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CN105112745A - Graphene/aluminum alloy composite material - Google Patents

Graphene/aluminum alloy composite material Download PDF

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Publication number
CN105112745A
CN105112745A CN201510388353.8A CN201510388353A CN105112745A CN 105112745 A CN105112745 A CN 105112745A CN 201510388353 A CN201510388353 A CN 201510388353A CN 105112745 A CN105112745 A CN 105112745A
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graphene
aluminum alloy
aluminum
composite material
alloy composite
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Inventor
李炯利
王旭东
何维维
戴圣龙
张晓艳
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BEIJING INSTITUTE OF AERONAUTICAL MATERIALS CHINA AVIATION INDUSTRY GROUP Corp
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BEIJING INSTITUTE OF AERONAUTICAL MATERIALS CHINA AVIATION INDUSTRY GROUP Corp
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Abstract

The invention provides a graphene/aluminum alloy composite material. The adding amount of graphene in the composite material is 0.1wt.% to 5.0wt.% of the total amount of the composite material. Compared with the tensile strength of aluminum alloy without the added graphene, the mechanical performance tensile strength and the electrical conductivity of the graphene/aluminum alloy composite material are improved to different degrees. Due to appearing of an intermediate alloy of the graphene/aluminum alloy composite material, the graphene can be added into molten aluminum in a graphene/aluminum alloy intermediate alloy form, the dispersion uniformity of the graphene in the molten aluminum is improved to the maximum degree, and therefore industrial mass production of graphene-modified aluminum conductor cables can be achieved with a melting casting method. A preparing method of the composite material includes the steps of mechanical mixing, low-temperature ball milling, vacuum air removing, hot isostatic pressing, extruding and the like. The graphene/aluminum alloy composite material is simple and controllable in technology, lower in production cost, suitable for industrial production and good in market prospect.

