h, then annealing temperature is down to 170 ℃ of insulation 4h, is cooled to room temperature;
(4) pole stock that step (3) is obtained carries out ageing treatment in strength of electric field is the uniform electric field of 12.5kV/cm, aging temp is 315 ℃, and aging time is 17h, obtains aluminium alloy.
The aluminium alloy of preparation is according to the method described above carried out performance test, and result is referring to table 2.
Embodiment 8
(1) aluminium ingot is dropped in smelting furnace, heating makes it fusing and insulation under 790 ℃, and melting process is completed in sealed environment; First add Al-Fe, Al-Cu, Al-Mg, Al-Co, Al-Be, Al-Ca, Al-Zn, Zn-Sr, Al-Zr, Al-Si, Al-B, Al-Li, Al-Na, Al-K, Al-Ti, Al-V, Al-Cr, Al-Mn, Al-Ni, Al-Ga, Al-Ge and Al-Rb master alloy, add again rare earth RE to stir 20min until stir standing insulation 30min after stirring; Then above-mentioned alloy melt is carried out furnace refining; Add refining agent in alloy melt, and stir, more standing insulation 30min, the melt refining operates in sealed environment; Slag hitting after refining, standing, temperature adjustment to 750 ℃, aluminium alloy are toppled over and are come out of the stove, then after degasification, slagging-off are processed, enter casting machine and cast, and obtain aluminium alloy cast ingot, and ingot casting becomes to be respectively in table 1;
(2) speed that the aluminium alloy cast ingot that step (1) is obtained carries out 5 ℃/min heats up, and 510 ℃ of temperature are rolled into pole stock after insulation 13h;
(3) pole stock that step (2) is obtained carries out anneal under inert atmosphere, be heated to 310 ℃ of insulation 5h, then annealing temperature is down to 170 ℃ of insulation 4h, is cooled to room temperature;
(4) pole stock that step (3) is obtained carries out ageing treatment in strength of electric field is the uniform electric field of 8kV/cm, aging temp is 285 ℃, and aging time is 14h, obtains aluminium alloy.
The aluminium alloy of preparation is according to the method described above carried out performance test, and result is referring to table 2.
Embodiment 9
(1) aluminium ingot is dropped in smelting furnace, heating makes it fusing and insulation under 760 ℃, and melting process is completed in sealed environment; First add Fe, Cu, Mg, Co, Be, Ca, Zn, Sr, Zr, Si, B, Li, Na, K, Ti, V, Cr, Mn, Ni, Ga, Ge and Rb pure metal, add again rare earth RE to stir 20min until stir standing insulation 25min after stirring; Then above-mentioned alloy melt is carried out furnace refining; Add refining agent in alloy melt, and stir, more standing insulation 30min, the melt refining operates in sealed environment; Slag hitting after refining, standing, temperature adjustment to 690 ℃, aluminium alloy are toppled over and are come out of the stove, then after degasification, slagging-off are processed, enter casting machine and cast, and obtain aluminium alloy cast ingot, and ingot casting becomes to be respectively in table 1;
(2) speed that the aluminium alloy cast ingot that step (1) is obtained carries out 5 ℃/min heats up, and 480 ℃ of temperature are rolled into pole stock after insulation 14h;
(3) pole stock that step (2) is obtained carries out anneal under inert atmosphere, be heated to 340 ℃ of insulation 4h, then annealing temperature is down to 190 ℃ of insulation 3h, is cooled to room temperature;
(4) pole stock that step (3) is obtained carries out ageing treatment in strength of electric field is the uniform electric field of 11kV/cm, aging temp is 295 ℃, and aging time is 15h, obtains aluminium alloy.
The aluminium alloy of preparation is according to the method described above carried out performance test, and result is referring to table 2.
