CN108342611A - A kind of preparation method of high-strength copper based alloy blank - Google Patents

A kind of preparation method of high-strength copper based alloy blank Download PDF

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CN108342611A
CN108342611A CN201810491519.2A CN201810491519A CN108342611A CN 108342611 A CN108342611 A CN 108342611A CN 201810491519 A CN201810491519 A CN 201810491519A CN 108342611 A CN108342611 A CN 108342611A
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powder
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pure niobium
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不公告发明人
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D7/00—Casting ingots, e.g. from ferrous metals
    • B22D7/005—Casting ingots, e.g. from ferrous metals from non-ferrous metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D7/00—Casting ingots, e.g. from ferrous metals
    • B22D7/06—Ingot moulds or their manufacture
    • B22D7/064—Cooling the ingot moulds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/12—Making non-ferrous alloys by processing in a semi-solid state, e.g. holding the alloy in the solid-liquid phase
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper

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Abstract

The invention discloses a kind of preparation methods of high-strength copper based alloy blank, include the following steps：(1) it is 97wt%, pure niobium ingot 1wt%, pure niobium powder 1wt%, graphene powder 1wt% at fine copper ingot is grouped into using fine copper ingot, pure niobium ingot, pure niobium powder, graphene powder as raw material；(2) 1300 DEG C are heated to after first mixing fine copper ingot, pure niobium ingot; it is set to be melted into alloy melt; after keeping the temperature 10min; melt liquid level is protected using argon gas; and pure niobium powder, graphene powder is added, 5min is sufficiently stirred to alloy melt, while alloy melt temperature is reduced to 1200 DEG C; and 10 15min are kept the temperature, make alloy melt quick solidification and forms the melt of semisolid line and staff control；(3) melt cast of semisolid line and staff control is prepared in using the grinding tool of circulating water and forms ingot casting, be cooled to room temperature with the speed of 190 DEG C/min, obtain the high-intensity high-conductivity copper based alloy blank of graphene-containing；Wherein, a diameter of 0.05 100 μm of pure niobium powder.Acid bronze alloy blank prepared by the present invention has the advantages that intensity is high.

Description

A kind of preparation method of high-strength copper based alloy blank
Technical field
The invention belongs to copper-based alloy material technical fields, and in particular to a kind of preparation side of high-strength copper based alloy blank Method.
Background technology
Copper and copper alloy length are used for the fields such as lead frame, electrical contact, high ferro cable and motor electric wire, but traditional Copper and copper it is total intensity it is not high, therefore the copper alloy of high strength and high conductivity is researched and developed.Common high strength high conducting copper The intensifying method of alloy has processing hardening, solution strengthening, refined crystalline strengthening and second-phase strength, wherein solution strengthening is to pass through conjunction Gold element incorporates Copper substrate and generates distortion of lattice, improves the reinforcing means of alloy strength to hinder dislocation motion, but formed When solid solution, alloy conductive performance can reduce, and the distortion distortion of solvent lattice destroys the periodicity of potential field of lattice, only a small number of The micro influences being added in copper to copper resistance rate of element such as Cd, Zn, Ag, Ni, Pb, Sn, Nb are little, and it is strong can also to improve matrix Degree.
There is higher conductivity and tensile strength by the copper microcomposite of representative of Cu-Nb, Cu-Ag, be most may be used It can realize the resistance to conductor materials for rushing high-intensity magnetic field of 100T, but the solid solubility of Nb and Ag in Cu is extremely low, elasticity capacity is sufficiently close to, High electric conductivity and toughness can also be obtained.A kind of high intensity, highly conductive, high temperature resistance disclosed in Chinese patent CN101818273B The preparation method of the Cu-Nb alloys of softening performance grinds copper powder and the Nb spheres of powder to obtain Cu-Nb Nanocrystalline Solid Solution powder, through moving back It is mixed with boron powder after fire, vacuum-sintering obtains Cu-Nb alloy billets, is finally sealed with copper clad, hot extrusion obtains product.The party When institutional framework being reached nano-scale in method, high strength ＆ high electric-conduction energy is obtained, boron powder improves Cu-Nb circle under nanoscale The stability in face.A kind of Cu-Ni-Si based alloys disclosed in Chinese patent CN102703754 and preparation method thereof, by fine copper, pure Silicon, pure nickel and pure vanadium melting pour to obtain blank, then nearly annealing, hot rolling, cold rolling, solid solution and ageing treatment obtain product.By existing Have technology it is found that at present acid bronze alloy to prepare raw material all be metal powder, can not directly prepare the copper alloy blank of thin product, it is raw The production period is long, cannot achieve mass production.