Description

A kind of graphene/aluminum alloy composite materials
Technical field
The present invention relates to a kind of matrix material, specifically relate to a kind of graphene/aluminum alloy composite materials and preparation method thereof.
Background technology
Large owing to hanging span in the air, overhead high voltage transmission line, except there are certain requirements the electroconductibility of leader cable, also there are certain requirements the intensity of leader cable.Overhead high voltage electricity transmission conductive wire comparatively conventional both at home and abroad at present comprises copper conductor and aluminium conductor.Compared with aluminium conductor, the good conductivity of copper conductor, intensity is high.But the cost of copper conductor is higher, and copper belongs to strategic resource, and bauxite resource enriches, and widely distributed, cost is low.Although some places transmitting line almost more than 90% uses aluminum composite conductor, the application quantity of some local aluminum composite conductor is less than 1%.Therefore, in order to reduce costs, be necessary the Application and Development strengthening overhead high voltage power transmission aluminium conductor cable.
The aluminium conductor cable material of industrial application comprises fine aluminium and aluminum composite at present, but the matching of the intensity of the two and electroconductibility is all lower.The good conductivity of fine aluminium, but intensity is lower.Existing aluminum composite is on the basis of fine aluminium, and the alloying elements such as interpolation Mg, Si obtain, and obtained matrix material, while the raising strength of materials, but brings the reduction of electroconductibility.In recent years, along with the suspension span of overhead high voltage transmission line is increasing, the performance of aluminium conductor cable is had higher requirement.
Graphene is a kind of two-dimension nano materials be made up of carbon atom, in individual layer sheet structure (thickness is only several nanometer).Due to bi-dimensional cellular crystalline structure and the high bonding strength of its uniqueness, Graphene is the nano material that specific tenacity is high, the hardest in the world known at present, and its breaking tenacity is up to 130Gpa.(ChangguLee, XiaodingWei, JeffreyW.Kysar, etc. JamesHone) people is at " science " (Science, Vol.321, issue18, July2008,385-388) on delivered about " mensuration of single-layer graphene retractility and inherent strength " (Measurementoftheelasticpropertiesandintrinsicstrengthonm onolayergraphene).The more important thing is, material that Graphene or in the world specific conductivity are the highest (resistivity only about 10 -8Ω m), be about 100 times of copper.Therefore, utilize the high strength of Graphene and good electroconductibility, and by itself and fine aluminium or aluminum composite compound, be prepared into graphene/aluminum alloy composite materials, be expected the intensity for improving aluminium cable and electroconductibility, the mechanical property of aluminium conductor and electric property are better mated.
Based on above Discuss and analyse, need to provide a kind of preparation technology to obtain graphene/aluminum alloy composite materials, and the high quality interface realizing the dispersed and graphene/aluminum of Graphene in aluminum substrate combines.Preparation method's mainly melt casting and powder metallurgic method of aluminum current based composites.If graphene/aluminum alloy composite materials adopts the preparation of conventional melt casting, because the two density variation is large, Graphene is difficult in the dispersion of aluminium liquid inner homogeneous, and in addition, the two also high-temperature interface reaction likely occurs in material preparation process, generates Al 4c 3brittlement phase, worsens material property.And adopt powder metallurgic method, graphene nanometer sheet and aluminum composite powder then can be made at room temperature to realize Homogeneous phase mixing, then prepare Graphene by follow-up press working and strengthen aluminum-base composite block materials, the high-temperature interface that inhibit conventional melt casting to bring to greatest extent reacts.
But, fact proved, because graphene nanometer sheet and aluminum composite powder (atomization) all also exist very large difference (see table 1) in pattern, size and density etc., consistency both causing when Material cladding is very poor, even if the aluminium of nonmetallic Graphene and metal is also difficult to form good interface cohesion under powder metallurgical technique.(BARTOLUCCISF, PARASJ, RAFIEEMA, etc. etal.) people is at " Materials science and engineering " periodical [[J] .MaterialScienceandEngineeringA, 2011,528:7933-7937.)] on disclose Graphene-aluminium nano-composition " Graphene-aluminumnanocomposites ".And for aluminum matrix composite, whether the distribution of wild phase in aluminum substrate be even, whether wild phase reunites, whether interface cohesion is tight, directly decide the quality of composite property.Therefore, how dispersed in aluminum substrate of Graphene realizes, and the high quality interface of graphene/aluminum combines and how to obtain, and is the gordian technique preparing the breakthrough of graphene/aluminum alloy composite materials needs.
The difference of table 1 graphene nanometer sheet and aluminum composite powder
The low temperature ball-milled powder metallurgical technology occurred in recent years is compared with traditional powder metallurgic method, in the dispersiveness improving wild phase and interface cohesion, have obvious advantage.The powder of wild phase and matrix phase just mixes by mechanical ball milling that conventional powder metallurgical technique adopts equably, is difficult to just form interface cohesion between powder in mechanical milling process; And the metallurgical rule of low temperature ball-milled powder introduces the inertia cryogenic medias such as liquid nitrogen (or liquid argon) in traditional Mechanical Milling Process, the milling atmosphere (low temperature and inert media) of its uniqueness makes it have plurality of advantages.Pertinent literature shows (YEJC, HEJH, SCHOENUNGJM.CryomillingforthefabricationofaparticulateB 4creinforcedAlnanocomposite:PartI.Effectsofprocessconditi onsonstructure [J] .MetallurgicalandMaterialsTransactionA, 2006,37A:3099-3109.), ceramic particle/aluminium mixed powder is through low temperature ball milling, while the nanocrystalline aluminum substrate of acquisition, achieve dispersed in aluminium of ceramic particle, also ceramic particle can be coated on aluminium inside, form high-quality interface cohesion.Therefore, can attempt realizing graphene nanometer sheet being uniformly distributed in aluminium by low temperature ball grinding technique, obtaining high-quality graphene/aluminum interface.
