CN107586979B - A kind of microalloying of rare earth high conductivity copper alloy and preparation method thereof - Google Patents
A kind of microalloying of rare earth high conductivity copper alloy and preparation method thereof Download PDFInfo
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- CN107586979B CN107586979B CN201710894243.8A CN201710894243A CN107586979B CN 107586979 B CN107586979 B CN 107586979B CN 201710894243 A CN201710894243 A CN 201710894243A CN 107586979 B CN107586979 B CN 107586979B
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Abstract
The invention discloses a kind of microalloying of rare earth high conductivity process for producing copper alloy, comprising the following steps: S01: comparing cathode copper, copper zinc intermediate alloy, copper manganese intermediate alloy and copper lanthanum intermediate alloy according to Mole percent and carries out ingredient preparation melting；S02: the cathode copper prepared is placed in crucible；S03: after copper weld pool to be electrolysed is complete, copper zinc intermediate alloy and copper manganese intermediate alloy is added into liquid electrolyte copper, continues melting；S04: copper zinc intermediate alloy and copper manganese intermediate alloy to be added and melting it is complete after, into liquid metal liquid be added copper lanthanum intermediate alloy, continue melting；S05: liquid metal is poured into mold after the abundant melting of above-mentioned alloy, cooling and demolding.The invention also discloses a kind of microalloying of rare earth high conductivity copper alloys, are obtained by above-mentioned preparation method.A kind of microalloying of rare earth high conductivity copper alloy of the invention, conductivity height, good mechanical properties, production cost is low and has stable high-temperature performance.
Description
Technical field
The present invention is related to more particularly to a kind of microalloying of rare earth high conductivity copper alloy and preparation method thereof, belongs to high-performance
Copper alloy field.
Background technique
Fine copper is about 8.9g/cm as a kind of metal material for having excellent conductive thermal conductivity, density3﹐ fusing point is high
Up to 1083 DEG C.It not only has excellent electrical and thermal conductivity in terms of physical property, but also has good ductility, is changing
Learning aspect of performance also has preferable corrosion resistance.It is formed using fine copper metal by matrix and after one or more of other elements are added
Alloy be copper alloy, performance is more more excellent than fine copper, has higher electrical and thermal conductivity, better ductility and anti-corrosion
Property [1].Currently, copper alloy with high strength and high conductivity as a kind of by the Novel copper alloy of research and development emphatically, due to it is high-intensitive,
The excellent performance of highly conductive and high thermal conductivity has been widely used in machinery production, electric and electronic engineering, light industry production and some
In building trade.And with fast development economic in world wide, the consumption figure of copper is also being constantly increasing.
But there are also copper alloys there is a problem of that intensity is not high, electric conductivity is lower and high temperature resistance is excessively poor.Such as
The alloy and some cupro-nickel silicon, cupro-nickel zinc and copper-titanium alloy of copper chromium and this kind of precipitation strength type of copper zirconium, although its intensity is enough,
Or have the defects that electric conductivity is lower, high temperature resistance is excessively poor, anti-softening temperature only has 400 DEG C or so.Industry at present
It is all to sacrifice a degree of conductivity thus to improve copper alloy that high-intensitive, high-conductivity copper alloy method is prepared in production
Mechanical property, therefore how to retain copper and copper alloy good characteristic while improves its electric conductivity and becomes obstruction copper alloy
One obstacle of development.
Summary of the invention
The technical problem to be solved by the present invention is to solve the deficiencies in the prior art, provide that a kind of conductivity is high, mechanical property
Well, production cost is low and the manufacturing method of microalloying of rare earth high-conductivity copper alloy that has stable high-temperature performance, manufactures
Copper alloy can satisfy the requirement in industrial application to conductive copper alloy electric conductivity and mechanical property.
In order to solve the above technical problems, the technical solution adopted by the present invention are as follows:
A kind of microalloying of rare earth high conductivity process for producing copper alloy, comprising the following steps:
S01: cathode copper, copper zinc intermediate alloy, copper manganese intermediate alloy and copper lanthanum intermediate alloy are compared according to Mole percent
It carries out ingredient and prepares melting；
S02:. the cathode copper prepared is placed in crucible, reaches 1 × 10 using vacuum resistance furnace-2MPa to 1 × 10-3MPa
Low vacuum state, heating temperature be 1210~1280 DEG C at carry out melting；
S03: after copper weld pool to be electrolysed is complete, copper zinc intermediate alloy and copper manganese intermediate alloy being added into liquid electrolyte copper,
And keep 1 × 10-2MPa to 1 × 10-3The low vacuum state of MPa, temperature continue to melt under conditions of being 1250~1350 DEG C
Refining；
S04: copper zinc intermediate alloy and copper manganese intermediate alloy to be added and melting it is complete after, copper is added into liquid metal liquid
Lanthanum intermediate alloy, and keep 1 × 10-2MPa to 1 × 10-3The low vacuum state of MPa, temperature drop to 1180~1250 DEG C of condition
Under continue melting；
S05: liquid metal is poured into mold after the abundant melting of above-mentioned alloy, cooling and demolding.