Invention content
The technical problem to be solved in the present invention is to provide a kind of preparation methods of high-strength copper based alloy blank.
In order to solve the above technical problems, the technical scheme is that：
A kind of preparation method of high-strength copper based alloy blank, includes the following steps：
(1) using fine copper ingot, pure niobium ingot, pure niobium powder, graphene powder as raw material, it is at fine copper ingot is grouped into 97wt%, pure niobium ingot 1wt%, pure niobium powder 1wt%, graphene powder 1wt%；
(2) 1300 DEG C are heated to after first mixing fine copper ingot, pure niobium ingot, it is made to be melted into alloy melt, keeps the temperature 10min Afterwards, melt liquid level is protected using argon gas, and pure niobium powder, graphene powder is added, 5min is sufficiently stirred to alloy melt, together When alloy melt temperature is reduced to 1200 DEG C, and keep the temperature 10-15min, make alloy melt quick solidification and form semisolid The melt of line and staff control；
(3) melt cast of semisolid line and staff control is prepared in using the grinding tool of circulating water and forms ingot casting, with The speed of 190 DEG C/min is cooled to room temperature, and obtains the high-intensity high-conductivity copper based alloy blank of graphene-containing.
Wherein, a diameter of 0.05-100 μm of pure niobium powder.
Preferably, pure niobium powder is 30 μm in the step (1), and takes out its oxide on surface by reduction treatment.
Preferably, in the step (1) graphene powder a diameter of 20nm, thickness be 5 carbon atom thickness.
Preferably, the particle diameter of fine copper powder is 0.05-100 μm in the step (1).
Preferably, the particle diameter of pure niobium powder is 0.5-30 μm in the step (1).
Preferably, the particle diameter of fine silver powder is 25-50nm in the step (1).
Specific implementation mode
The present embodiment 1：
(1) using fine copper ingot, fine silver ingot, fine copper powder, graphene powder as raw material, it is at fine copper ingot is grouped into 85wt%, fine silver ingot 12wt%, fine copper powder 2wt%, graphene powder 1wt%, total amount 100%, wherein fine copper powder A diameter of 0.5 μm, and take out its oxide on surface by reduction treatment.
(2) 1100 DEG C are heated to after first mixing fine copper ingot, fine silver ingot, it is made to be melted into alloy melt, keeps the temperature 10min Afterwards, melt liquid level is protected using argon gas, and fine copper powder, graphene powder is added, it is molten to alloy using mechanical agitation mode Body is sufficiently stirred 3min, while alloy melt temperature is reduced to 900 DEG C, and keeps the temperature 10min, makes alloy melt quick solidification simultaneously And form the melt of semisolid line and staff control.
(3) melt cast of semisolid line and staff control is prepared in using the grinding tool of circulating water and forms ingot casting, with The speed of 80 DEG C/min is cooled to room temperature, and obtains the high-intensity high-conductivity copper based alloy blank of graphene-containing.
(4) by the high-intensity high-conductivity copper based alloy blank heating of graphene-containing to 710 DEG C, keep the temperature 1h, by ingot casting along Forging molding longitudinally, laterally is carried out with axial three orthogonal directions distribution, forging drafts 30% in each direction then will Forging stock is air-cooled to room temperature, then forging stock is heated to 500 DEG C of heat preservation 1h, along longitudinally, laterally with axial three orthogonal directions distribution Forging molding is carried out, forging stock is then air-cooled to room temperature, then forging stock is heated to by forging drafts 30% in each direction 400 DEG C of heat preservation 1h carry out forging molding, forging in each direction along being longitudinally, laterally distributed with axial three orthogonal directions Forging stock is then air-cooled to room temperature, then forging stock is heated to 300 DEG C of heat preservation 1h by drafts 30%, along longitudinally, laterally and axial Three orthogonal direction distributions carry out forging molding, and forging stock is then air-cooled to room temperature by forging drafts 30% in each direction.