Fact proved, adopt low temperature ball-milled powder metallurgy method not only can realize effective interpolation of high quality mark Graphene (1.0%), but also greatly can improve the dispersiveness of Graphene in aluminium and the interface cohesion situation of graphene/aluminum.(LIJL, XIONGYC, WANGXD, YANSJ, YANGC, HEWW, CHENJZ, WANGSQ, ZHANGXY, etc. DAISL.) people has delivered the obtained nanostructure aluminium/graphene complex microtexture of cryogrinding and extension property " Microstructureandtensilepropertiesofbulknanostructuredal uminum/graphenecompositespreparedviacryomilling [J] .MaterialsScienceandEngineeringA, 2015,626:400-405) " on " Materials science and engineering " periodical.But, though adopt low temperature ball-milled powder metallurgy method can realize the improvement of the interface cohesion of the dispersed and graphene/aluminum of Graphene in aluminium, but, the method complex process, cost is higher, is not suitable for applying in the large-scale engineeringization of low value-added field (such as electrical equipment, cable etc.).
Apply for the through engineering approaches realizing graphene/aluminum alloy composite materials and adapt to the large-scale production of aluminium conductor cable product, just must adopt the method that melting is cast.But, directly join in aluminium liquid if Graphene is left intact, then can observe serious defect (pore, Graphene reunion etc.) in the ingot casting finally obtained, worsen material property.
Summary of the invention
In order to overcome the above-mentioned deficiency of prior art, the invention provides the technical scheme of the relative merits of a kind of consolidated powder metallurgy method and melt casting, prepared a kind of graphene/aluminum alloy composite materials of Graphene modified aluminium leader cable by powder metallurgy in conjunction with the method that melting is cast.In technical scheme provided by the invention: first, adopt low temperature ball grinding technique to prepare Graphene in conjunction with Hot-extrusion to be uniformly distributed in aluminum substrate and good " graphene/aluminum " matrix material extruded bars (or silk material) of interface cohesion, then it can be used as the master alloy of " graphene/aluminum ", make Graphene can join in the aluminium liquid of melting by the form of " graphene/aluminum " master alloy, farthest improve the dispersing uniformity of Graphene in aluminium liquid, thus make the suitability for industrialized production of graphitic modified aluminium leader cable become possibility.
Adopt low temperature ball grinding technique to prepare Graphene in conjunction with Hot-extrusion to be uniformly distributed in alloy matrix aluminum and good " graphene/aluminum " matrix material extruded bars (or silk material) of interface cohesion, it can be used as the master alloy of " graphene/aluminum ".
The object of the invention is to realize by the following technical solutions:
The invention provides a kind of graphene/aluminum alloy composite materials, its improvements are: described matrix material take aluminium as matrix, and Graphene addition is 0.1 ~ 5.0wt.% of described graphene/aluminum alloy composite materials; Described aluminium alloy chemical composition is by mass percentage: copper (maximum) 0.10; Iron (maximum): 0.50; Silicon: 0.50-0.9; Manganese (maximum) 0.03; Magnesium: 0.6-0.9; Zinc (maximum) 0.10; Chromium (maximum) 0.03; Boron: (maximum) 0.06; Other elements: (often kind maximum) 0.03; Other elements (total content is maximum): 0.10; Surplus is aluminium.
Another kind of graphene/aluminum alloy provided by the invention, its improvements are: Graphene addition is 0.1 ~ 3.0wt.% of described graphene/aluminum alloy composite materials.
Another graphene/aluminum alloy provided by the invention, its improvements are: Graphene addition is 0.2 ~ 3.0wt.% of described graphene/aluminum alloy composite materials.
4th kind of graphene/aluminum alloy composite materials provided by the invention, its improvements are: Graphene addition is 0.4 ~ 5.0wt.% of described graphene/aluminum alloy composite materials.
5th kind of graphene/aluminum alloy composite materials provided by the invention, its improvements are: Graphene addition is 1.0 ~ 3.0wt.% of described graphene/aluminum alloy composite materials.
6th kind of graphene/aluminum alloy composite materials provided by the invention, its improvements are: Graphene addition is the 3.0wt.% of described graphene/aluminum alloy composite materials.
The preparation method of a kind of graphene/aluminum alloy composite materials provided by the invention, the method comprises following processing step:
(1) be the aluminium alloy atomization powder of 30 ~ 70 μm and Graphene addition by granularity be 0.1 ~ 5.0wt.% mixture of graphene/aluminum alloy composite materials amount, mix in powder machine in " V " type of rotating speed 10 ~ 30r/min and mix 24 ~ 48h;
(2) mixed powder that step (1) is obtained is put into the VC high efficient mixer mixing 10 ~ 30min of rotating speed 100 ~ 200r/min;
(3) made mixed powder, abrading-ball and stearic acid are placed in stirring ball mill, are filled with liquid nitrogen, when liquid nitrogen submergence whole abrading-ball, start ball milling, ratio of grinding media to material is 30 ~ 40: 1;
(4) low temperature ball milling is after 2 ~ 4 hours, and take out powder and be placed in protection of inert gas case, after its temperature return to room temperature, load intracavity diameter is 80 ~ 120mm, and cavity heights is in the aluminum composite jacket of 85 ~ 300mm;
(5) in 300 ~ 350 DEG C and 2.0 × 10 -3under Pa vacuum tightness, to jacket vacuum stripping 2 ~ 4h, after degasification terminates, jacket is pounded flat, heal seal;
(6) under 400 ~ 500 DEG C and 100 ~ 120MPa pressure, hot isostatic pressing is carried out to the described jacket dwell time 2 ~ 4h of sealing;
(7) jacket after hot isostatic pressing is carried out mechanical workout, remove jacket skin, obtain cylindrical press blank, diameter is 55 ~ 85mm, is highly 55 ~ 200mm;
(8) by the extrusion billet of gained at 300 ~ 350 DEG C with tonnage be the extrusion machine of 200 ~ 500t with the extrusion ratio hot extrusion of 15: 1 ~ 20: 1, obtain described graphene/aluminum alloy composite materials bar.
