CN106048295A - Ultrahigh-conductivity leadless free-cutting copper alloy material, and preparation method and application thereof - Google Patents
Ultrahigh-conductivity leadless free-cutting copper alloy material, and preparation method and application thereof Download PDFInfo
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- CN106048295A CN106048295A CN201610663323.8A CN201610663323A CN106048295A CN 106048295 A CN106048295 A CN 106048295A CN 201610663323 A CN201610663323 A CN 201610663323A CN 106048295 A CN106048295 A CN 106048295A
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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
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- 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
- C22C1/03—Making non-ferrous alloys by melting using master alloys
Abstract
The invention discloses an ultrahigh-conductivity leadless free-cutting copper alloy material, and a preparation method and application thereof. The material is characterized by comprising the following chemical components by weight: 0.10 to 0.30% of Te, 0.003 to 0.009% of P and 99.70 to 99.90% of Cu, wherein the total amount of impurities is less than 0.1%. The preparation method adopts melting, extruding and drawing technology and cooperatively uses a phosphorus-lithium composite deep deoxidation method; and the prepared has oxygen content of less than 20 ppm, reaching the level of oxygen-free copper TU1, and has electrical conductivity of greater than 95% IACS, obviously higher than C14500 conductivity standard (greater than 85% IACS). The material has excellent machinability, electrical conductivity and heat conductivity and resistance to corrosion and electrical ablation, and can be extensively applied to electronic and electrical connection devices, integrated circuit lead frames, welding high-grade gun nozzles, electromotors, switch components and the like with ultrahigh requirements on electrical conductivity.
Description
Technical field
The invention belongs to technical field of alloy material, be specifically related to a kind of high lead Lead free cutting copper alloys material and
Preparation method and application.
Background technology
Conduction red copper, although have good electric conductivity, but its intensity and heat resistance are relatively low.Along with power industry and
The development of electric equipment, in the urgent need to the high-conductivity copper alloy material that various middle high intensity, middle high rigidity and combination property are good.
Tellurium copper C14500, one is kind of a high-conductivity free-cutting Cu alloy material, has taken into account excellent free cutting property, has conducted electricity, leads
Electricity ablation property hot, anticorrosive, anti-, cold and hot working better performances.But owing to C14500 conductivity only has 85～90%ICAS,
When for high pressure, large-current electric electrical connector, under long-time high load capacity working condition, it is easily caused connector temperature liter
Height, resistance increases, and finally results in electrical contact and lost efficacy, affects its service life.
Domestic also have researcher to be studied high-strength, High-conduction copper alloy material, and intensifying method is mainly alloying
Method and composite method: alloying improves mechanical property to a certain extent in the way of sacrificing conductivity, it is impossible to real
Reaching the result that both take into account, copper alloy conductivity prepared by alloying is usually no more than 80%IACS, and needs addition valency
Cr, Zr, Ni and rare earth metal, its complex process, industrial applications and production that lattice are expensive are difficult；Composite method processing technique
The most loaded down with trivial details, production cost is higher, at present still in the experimentation stage.
Therefore, developing a kind of cost relatively low, the high intensity that industrialized production easily realizes, high conduction, free cutting copper close
Gold copper-base alloy, it will produce huge economic benefit and social benefit.
Summary of the invention
It is an object of the invention to for the deficiencies in the prior art, it is provided that a kind of high lead Lead free cutting copper alloys material and
Its preparation method and application, be characterized in copper as matrix, on the basis of adding a small amount of tellurium, uses phosphorus, lithium composite depth deoxidation skill
Art, prepares high connductivity, the Cu alloy material of arc resistant scaling loss, meets the electronic apparatus adapter market demand.
A kind of high chemical composition weight percentage leading Lead free cutting copper alloys material that the present invention provides
For:
Te 0.10～0.30%
P 0.003～0.009%
Cu 99.70～99.90%
Other impurity summation is less than 0.1%.
Scientific investigations showed that, when in oxygen-free copper bar, oxygen content is more than 80ppm, the processing performance of material is deteriorated, and shows as casting
Make and drawing process interrupt line rate drastically increases.Oxygen content height can also cause oxygen-free copper bar conductivity to decline, and Cliver Peac was once
Computing formula: copper conductivity (%IACS)=102.14-0.001388 × ω [O], it can be seen that oxygen content is to affect material is proposed
The major influence factors of material conductivity, oxygen content is the highest, and conductivity is the lowest, and oxygen content height is also easy to cause " hydrogen is sick " in addition.
Rare earth is referred to as " vitamin " of metal material, in the research process preparing high-conductivity copper alloy, is usually made
Use for comprehensive purifying agent, alterant, the mechanical property of material, processing characteristics, anti-wear performance can be improved, conduction copper can be made
Rod, the conductivity of copper bar, copper bar bring up to 97～98%IACS from 95～97%IACS, but rare earth resources is limited, price is held high
Expensive.Phosphorus is as conventional deoxidizer, and deoxidation effect is good, and low price, but residual too much can significantly reduce materials conductive rate；Lithium is made
For deoxidizer, can not only deoxidation, moreover it is possible to playing removing Determination of Trace Sulfur, the effect of hydrogen, comprehensive removing impurities ability is strong, and lithium can also play in addition
The effect of refinement column crystal.