Embodiment 2：
(1) using fine copper ingot, pure niobium ingot, pure niobium powder, graphene powder as raw material, it is at fine copper ingot is grouped into 97wt%, pure niobium ingot 1wt%, pure niobium powder 1wt%, graphene powder 1wt%, total amount 100%, wherein pure niobium powder is straight Diameter is 30 μm, and takes out its oxide on surface by reduction treatment.
(2) 1300 DEG C are heated to after first mixing fine copper ingot, pure niobium ingot, it is made to be melted into alloy melt, keeps the temperature 10min Afterwards, melt liquid level is protected using argon gas, and pure niobium powder, graphene powder is added, it is molten to alloy using mechanical agitation mode Body is sufficiently stirred 5min, while alloy melt temperature is reduced to 1200 DEG C, and keeps the temperature 15min, makes alloy melt quick solidification And form the melt of semisolid line and staff control.
(3) melt cast of semisolid line and staff control is prepared in using the grinding tool of circulating water and forms ingot casting, with The speed of 190 DEG C/min is cooled to room temperature, and obtains the high-intensity high-conductivity copper based alloy blank of graphene-containing.
Embodiment 3：
(1) using fine copper ingot, fine silver ingot, fine silver powder, graphene powder as raw material, it is at fine copper ingot is grouped into 87wt%, fine silver ingot 10wt%, fine silver powder 2wt%, graphene powder 1wt%, total amount 100%, wherein fine silver powder A diameter of 25 μm, and take out its oxide on surface by reduction treatment.
(2) 1100 DEG C are heated to after first mixing fine copper ingot, fine silver ingot, it is made to be melted into alloy melt, keeps the temperature 10min Afterwards, melt liquid level is protected using argon gas, and fine silver powder, graphene powder is added, it is molten to alloy using mechanical agitation mode Body is sufficiently stirred 3min, while alloy melt temperature is reduced to 1000 DEG C, and keeps the temperature 10min, makes alloy melt quick solidification And form the melt of semisolid line and staff control.
(3) melt cast of semisolid line and staff control is prepared in using the grinding tool of circulating water and forms ingot casting, with The speed of 100 DEG C/min is cooled to room temperature, and obtains the high-intensity high-conductivity copper based alloy blank of graphene-containing.
(4) by the high-intensity high-conductivity copper based alloy blank heating of graphene-containing to 720 DEG C, keep the temperature 1h, by ingot casting along Forging molding longitudinally, laterally is carried out with axial three orthogonal directions distribution, forging drafts 20% in each direction then will Forging stock is air-cooled to room temperature, then forging stock is heated to 500 DEG C of heat preservation 1h, along longitudinally, laterally with axial three orthogonal directions distribution Forging molding is carried out, forging stock is then air-cooled to room temperature, then forging stock is heated to by forging drafts 20% in each direction 400 DEG C of heat preservation 1h carry out forging molding, forging in each direction along being longitudinally, laterally distributed with axial three orthogonal directions Forging stock is then air-cooled to room temperature, then forging stock is heated to 300 DEG C of heat preservation 1h by drafts 20%, along longitudinally, laterally and axial Three orthogonal direction distributions carry out forging molding, and forging stock is then air-cooled to room temperature by forging drafts 20% in each direction.
Embodiment 4：
(1) using fine copper ingot, fine silver ingot, fine copper powder, graphene powder as raw material, it is at fine copper ingot is grouped into 65wt%, fine silver ingot 30wt%, fine copper powder 4wt%, graphene powder 1wt%, total amount 100%, wherein fine copper powder A diameter of 50 μm, and take out its oxide on surface by reduction treatment.