Another kind provided by the invention prepares the method for graphene/aluminum alloy composite materials, the method comprises following processing step: its improvements are, described V-arrangement mixing machine is the not contour mixing staving combined after cuing open into 40 degree of angles by staving, by the mixing machine of pedestal two tanks bearing center axle, in mixing tank, be provided with mandatory whipping appts; Mix in powder machine in " V " type of rotating speed 20 ~ 30r/min and mix 15 ~ 24h.
It is provided by the invention that separately another prepares the method for graphene/aluminum alloy composite materials, the method comprises following processing step: its improvements are, the described VC high efficient mixer of described step (2) is conical shell, and Tong Nei is equipped with at center stirring main shaft.
Another kind provided by the invention prepares the method for graphene/aluminum alloy composite materials, and the method comprises following processing step: its improvements are, the described abrading-ball of described step (3) is high-carbon-chromium bearing steel material abrading-ball.
The method preparing graphene/aluminum alloy composite materials provided by the invention, wherein said aluminium alloy chemical composition is by mass percentage: a kind of method preparing graphene/aluminum alloy composite materials according to claim 1, it is characterized in that, the atomization of aluminium alloy described in described step (1) powder granularity is 40 μm, described black alkene addition is the 3.0wt.% of graphene/aluminum alloy composite materials amount, mixes in powder machine mix 40h in " V " type of rotating speed 10 ~ 20r/min.
The method preparing graphene/aluminum alloy composite materials provided by the invention, its improvements are, described aluminium alloy chemical composition is by mass percentage: copper (maximum) 0.10; Iron (maximum): 0.50; Silicon: 0.50-0.9; Manganese (maximum) 0.03; Magnesium: 0.6-0.9; Zinc (maximum) 0.10; Chromium (maximum) 0.03; Boron: (maximum) 0.06; Other elements: (often kind maximum) 0.03; Other elements (total content is maximum): 0.10; Aluminium: surplus
With immediate prior art ratio, technical scheme provided by the invention has following excellent effect:
(1) adopt low temperature ball grinding technique in conjunction with hot isostatic pressing, Hot-extrusions etc. are prepared Graphene and are uniformly distributed in alloy matrix aluminum and good " graphene/aluminum alloy " the matrix material extruded bars (or silk material) of interface cohesion, then it can be used as the master alloy of " graphene/aluminum alloy ", make Graphene can join in the aluminum alloy melt of melting by the form of " graphene/aluminum alloy " master alloy, farthest improve the dispersing uniformity of Graphene in aluminum alloy melt, thus make the suitability for industrialized production of graphitic modified aluminium alloy lead wire cable become possibility.
(2) material preparation process is simple, and it is controlled that technique is adjustable.Material preparation cost is lower, is applicable to suitability for industrialized production, good market prospects.
(3) the present invention uses V-arrangement mixing machine, VC high efficient mixer and high-carbon-chromium bearing steel material abrading-ball are conducive to Graphene being uniformly distributed and interface cohesion therebetween in alloy matrix aluminum.
Embodiment
Prepare to provided by the invention detailed, the specific description that aluminium alloy/graphene composite material does indefiniteness below by specific embodiments.
Embodiment 1:
Get business aluminium alloy atomization powder (nitrogen atomization, purity >=99%) 999 grams, Graphene (Hummer ' s legal system standby) 1g, concrete preparation process is as follows:
(1) by granularity 30 μm, the Graphene addition of pure aluminum alloy atomization powder and interpolation is that the 0.1wt.% mixture of graphene/aluminum mixture total amount mixes in powder machine in " V " type of rotating speed 10r/min and mixes 24h;
(2) mixed powder is put into the VC high efficient mixer mixing 10min of rotating speed 100r/min;
(3) mixed powder, high-carbon-chromium bearing steel material abrading-ball and stearic acid are placed in stirring ball mill simultaneously, are filled with liquid nitrogen, when liquid nitrogen submergence whole abrading-ball, start ball milling.Wherein ratio of grinding media to material is 30: 1;
(4) low temperature ball milling is after 2 hours, take out powder and be placed in protection of inert gas case, after its temperature return to room temperature, load material is 3A21 aluminum composite, and thickness is 2mm, jacket intracavity diameter is Φ 80mm, and jacket cavity heights is in the jacket of 85mm;
(5) in vacuum tightness 2.0 × 10 -3at Pa and 300 DEG C, jacket is carried out vacuum stripping 2h, after degasification terminates, jacket is pounded flat, heal seal;
(6) in 400 DEG C, under 100MPa pressure, by the jacket hot isostatic pressing heat-insulation pressure keeping 2h after sealing;
(7) jacket skin is removed in turning, and obtaining diameter is Φ 55mm, is highly the cylindrical press blank of 55mm;
(8) by this extrusion billet at 300 DEG C, with the hot extrusion under for 15: 1 extrusion ratios of the extrusion machine of tonnage 200t, obtain " graphene/aluminum " compound walking spa-cial system, i.e. graphene/aluminum matrix material.
The bar room temperature tensile intensity of the graphene/aluminum alloy composite materials taking above technique to prepare is 300MPa, and elongation is 12%, and electric conductivity (IACS) is 63%.As compared to the aluminium alloy (tensile strength 220MPa, elongation is 10%, IACS49.9%) not adding Graphene, the tensile strength of graphene/aluminum alloy composite materials extruded bars improves, and elongation and electric conductivity all increase.
Embodiment 2 ~ 5 is listed in the table below, and sequence of process steps wherein and term implication and embodiment 1 are with, the different numerical value of the parameter corresponding from embodiment 1 that listed is:
Finally should be noted that: above embodiment is only in order to illustrate that technical scheme of the present invention is not intended to limit; those of ordinary skill in the field are to be understood that; can modify to the specific embodiment of the present invention with reference to above-described embodiment or equivalent replacement; these do not depart from any amendment of spirit and scope of the invention or equivalent replacement, and it all should be encompassed within claims of the present invention.