In S03, the molar fraction of zinc accounts for 50% or more in the copper zinc intermediate alloy, manganese in the copper manganese intermediate alloy
Molar fraction accounts for 40% or more.
In S04, the molar fraction of lanthanum accounts for 20% or more in the copper lanthanum intermediate alloy.
In S02, S03 and S04, the quality for the copper alloy that alloy melting time t is synthesized as needed is estimated, reduction formula
Are as follows: t=Km1/2, in formula, K represents copper-zinc-manganese-lanthanum System modulus, and value range is 1000~1500s/ (kg1/2)；M is
The quality for the copper alloy for needing to synthesize, unit kg.
A kind of microalloying of rare earth high conductivity copper alloy is high using a kind of any of the above one kind microalloying of rare earth
Conductivity process for producing copper alloy is prepared.
Each ingredient and its atom percentage content in the microalloying of rare earth high conductivity copper alloy being prepared are as follows: carbon:
0.15~0.33；Zinc: 18.8~27.4；Manganese: 13.8~20.4；Lanthanum: 4.2~9.7；Other it is inevitable it is miscellaneous≤0.035；Copper:
Its surplus.
Beneficial effects of the present invention: the invention proposes a kind of microalloying of rare earth high-conductivity copper alloy, the alloy is opposite
For other conductive copper alloys, highly conductive and good mechanical properties nano-scale Ternary copper zinc lanthanums are had concurrently in grain boundaries formation
Interphase improves its electric conductivity simultaneously in the mechanical property for keeping copper alloy, keeps alloy simultaneous while having high conductivity
Have good mechanical property, has greatly widened the use scope of such alloy.
1, it is raw material, melting that cathode copper, copper zinc intermediate alloy, copper manganese intermediate alloy and copper lanthanum intermediate alloy are chosen in melting
Method is added copper zinc intermediate alloy and copper manganese intermediate alloy continues melting, be eventually adding in copper lanthanum using first melting cathode copper
Between alloy melting obtain the preparation process of final products.Copper-zinc-manganese-lanthanum element energy of the alloy in melting initial stage liquid metal
Enough sufficiently diffusions, are uniformly distributed, so that metal component is uniform after solidification, and raw material is added in the form of intermediate alloy, melting loss of elements
It is few.In process of setting, since copper alloy grain surface can constantly be expanded, and three zinc in alloy, manganese, lanthanum element accountings compared with
It is more, can not be solid-solution in Copper substrate completely, will cause zinc, manganese, lanthanum alloy grain boundaries segregation and be precipitated thermodynamically stable
Ternary copper zinc lanthanum interphase, reduces the surface energy of crystal boundary.Meanwhile in the case where the surface of crystal boundary can act on, Ternary copper zinc lanthanum is hindered
Growing up after interphase forming core, causes phase size to only reach Nano grade.
2, copper alloy of the invention has highly conductive and good mechanical properties nano-scale Ternary coppers concurrently in grain boundaries formation
Zinc lanthanum interphase.Since copper zinc lanthanum interphase is having a size of Nano grade, there is excellent mechanical property, exist at the grain boundary energy
It is enough that invigoration effect is played to the mechanical property of alloy.On the other hand, copper zinc lanthanum interphase belongs to polyelectron layer phase, has more
Free electron is present in alloy grain boundaries and effect is greatly enhanced to the electric conductivity person of having of alloy.Therefore, so that alloy is simultaneous
Have good mechanical property and electric conductivity.
3, stock utilization of the present invention is high, consumes energy low, with short production cycle, production cost is low, is able to achieve automated production, changes
Kind working condition.Process above process is to be combined to complete entire production process on a flow production line by several single machines, single
Robotic arm, conveyer belt transmit blank automatically between machine (process).Blank need not heat repeatedly, energy-saving and emission-reduction, realize green
Manufacture.
In conclusion microalloying of rare earth high conductivity copper alloy of the invention and its manufacturing method, select intermediate alloy
For raw material, and intermittent melting, highly conductive and good mechanical properties nano-scale Ternary copper zinc lanthanums are had concurrently in grain boundaries formation
Interphase improves its electric conductivity simultaneously in the mechanical property for keeping copper alloy, keeps alloy simultaneous while having high conductivity
Has good mechanical property, the copper alloy manufactured can satisfy in industrial application to conductive copper alloy electric conductivity and mechanical property
The requirement of energy.