(2) 1050 DEG C are heated to after first mixing fine copper ingot, fine silver ingot, it is made to be melted into alloy melt, keeps the temperature 10min Afterwards, melt liquid level is protected using argon gas, and fine copper powder, graphene powder is added, it is molten to alloy using mechanical agitation mode Body is sufficiently stirred 5min, while alloy melt temperature is reduced to 900 DEG C, and keeps the temperature 10min, makes alloy melt quick solidification simultaneously And form the melt of semisolid line and staff control.
(3) melt cast of semisolid line and staff control is prepared in using the grinding tool of circulating water and forms ingot casting, with The speed of 100 DEG C/min is cooled to room temperature, and obtains the high-intensity high-conductivity copper based alloy blank of graphene-containing.
(4) by the high-intensity high-conductivity copper based alloy blank heating of graphene-containing to 710 DEG C, keep the temperature 1h, by ingot casting along Forging molding longitudinally, laterally is carried out with axial three orthogonal directions distribution, forging drafts 40% in each direction then will Forging stock is air-cooled to room temperature, then forging stock is heated to 500 DEG C of heat preservation 1h, along longitudinally, laterally with axial three orthogonal directions distribution Forging molding is carried out, forging stock is then air-cooled to room temperature, then forging stock is heated to by forging drafts 10% in each direction 400 DEG C of heat preservation 1h carry out forging molding, forging in each direction along being longitudinally, laterally distributed with axial three orthogonal directions Forging stock is then air-cooled to room temperature, then forging stock is heated to 300 DEG C of heat preservation 1h by drafts 30%, along longitudinally, laterally and axial Three orthogonal direction distributions carry out forging molding, and forging stock is then air-cooled to room temperature by forging drafts 30% in each direction.
Embodiment 5：
(1) using fine copper ingot, pure niobium ingot, pure niobium powder, graphene powder as raw material, it is at fine copper ingot is grouped into 83.5wt%, pure niobium ingot 12.5wt%, pure niobium powder 2.5wt%, graphene powder 1.5wt%, total amount 100%, wherein pure A diameter of 2 μm of niobium powder, and take out its oxide on surface by reduction treatment.
(2) 1600 DEG C are heated to after first mixing fine copper ingot, pure niobium ingot, it is made to be melted into alloy melt, keeps the temperature 10min Afterwards, melt liquid level is protected using argon gas, and pure niobium powder, graphene powder is added, it is molten to alloy using mechanical agitation mode Body is sufficiently stirred 5min, while alloy melt temperature is reduced to 1500 DEG C, and keeps the temperature 10min, makes alloy melt quick solidification And form the melt of semisolid line and staff control.
(3) melt cast of semisolid line and staff control is prepared in using the grinding tool of circulating water and forms ingot casting, with The speed of 180 DEG C/min is cooled to room temperature, and obtains the high-intensity high-conductivity copper based alloy blank of graphene-containing.
Embodiment 6：
(1) using fine copper ingot, fine silver ingot, fine silver powder, graphene powder as raw material, it is at fine copper ingot is grouped into 75wt%, fine silver ingot 14wt%, fine silver powder 10wt%, graphene powder 1wt%, total amount 100%, wherein fine silver powder A diameter of 50 μm, and take out its oxide on surface by reduction treatment.
(2) 1700 DEG C are heated to after first mixing fine copper ingot, fine silver ingot, it is made to be melted into alloy melt, keeps the temperature 10min Afterwards, melt liquid level is protected using argon gas, and fine silver powder, graphene powder is added, it is molten to alloy using mechanical agitation mode Body is sufficiently stirred 3min, while alloy melt temperature is reduced to 1600 DEG C, and keeps the temperature 10min, makes alloy melt quick solidification And form the melt of semisolid line and staff control.
(3) melt cast of semisolid line and staff control is prepared in using the grinding tool of circulating water and forms ingot casting, with The speed of 200 DEG C/min is cooled to room temperature, and obtains the high-intensity high-conductivity copper based alloy blank of graphene-containing.