Claims (5)

1. prepare a graphene/aluminum alloy composite materials, it is characterized in that: described matrix material take aluminium alloy as matrix, Graphene addition is 0.1 ~ 5.0wt.% of described graphene/aluminum alloy composite materials; Described aluminium alloy chemical composition is by mass percentage: copper (maximum) 0.10; Iron (maximum): 0.50; Silicon: 0.50-0.9; Manganese (maximum) 0.03; Magnesium: 0.6-0.9; Zinc (maximum) 0.10; Chromium (maximum) 0.03; Boron: (maximum) 0.06; Other elements: (often kind maximum) 0.03; Other elements (total content is maximum): 0.10; Surplus is aluminium.
2. prepare a graphene/aluminum alloy composite materials, it is characterized in that: Graphene addition is 0.1 ~ 3.0wt.% of described graphene/aluminum alloy composite materials.
3. prepare a graphene/aluminum alloy composite materials, it is characterized in that: Graphene addition is 0.2 ~ 3.0wt.% of described graphene/aluminum alloy composite materials.
4. prepare a graphene/aluminum alloy composite materials, it is characterized in that: Graphene addition is 0.4 ~ 5.0wt.% of described graphene/aluminum alloy composite materials.
5. prepare a graphene/aluminum alloy composite materials, it is characterized in that: Graphene addition is 1.0 ~ 3.0wt.% of described graphene/aluminum alloy composite materials.
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Cited By (9)