Detailed description of the invention
Fig. 1 is the copper alloy obtained using a kind of microalloying of rare earth high conductivity process for producing copper alloy of the invention
SEM figure.
Specific embodiment
The invention will be further described below in conjunction with the accompanying drawings, and following embodiment is only used for clearly illustrating the present invention
Technical solution, and not intended to limit the protection scope of the present invention.
Specific embodiment 1
To need the gross mass of copper alloy synthesized to calculate for the ingot of 10kg again, according to Mole percent compare cathode copper,
Copper zinc intermediate alloy (Zn content 50%), copper manganese intermediate alloy (manganese content 40%) and copper lanthanum intermediate alloy (lanthanum content
Prepare melting 20%) to carry out ingredient.
The cathode copper prepared is placed in crucible, is carried out using vacuum resistance furnace 1 × 10-2The low vacuum state of MPa, adds
Hot temperature is to 1280 DEG C of progress meltings, smelting time 53min；Then, into liquid electrolyte copper be added copper zinc intermediate alloy and
Copper manganese intermediate alloy, and keep 1 × 10-2The low vacuum state of MPa, temperature continue melting under conditions of being 1350 DEG C
53min；Copper lanthanum intermediate alloy is finally added into liquid metal liquid, and keeps 1 × 10-2The low vacuum state of MPa, temperature drop to
Continue melting 53min under conditions of 1250 DEG C.
Liquid metal is poured into mold after the abundant melting of above-mentioned alloy, is obtained after cooling and demolding of the invention dilute
Native microalloying high-conductivity copper alloy.
Specific embodiment 2:
To need the gross mass of copper alloy synthesized to calculate for the ingot of 20kg again, according to Mole percent compare cathode copper,
(lanthanum content is for copper zinc intermediate alloy (Zn content 55%), copper manganese intermediate alloy (manganese content 45%) and copper lanthanum intermediate alloy
25%) it carries out ingredient and prepares melting.
The cathode copper prepared is placed in crucible and is carried out using vacuum resistance furnace 1 × 10-3The low vacuum state of MPa, adds
Hot temperature is to 1250 DEG C of progress meltings, smelting time 93min；Then, into liquid electrolyte copper be added copper zinc intermediate alloy and
Copper manganese intermediate alloy, and keep 1 × 10-3The low vacuum state of MPa, temperature continue melting under conditions of being 1300 DEG C
93min；Copper lanthanum intermediate alloy is finally added into liquid metal liquid, and keeps 1 × 10-3The low vacuum state of MPa, temperature drop to
Continue melting 93min under conditions of 1200 DEG C.
Liquid metal is poured into mold after the abundant melting of above-mentioned alloy, is obtained after cooling and demolding of the invention
Microalloying of rare earth high-conductivity copper alloy.
Specific embodiment 3:
To need the gross mass of copper alloy synthesized to calculate for the ingot of 30kg again, according to Mole percent compare cathode copper,
(lanthanum content is for copper zinc intermediate alloy (Zn content 60%), copper manganese intermediate alloy (manganese content 50%) and copper lanthanum intermediate alloy
30%) it carries out ingredient and prepares melting.
The cathode copper prepared is placed in crucible and is carried out using vacuum resistance furnace 5 × 10-3The low vacuum state of MPa, adds
Hot temperature is to 1210 DEG C of progress meltings, smelting time 137min；Then, into liquid electrolyte copper be added copper zinc intermediate alloy and
Copper manganese intermediate alloy, and keep 5 × 10-3The low vacuum state of MPa, temperature continue melting under conditions of being 1250 DEG C
137min；Copper lanthanum intermediate alloy is finally added into liquid metal liquid, and keeps 5 × 10-3The low vacuum state of MPa, temperature drop
Continue melting 137min under conditions of to 1180.
Liquid metal is poured into mold after the abundant melting of above-mentioned alloy, is obtained after cooling and demolding of the invention
Microalloying of rare earth high-conductivity copper alloy.
As shown in Figure 1, using preparation method of the invention, the phase ruler of obtained microalloying of rare earth high conductivity copper alloy
It is very little to only reach Nano grade.
Table 1 is to obtain microalloying of rare earth high conductivity copper alloy comprehensive performance data comparison by above-mentioned manufacturing method.
As shown in Table 1, above-mentioned 3 embodiment products require to compare with international technical norms, the product electric conductivity that the present invention obtains
It can be with mechanical property much higher than international technical norms requirement.The copper alloy manufactured can satisfy in industrial application to conductive copper
The requirement of alloy conductive and mechanical property.