Embodiment 10
(1) aluminium ingot is dropped in smelting furnace, heating makes it fusing and insulation under 740 ℃, and melting process is completed in sealed environment; First add Fe, Cu, Mg, Co, Be, Ca, Zn, Sr, Zr, Si, B, Li, Na, K, Ti, V, Cr, Mn, Ni, Ga, Ge and Rb pure metal, add again rare earth RE to stir 20min until stir standing insulation 30min after stirring; Then above-mentioned alloy melt is carried out furnace refining; Add refining agent in alloy melt, and stir, more standing insulation 30min, the melt refining operates in sealed environment; Slag hitting after refining, standing, temperature adjustment to 800 ℃, aluminium alloy are toppled over and are come out of the stove, then after degasification, slagging-off are processed, enter casting machine and cast, and obtain aluminium alloy cast ingot, and ingot casting becomes to be respectively in table 1;
(2) speed that the aluminium alloy cast ingot that step (1) is obtained carries out 5 ℃/min heats up, and 530 ℃ of temperature are rolled into pole stock after insulation 15h;
(3) pole stock that step (2) is obtained carries out anneal under inert atmosphere, be heated to 340 ℃ of insulation 7h, then annealing temperature is down to 160 ℃ of insulation 3h, is cooled to room temperature;
(4) pole stock that step (3) is obtained carries out ageing treatment in strength of electric field is the uniform electric field of 13kV/cm, aging temp is 275 ℃, and aging time is 19h, obtains aluminium alloy.
The aluminium alloy of preparation is according to the method described above carried out performance test, and result is referring to table 2.
Comparative Examples 1
Choose the standard aluminium ingot of 99.7% purity, its impurity silica removal, iron, the outer content of copper are no more than 0.02wt%; Described aluminium ingot is put into molten aluminium stove melt, add the zirconium of 0.15wt%, the copper of 0.25wt%, the iron of 0.70wt% and the yttrium of 0.25wt%, the alloying temperature is 750 ℃; Through homogenizing stirring, refining degasification, slag making, slagging-off, the aluminum alloy melt refining temperature is 725 ℃, and with solid insulating covering agent aluminium coating aluminium alloy surface, standing 60min carries out the stokehold chemical composition analysis, and monitoring, adjustment are with control element content; Aluminium liquid is carried out continuous casting, obtain the aluminium alloy cast bar; The aluminium alloy cast bar is rolled into aluminium alloy rod, and it is 500 ℃ that the aluminium alloy cast bar advances to roll temperature, and the finishing temperature of aluminium alloy rod is 250 ℃; Aluminium alloy rod is carried out bracing wire process, pull wire speed is 20 meter per seconds, repeatedly after bracing wire, is drawn into required high-strength heat-resisting aluminum-alloy circle line; Described aluminum alloy round line is carried out modified thermal treatment, and temperature is 200 ℃, and the time is 120min, and the aluminum alloy round line after thermal treatment is cooling, obtains heat-resisting aluminium alloy circle line.The aluminum alloy round line of preparation is carried out performance test, and result is referring to table 2.
Comparative Examples 2
Select eight tons of aluminium ingots, its foreign matter content (except silicon, iron, copper) is no more than 0.02wt%, put into the circular aluminum melting furnace fusing, add simultaneously the zirconium of 0.10wt%, the copper of 0.02wt%, the iron of 0.35wt%, the silicon of 0.20wt% and the rare earth of 0.35wt%, the alloying temperature is 730 ℃; Through homogenizing stirring, refining degasification, slag making, slagging-off, the aluminum alloy melt refining temperature is 725 ℃, and with solid insulating covering agent aluminium coating aluminium alloy surface, standing 40min carries out the stokehold chemical composition analysis, and monitoring, adjustment are with control element content; Aluminium liquid is carried out continuous casting, obtain the aluminium alloy cast bar; The aluminium alloy cast bar is rolled into aluminium alloy rod, and it is 500 ℃ that the aluminium alloy cast bar advances to roll temperature, and the finishing temperature of aluminium alloy rod is 250 ℃; Aluminium alloy rod is carried out bracing wire process, pull wire speed is 10 meter per seconds, repeatedly after bracing wire, is drawn into required high-strength heat-resisting aluminum-alloy circle line; Described aluminum alloy round line is carried out modified thermal treatment, and temperature is 200 ℃, and the time is 200min, and the aluminum alloy round line after thermal treatment is cooling, obtains heat-resisting aluminium alloy circle line.The aluminum alloy round line of preparation is carried out performance test, and result is referring to table 2.