The present invention, by phosphorus and the control of lithium addition, can make C14500 conductivity bring up to 95 from 85～90%IACS
～97%IACS, the residual quantity simultaneously making lithium is denier.
As shown in the embodiment of the present invention, for C14500, the electric conductivity of gained alloy of the present invention is the most excellent
Different, at least up to more than 95% under Y2 state, and the conductivity of C14500 is only 88.7%.
Alloy material of the present invention has taken into account excellent cutting ability and splendid conduction, heat conductivility, is provided simultaneously with anti-corruption
Erosion and anti-electricity ablation property, cold and hot working better performances, can be widely applied to there is electric conductivity the electric of high requirement
Interface unit, circuit lead frame, welding senior rifle mouth, motor and switch block etc..
Further object is that and provide the method preparing above-mentioned alloy, the method comprises the steps:
(1) melting: by weight, adds in D.C.casting stove by tough cathode 99.54～99.84 parts, covers at coverture
Heat up under protection fusing；After tough cathode is completely melt, add 0.002～0.006 part of phosphor bronze alloy deoxidation, control furnace temperature
To 1180 DEG C～1220 DEG C, insulation adds the high purity tellurium of 0.10～0.30 part after standing, and controls furnace temperature to 1180 DEG C～1220 DEG C,
Insulation adds 0.001～0.003 part of phosphor bronze alloy and 0.002～0.005 part of lithium after standing, and after being completely melt, stirring is molten
Pond, adjusting furnace temperature is 1200 DEG C～1240 DEG C, repeatedly implements traction after baking burner；
(2) extruding: put in induction furnace by step (1) gains, be heated to 760～820 DEG C, is incubated 30～45min, makes
Crystal grain uniformly refines, and then carries out extrusion process；
(3) pickling and cold drawn processing: step (2) gains are carried out pickling, washes away oxide on surface, then carries out cold drawn
Processing.
Preferably, described method, after step (3), further comprises the steps of: and material after cold drawn processing is aligned and sawed
Cut.Can align on straightener, be sawed into designated length, surface quality inspection and physical property detection qualified after, packaging warehouse-in.
Preferably, step (1) described phosphor bronze alloy is CuP14.The preparation method of CuP14 can be found in Chinese patent
ZL200810148006.8 " preparation method of a kind of phosphor bronze alloy ".
Preferably, described lithium is to add with lithium copper intermediate alloy CuLi1.5 form, and described high purity tellurium is 99.99% tellurium, institute
Stating coverture is the one in Linesless charcoal, graphite flakes, graphite powder, Testa oryzae.
Preferably, step (2) described extrusion process is to carry out in horizontal extruder, during extrusion process, and can be as requested
Set Product processing rate, Product processing is become 1/4 hard state, half-hard state or hard state product.
Preferably, the time that described insulation stands is 15-20 minute.
Present invention employs the material addition sequence of especial manufacture: 2/3 times of phosphorus of tough cathode coverture
1/3 times of phosphorus of tellurium+lithium continuous casting.Wherein, " 2/3 times of phosphorus " slough major part oxygen, " 1/3 times of phosphorus+lithium " composite depth deoxidation,
Material oxygen content is less than 20ppm, reaches oxygen-free copper TU1 level.Materials conductive rate is more than 95%IACS, hence it is evident that lead higher than C14500
Electricity rate standard (more than 85%IACS), arc resistant scaling loss performance and physical property are suitable with C14500, meet the sub-electrical equipment of high connductivity
Adapter market demands, service life is long.
Offer above-mentioned alloy material application in electrical or mechanical field is provided.As at electricity
The application of the aspects such as son electrical connection device, circuit lead frame, welding senior rifle mouth, motor or switch block.
Beneficial effects of the present invention:
1, gained alloy material oxygen content of the present invention is less than 20ppm, reaches oxygen-free copper TU1 level；
2, arc resistant scaling loss performance and the physical property of gained alloy material of the present invention are suitable with C14500, and conductivity is more than
95%IACS, hence it is evident that higher than C14500 standard (more than 85%IACS), meets high connductivity electric coupler market demands, uses
Life-span is long；
3, the tellurium content of gained alloy material of the present invention is only 0.10%～0.30%, but material cutting ability still reaches
More than the 80% of ledrite C36000.
Detailed description of the invention
Below by embodiment, the present invention is specifically described, it is necessary to it is pointed out here that be that following example are simply used
In the present invention is further detailed, it is impossible to be interpreted as limiting the scope of the invention, being skilled in technique of this field
Some nonessential improvement and adjustment that personnel are made according to foregoing invention content, still fall within protection scope of the present invention.