(4) by the high-intensity high-conductivity copper based alloy blank heating of graphene-containing to 720 DEG C, keep the temperature 1h, by ingot casting along Forging molding longitudinally, laterally is carried out with axial three orthogonal directions distribution, forging drafts 40% in each direction then will Forging stock is air-cooled to room temperature, then forging stock is heated to 500 DEG C of heat preservation 1h, along longitudinally, laterally with axial three orthogonal directions distribution Forging molding is carried out, forging stock is then air-cooled to room temperature, then forging stock is heated to by forging drafts 20% in each direction 400 DEG C of heat preservation 1h carry out forging molding, forging in each direction along being longitudinally, laterally distributed with axial three orthogonal directions Forging stock is then air-cooled to room temperature, then forging stock is heated to 300 DEG C of heat preservation 1h by drafts 30%, along longitudinally, laterally and axial Three orthogonal direction distributions carry out forging molding, and forging stock is then air-cooled to room temperature by forging drafts 10% in each direction.
After testing, embodiment 1-6 prepare graphene-containing high-intensity high-conductivity copper based alloy blank microscopic structure its Average crystal grain diameter, yield strength, tensile strength, the result of conductivity are as follows：
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Its average crystal grain diameter (μm) of microscopic structure 25 30 15 25 10 20
Yield strength (MPa) 820 950 710 890 1120 920
Tensile strength (MPa) 980 1300 900 1040 1700 1230
Conductivity (%IACS) 78 90 89 83 85 81
Compared with prior art, the invention has the advantages that：
(1) the high-intensity high-conductivity copper based alloy blank of graphene-containing prepared by the present invention is combined using solid-liquid double-phase solidification Pure copper powder/pure niobium powder and/or fine silver powder and Graphene powder are added in acid bronze alloy melt, and stirs for semi-solid casting technology It mixes to form microstructure of semisolid, notable refining alloy as-cast microstructure, is that more niobiums, silver and graphene are more solid-solution in copper In matrix, it is more advantageous to microstructure thinning technique during deformation after unloading and lays a good foundation, and pass through drawing, rolling mill practice Prepare the acid bronze alloy that microstructure thinning causes Nano grade.
(2) the high-intensity high-conductivity copper based alloy blank of graphene-containing prepared by the present invention is directly to prepare crystallite dimension Tiny large size copper based alloy blank, improves the processing efficiency of copper alloy blank, also the specification for acid bronze alloy blank has More washabilitys, and there is very high strength and electric conductivity, expand the application field of copper-based material.
(3) preparation method of the invention improve copper-based alloy material preparation it is horizontal, improve mass prepare it is copper-based The possibility of alloy material improves the big production of technology of copper-based alloy material.
It should be understood that the above-mentioned specific implementation mode of the present invention is used only for exemplary illustration or explains the present invention's Principle, but not to limit the present invention.Therefore, that is done without departing from the spirit and scope of the present invention is any Modification, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.In addition, appended claims purport of the present invention Covering the whole variations fallen into attached claim scope and boundary or this range and the equivalent form on boundary and is repairing Change example.

Claims (6)

1. a kind of preparation method of high-strength copper based alloy blank, which is characterized in that include the following steps：
(1) using fine copper ingot, pure niobium ingot, pure niobium powder, graphene powder as raw material, at be grouped into fine copper ingot be 97wt%, Pure niobium ingot 1wt%, pure niobium powder 1wt%, graphene powder 1wt%；
(2) 1300 DEG C are heated to after first mixing fine copper ingot, pure niobium ingot, it is made to be melted into alloy melt, after keeping the temperature 10min, Melt liquid level is protected using argon gas, and pure niobium powder, graphene powder is added, 5min is sufficiently stirred to alloy melt, simultaneously Alloy melt temperature is reduced to 1200 DEG C, and keeps the temperature 10-15min, make alloy melt quick solidification and forms semisolid is mixed It is combined the melt knitted；
(3) melt cast of semisolid line and staff control is prepared in using the grinding tool of circulating water and forms ingot casting, with 190 DEG C/speed of min is cooled to room temperature, obtain the high-intensity high-conductivity copper based alloy blank of graphene-containing.
Wherein, a diameter of 0.05-100 μm of pure niobium powder.
2. a kind of preparation method of high-strength copper based alloy blank according to claim 1, which is characterized in that the step (1) pure niobium powder is 30 μm in, and takes out its oxide on surface by reduction treatment.