Comparative Examples 3
Add purity greater than the aluminium ingot of 99.70wt% in shaft furnace, be warming up to 750 ℃, make the aluminium ingot fusing, temperature is increased to 750 ℃, Y, the Er of 0.23wt% of Sc, 0.33wt% of Ca, 0.13wt% of Zr, 0.29wt% of Mg, 0.13wt% of Cu, 0.15wt% that adds successively Fe, the 0.11wt% of 0.86wt%, it is dissolved fully, and regulate alloying constituent to setting range, alloying element is all that the form with aluminium intermediate alloy adds; At 760 ℃ of insulation 30min, then add the refining agent of 0.15wt%, remove the gred, degasification, and then be cast into aluminum alloy casting; Aluminum alloy casting is imported milling train, and the temperature that imports milling train is 450 ℃, and it is 300 ℃ that the importing milling train becomes the finishing temperature of aluminium alloy rod; Aluminium alloy rod is carried out the cold drawn aluminum alloy line that is processed into 3.0mm, be drawn into aluminum alloy line with 7 and carry out strandedly, be prepared into conductor thread core; Described aluminium alloy conductor is carried out anneal, and annealing temperature is 370 ℃, and the time is 12h, stop the body of heater heating, then annealing furnace is Sino-Japan so cooling, takes out from stove after 24h, obtains aluminium alloy conductor.The aluminium alloy conductor of preparation is carried out performance test, and result is referring to table 2.
The component list (wt%) of the aluminium alloy of table 1 embodiment preparation
The component list (continued) of the aluminium alloy of table 1 embodiment preparation (wt%)
The component list (continued) of the aluminium alloy of table 1 embodiment preparation (wt%)
The performance test data table of the aluminium alloy of table 2 embodiment and Comparative Examples preparation
The performance test data table (continued) of the aluminium alloy of table 2 embodiment and Comparative Examples preparation
By relatively can finding out of table 2, aluminum alloy materials of the present invention has obvious advantage from over-all properties, particularly the long-time running heat resisting temperature can reach 235 ℃, and after heat-resisting test run(s), the intensity survival rate can reach 91%, 90 degree repeatedly bend number of times and reach 37 times, minimum bending radius is greater than 4.5 times of outside diameters of cable, and 400h anti-corrosion test mass loss is less than 0.9g/m
2Hr, the monofilament minimum machining diameter is greater than 0.1mm.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be apparent concerning those skilled in the art, and General Principle as defined herein can be in the situation that do not break away from the spirit or scope of the present invention, realization in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. Al-Fe-Rb-RE aluminium alloy comprises:
0.01 the Fe of ~ 1.6wt%; 0.001 the Cu of ~ 0.3wt%; 0.001 the Mg of ~ 0.3wt%; 0.001 the Co of ~ 0.3wt%; 0.001 the Be of ~ 0.2wt%; 0.001 the Ca of ~ 0.3wt%; 0.001 the Zn of ~ 0.2wt%; 0.001 the Sr of ~ 0.3wt%; 0.001 the Zr of ~ 0.3wt%; 0.002 the Li of ~ 0.25wt%; 0.001 the Na of ~ 0.2wt%; 0.002 the K of ~ 0.25wt%; 0.001 the Ti of ~ 0.2wt%; 0.001 the V of ~ 0.15wt%; 0.001 the Cr of ~ 0.12wt%; 0.001 the Mn of ~ 0.12wt%; 0.001 the Ni of ~ 0.15wt%; 0.001 the Ga of ~ 0.2wt%; 0.003 the Ge of ~ 0.2wt%; 0.001 the Rb of ~ 0.2wt%; 0.01 the RE of ~ 3.0wt%; Greater than zero and less than or equal to the Si of 0.2wt%; Greater than zero and less than or equal to the B of 0.8wt%; The aluminium of surplus.
2. aluminium alloy according to claim 1, is characterized in that, comprises the Fe of 0.25 ~ 0.6wt%.
3. aluminium alloy according to claim 1, is characterized in that, comprises the RE of 0.1 ~ 0.6wt%.
4. aluminium alloy according to claim 1, is characterized in that, comprises the Rb of 0.005 ~ 0.15wt%.