1 microalloying of rare earth high conductivity copper alloy comprehensive performance data comparison of table
The above is only a preferred embodiment of the present invention, it should be pointed out that: for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (5)
1. a kind of microalloying of rare earth high conductivity process for producing copper alloy, it is characterised in that: the following steps are included:
S01: cathode copper, copper zinc intermediate alloy, copper manganese intermediate alloy and copper lanthanum intermediate alloy are compared according to Mole percent and is carried out
Ingredient prepares melting；
S02:. the cathode copper prepared is placed in crucible, reaches 1 × 10 using vacuum resistance furnace-2MPa to 1 × 10-3MPa's is low
Vacuum state, heating temperature are to carry out melting at 1210~1280 DEG C；
S03: after copper weld pool to be electrolysed is complete, copper zinc intermediate alloy and copper manganese intermediate alloy are added into liquid electrolyte copper, and protect
Hold 1 × 10-2MPa to 1 × 10-3The low vacuum state of MPa, temperature continue melting under conditions of being 1250~1350 DEG C；
S04: copper zinc intermediate alloy and copper manganese intermediate alloy to be added and melting it is complete after, into liquid metal liquid be added copper lanthanum in
Between alloy, and keep 1 × 10-2MPa to 1 × 10-3The low vacuum state of MPa, temperature drop to 1180~1250 DEG C under conditions of after
It is continuous to carry out melting；
Liquid metal: being poured into mold, cooling and demolding by S05 after the abundant melting of above-mentioned alloy, and the rare earth being prepared is micro-
Each ingredient and its atom percentage content in alloying high conductivity copper alloy are as follows: carbon: 0.15~0.33；Zinc: 18.8~27.4；
Manganese: 13.8~20.4；Lanthanum: 4.2~9.7；Other it is inevitable it is miscellaneous≤0.035；Copper: its surplus.
2. a kind of microalloying of rare earth high conductivity process for producing copper alloy according to claim 1, it is characterised in that:
In S03, the molar fraction of zinc accounts for 50% or more in the copper zinc intermediate alloy, the molar fraction of manganese in the copper manganese intermediate alloy
Account for 40% or more.
3. a kind of microalloying of rare earth high conductivity process for producing copper alloy according to claim 1, it is characterised in that:
In S04, the molar fraction of lanthanum accounts for 20% or more in the copper lanthanum intermediate alloy.
4. a kind of microalloying of rare earth high conductivity process for producing copper alloy according to claim 1, it is characterised in that:
In S02, S03 and S04, the quality for the copper alloy that alloy melting time t is synthesized as needed is estimated, reduction formula are as follows: t=
K·m1/2, in formula, K represents copper-zinc-manganese-lanthanum System modulus, and value range is 1000~1500s/ (kg1/2)；M is to need to close
At copper alloy quality, unit kg.
5. a kind of microalloying of rare earth high conductivity copper alloy, it is characterised in that: micro- using a kind of any of the above rare earth
Alloying high conductivity process for producing copper alloy is prepared.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899588A (en) * | 2010-08-25 | 2010-12-01 | 江西理工大学 | Nickel-free white copper alloy containing rare earth additional elements and method for manufacturing plates made of same |
| CN105220010A (en) * | 2015-10-30 | 2016-01-06 | 苏州列治埃盟新材料技术转移有限公司 | A kind of lead-free rare-earth Alloy Materials compo pipe and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899588A (en) * | 2010-08-25 | 2010-12-01 | 江西理工大学 | Nickel-free white copper alloy containing rare earth additional elements and method for manufacturing plates made of same |
| CN105220010A (en) * | 2015-10-30 | 2016-01-06 | 苏州列治埃盟新材料技术转移有限公司 | A kind of lead-free rare-earth Alloy Materials compo pipe and preparation method thereof |
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Effective date of registration: 20201216 Address after: No.7, Yangqiao 4th Road, Xianghe Town, Quanjiao County, Chuzhou City, Anhui Province Patentee after: ANHUI LEDA PRECISION ALLOY CO.,LTD. Address before: 1 No. 211167 Jiangsu city of Nanjing province Jiangning Science Park Hongjing Road Patentee before: NANJING INSTITUTE OF TECHNOLOGY |
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Denomination of invention: A Rare Earth Microalloyed High Conductivity Copper Alloy and Its Preparation Method Effective date of registration: 20221213 Granted publication date: 20190614 Pledgee: Quanjiao enterprise financing Company limited by guarantee Pledgor: ANHUI LEDA PRECISION ALLOY CO.,LTD. Registration number: Y2022980027108 |