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CN105112732A (en) * 2015-06-25 2015-12-02 中国航空工业集团公司北京航空材料研究院 Graphene/aluminium alloy composite
CN106587025A (en) * 2016-12-27 2017-04-26 东南大学 Preparation method of graphene inorganic nonmetal composite material
CN106629680A (en) * 2016-12-27 2017-05-10 东南大学 Preparation method of graphene metal composite material
CN107269704A (en) * 2017-06-14 2017-10-20 三峡大学 The graphite of a kind of graphene-containing/aluminium base self-lubricating plain bearing and preparation method thereof
CN107675622A (en) * 2017-10-26 2018-02-09 杨晓艳 A kind of steel wire bridge cable of the low deadweight of high intensity
CN108326311A (en) * 2017-12-25 2018-07-27 新疆烯金石墨烯科技有限公司 A kind of continuously extruded preparation method of graphene aluminium alloy conductor
CN112853164A (en) * 2019-11-26 2021-05-28 南京工程学院 Method for strengthening and toughening aluminum alloy by using composite nano-phase under action of cyclic alternating stress
CN115466883A (en) * 2021-06-10 2022-12-13 特变电工股份有限公司 High-conductivity graphene aluminum alloy rod, preparation method thereof and high-conductivity graphene aluminum alloy stranded wire
CN116497249A (en) * 2023-03-28 2023-07-28 苏州创泰合金材料有限公司 High-heat-conductivity aluminum alloy material and preparation method thereof

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Cited By (12)

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Publication number Priority date Publication date Assignee Title
CN105112732A (en) * 2015-06-25 2015-12-02 中国航空工业集团公司北京航空材料研究院 Graphene/aluminium alloy composite
CN106587025A (en) * 2016-12-27 2017-04-26 东南大学 Preparation method of graphene inorganic nonmetal composite material
CN106629680A (en) * 2016-12-27 2017-05-10 东南大学 Preparation method of graphene metal composite material
CN107269704A (en) * 2017-06-14 2017-10-20 三峡大学 The graphite of a kind of graphene-containing/aluminium base self-lubricating plain bearing and preparation method thereof
CN107675622A (en) * 2017-10-26 2018-02-09 杨晓艳 A kind of steel wire bridge cable of the low deadweight of high intensity
CN108326311A (en) * 2017-12-25 2018-07-27 新疆烯金石墨烯科技有限公司 A kind of continuously extruded preparation method of graphene aluminium alloy conductor
CN108326311B (en) * 2017-12-25 2021-10-08 新疆烯金石墨烯科技有限公司 Continuous extrusion preparation method of graphene aluminum alloy wire
CN112853164A (en) * 2019-11-26 2021-05-28 南京工程学院 Method for strengthening and toughening aluminum alloy by using composite nano-phase under action of cyclic alternating stress
CN112853164B (en) * 2019-11-26 2021-09-17 南京工程学院 Method for strengthening and toughening aluminum alloy by using composite nano-phase under action of cyclic alternating stress
CN115466883A (en) * 2021-06-10 2022-12-13 特变电工股份有限公司 High-conductivity graphene aluminum alloy rod, preparation method thereof and high-conductivity graphene aluminum alloy stranded wire
CN116497249A (en) * 2023-03-28 2023-07-28 苏州创泰合金材料有限公司 High-heat-conductivity aluminum alloy material and preparation method thereof
CN116497249B (en) * 2023-03-28 2024-11-22 苏州创泰合金材料有限公司 A kind of high thermal conductivity aluminum alloy material and preparation method thereof

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