5. the preparation method of an Al-Fe-Rb-RE aluminium alloy, is characterized in that, comprises the following steps:
a) aluminium alloy cast ingot of the following composition of casting: the Fe of 0.01 ~ 1.6wt%, 0.001 the Cu of ~ 0.3wt%, 0.001 the Mg of ~ 0.3wt%, 0.001 the Co of ~ 0.3wt%, 0.001 the Be of ~ 0.2wt%, 0.001 the Ca of ~ 0.3wt%, 0.001 the Zn of ~ 0.2wt%, 0.001 the Sr of ~ 0.3wt%, 0.001 the Zr of ~ 0.3wt%, 0.002 the Li of ~ 0.25wt%, 0.001 the Na of ~ 0.2wt%, 0.002 the K of ~ 0.25wt%, 0.001 the Ti of ~ 0.2wt%, 0.001 the V of ~ 0.15wt%, 0.001 the Cr of ~ 0.12wt%, 0.001 the Mn of ~ 0.12wt%, 0.001 the Ni of ~ 0.15wt%, 0.001 the Ga of ~ 0.2wt%, 0.003 the Ge of ~ 0.2wt%, 0.001 the Rb of ~ 0.2wt%, 0.01 the RE of ~ 3.0wt%, greater than zero and less than or equal to the Si of 0.2wt%, greater than zero and less than or equal to the B of 0.8wt% and the aluminium of surplus,
B) described aluminium alloy cast ingot is carried out homogenizing and process, the aluminium alloy cast ingot after homogenizing is processed is rolled, and obtains the aluminium alloy pole stock;
C) the aluminium alloy pole stock that step b) is obtained carries out the intermittent type anneal;
D) the aluminium alloy pole stock that step c) is obtained carries out ageing treatment, obtains aluminium alloy.
6. preparation method according to claim 5, is characterized in that, the temperature that described homogenizing is processed is 450 ~ 550 ℃, and the time that described homogenizing is processed is 6 ~ 16h, and the heat-up rate that described homogenizing is processed is 3 ~ 8 ℃/min.
7. preparation method according to claim 5, is characterized in that, described step c) is specially:
The aluminium alloy pole stock that step b) is obtained is heated to 280 ~ 350 ℃, lowers the temperature after insulation 2 ~ 8h, and temperature is down to 150 ~ 200 ℃, and is cooling after insulation 2 ~ 4h.
8. preparation method according to claim 5, is characterized in that, described ageing treatment is to carry out in 5 ~ 15KV/cm uniform electric field in strength of electric field.
9. preparation method according to claim 5, is characterized in that, the temperature of described ageing treatment is 250 ~ 320 ℃, and the time of described ageing treatment is 4 ~ 20h.
10. a power cable, comprise core, insulation layer, screen layer and protective layer, it is characterized in that, described core is the described aluminium alloy of claim 1 ~ 4 any one or the prepared aluminium alloy of claim 5 ~ 9 any one.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101587757A (en) * | 2009-06-19 | 2009-11-25 | 金杯电工股份有限公司 | Aluminum alloy lead with lanthanon yttric and preparation method thereof |
| CN101805858A (en) * | 2009-09-23 | 2010-08-18 | 贵州华科铝材料工程技术研究有限公司 | Li-RE high-strength heat-resistance aluminum alloy material and preparation method thereof |
| CN101886198A (en) * | 2010-07-13 | 2010-11-17 | 安徽欣意电缆有限公司 | High-conductivity aluminum alloy material for cable and preparation method thereof |
| CN102268575A (en) * | 2011-07-20 | 2011-12-07 | 安徽欣意电缆有限公司 | Aluminum alloy material and preparation method thereof |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101587757A (en) * | 2009-06-19 | 2009-11-25 | 金杯电工股份有限公司 | Aluminum alloy lead with lanthanon yttric and preparation method thereof |
| CN101805858A (en) * | 2009-09-23 | 2010-08-18 | 贵州华科铝材料工程技术研究有限公司 | Li-RE high-strength heat-resistance aluminum alloy material and preparation method thereof |
| CN101886198A (en) * | 2010-07-13 | 2010-11-17 | 安徽欣意电缆有限公司 | High-conductivity aluminum alloy material for cable and preparation method thereof |
| CN102268575A (en) * | 2011-07-20 | 2011-12-07 | 安徽欣意电缆有限公司 | Aluminum alloy material and preparation method thereof |
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