3. a kind of preparation method of high-strength copper based alloy blank according to claim 1, which is characterized in that the step (1) a diameter of 20nm of graphene powder in, thickness are 5 carbon atom thickness.
4. a kind of preparation method of high-strength copper based alloy blank according to claim 1, which is characterized in that the step (1) particle diameter of fine copper powder is 0.05-100 μm in.
5. a kind of preparation method of high-strength copper based alloy blank according to claim 1, which is characterized in that the step (1) particle diameter of pure niobium powder is 0.5-30 μm in.
6. a kind of preparation method of high-strength copper based alloy blank according to claim 1, which is characterized in that the step (1) particle diameter of fine silver powder is 25-50nm in.
CN201810491519.2A 2017-03-22 2017-03-22 A kind of preparation method of high-strength copper based alloy blank Withdrawn CN108342611A (en)

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CN201810488791.5A Withdrawn CN108504894A (en) 2017-03-22 2017-03-22 A kind of acid bronze alloy blank that tensile strength is high
CN201810485109.7A Withdrawn CN108611521A (en) 2017-03-22 2017-03-22 A method of preparing acid bronze alloy blank
CN201810494473.XA Withdrawn CN108425033A (en) 2017-03-22 2017-03-22 A method of preparing high-yield strength acid bronze alloy blank
CN201810485102.5A Withdrawn CN108570573A (en) 2017-03-22 2017-03-22 A kind of preparation method of high-tensile acid bronze alloy blank
CN201810485103.XA Withdrawn CN108342609A (en) 2017-03-22 2017-03-22 A kind of acid bronze alloy blank of graphene-containing
CN201810491520.5A Withdrawn CN108570575A (en) 2017-03-22 2017-03-22 A kind of acid bronze alloy blank and preparation method thereof
CN201810488807.2A Withdrawn CN108570574A (en) 2017-03-22 2017-03-22 A method of preparing the acid bronze alloy blank of graphene-containing
CN201710173452.3A Expired - Fee Related CN107012356B (en) 2017-03-22 2017-03-22 A kind of high-intensity high-conductivity copper based alloy blank of graphene-containing and preparation method thereof
CN201810565872.0A Pending CN108677057A (en) 2017-03-22 2017-03-22 A kind of acid bronze alloy blank and preparation method thereof
CN201810494229.3A Withdrawn CN108677040A (en) 2017-03-22 2017-03-22 A kind of preparation method of the acid bronze alloy blank to conduct electricity very well
CN201810491519.2A Withdrawn CN108342611A (en) 2017-03-22 2017-03-22 A kind of preparation method of high-strength copper based alloy blank
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CN201810488791.5A Withdrawn CN108504894A (en) 2017-03-22 2017-03-22 A kind of acid bronze alloy blank that tensile strength is high
CN201810485109.7A Withdrawn CN108611521A (en) 2017-03-22 2017-03-22 A method of preparing acid bronze alloy blank
CN201810494473.XA Withdrawn CN108425033A (en) 2017-03-22 2017-03-22 A method of preparing high-yield strength acid bronze alloy blank
CN201810485102.5A Withdrawn CN108570573A (en) 2017-03-22 2017-03-22 A kind of preparation method of high-tensile acid bronze alloy blank
CN201810485103.XA Withdrawn CN108342609A (en) 2017-03-22 2017-03-22 A kind of acid bronze alloy blank of graphene-containing
CN201810491520.5A Withdrawn CN108570575A (en) 2017-03-22 2017-03-22 A kind of acid bronze alloy blank and preparation method thereof
CN201810488807.2A Withdrawn CN108570574A (en) 2017-03-22 2017-03-22 A method of preparing the acid bronze alloy blank of graphene-containing
CN201710173452.3A Expired - Fee Related CN107012356B (en) 2017-03-22 2017-03-22 A kind of high-intensity high-conductivity copper based alloy blank of graphene-containing and preparation method thereof
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CN108950288A (en) * 2017-11-14 2018-12-07 盐城金麦穗科技发展有限公司 Rice wheat straw graphene copper alloy and its production method
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