In following example, when adding raw material, unless otherwise specified, add the most by weight.
Embodiment 1
(1) melting
Tough cathode 99.8 parts adds in D.C.casting stove, and heat up under coverture Linesless charcoal covering protection fusing；Treat that tough cathode is complete
After running down, adding times deoxidation of 0.006 part of phosphor bronze alloy (2/3), control furnace temperature is to 1180 DEG C～1220 DEG C, and insulation stands
15min～20min；Being subsequently added the high purity tellurium (99.99% tellurium) of 0.31 part, control furnace temperature, to 1180 DEG C～1220 DEG C, is incubated
Stand 15min～20min；It is subsequently adding+0.005 part of lithium of 0.003 part of phosphor bronze alloy (1/3 times), after being completely melt, stirring
Molten bath, adjusting furnace temperature is 1200 DEG C～1240 DEG C, repeatedly implements traction after baking burner；
(2) extruding
Rod base composition and surface quality detection qualified after, put in induction furnace, be heated to 820 DEG C, insulation timeliness 30～
45min, makes crystal grain uniformly refine, and uses Ф 7 five hole extrusion die, extrusion ratio 58.7, extrudes in inserting horizontal extruder
Processing；
(3) pickling and cold drawn processing
To above-mentioned extrusion process blank pickling, wash away oxide on surface, drawbench is drawn to Ф 5.5 (Y) product.
(4) aligning sawing
After cold-drawn processing, material saw cutting is to designated length, then aligns on straightener, surface quality inspection and physical property
After energy detection is qualified, packaging warehouse-in.
Embodiment 2
(1) melting
Tough cathode 99.7 parts adds in D.C.casting stove, and heat up under coverture graphite flakes covering protection fusing；Treat negative electrode
After copper is completely melt, adding times deoxidation of 0.004 part of phosphor bronze alloy (2/3), control furnace temperature, to 1180 DEG C～1220 DEG C, is incubated
Stand 15min～20min；It is subsequently added the high purity tellurium (99.99% tellurium) of 0.25 part, controls furnace temperature to 1180 DEG C～1220 DEG C,
Insulation stands 15min～20min；It is subsequently adding+0.004 part of lithium of 0.002 part of phosphor bronze alloy (1/3 times), after being completely melt,
Agitation molten pool, adjusting furnace temperature is 1200 DEG C～1240 DEG C, repeatedly implements traction after baking burner；
(2) extruding
Rod base composition and surface quality detection qualified after, put in induction furnace, be heated to 800 DEG C, insulation timeliness 30～
45min, makes crystal grain uniformly refine, and uses Ф 11.2 5 hole extrusion die, extrusion ratio 38.3, squeezes in inserting horizontal extruder
Pressure processing；
(3) pickling and cold drawn processing
To above-mentioned extrusion process blank pickling, wash away oxide on surface, drawbench is drawn to Ф 9.8 (Y2) product.
(4) aligning sawing
After cold-drawn processing, material is aligned on straightener, is then sawn to designated length, surface quality inspection and physical property
After energy detection is qualified, packaging warehouse-in.
Embodiment 3
(1), during tough cathode 99.6 parts adds D.C.casting stove, heat up under coverture graphite powder covering protection fusing；Treat negative electrode
After copper is completely melt, adding times deoxidation of 0.002 part of phosphor bronze alloy (2/3), control furnace temperature, to 1180 DEG C～1220 DEG C, is incubated
Stand 15min～20min；It is subsequently added the high purity tellurium (99.99% tellurium) of 0.20 part, controls furnace temperature to 1180 DEG C～1220 DEG C,
Insulation stands 15min～20min；It is subsequently adding+0.003 part of lithium of 0.001 part of phosphor bronze alloy (1/3 times), after being completely melt,
Agitation molten pool, adjusting furnace temperature is 1200 DEG C～1240 DEG C, repeatedly implements traction after baking burner；
(2) extruding
Rod base composition and surface quality detection qualified after, put in induction furnace, be heated to 760 DEG C, insulation timeliness 30～
45min, makes crystal grain uniformly refine, and uses Ф 15.5 single hole extrusion die, extrusion ratio 60, extrudes in inserting horizontal extruder
Processing；
(3) pickling and cold drawn processing
To above-mentioned extrusion process blank pickling, wash away oxide on surface, drawbench is drawn to Ф 14 (Y2) product.
(4) aligning sawing
After cold-drawn processing, material is aligned on straightener, is then sawn to designated length, surface quality inspection and physical property
After energy detection is qualified, packaging warehouse-in.
Embodiment 4
(1) melting
Tough cathode 99.50 parts adds in D.C.casting stove, and heat up under coverture Testa oryzae covering protection fusing；Treat that tough cathode is complete
After running down, adding times deoxidation of 0.002 part of phosphor bronze alloy (2/3), control furnace temperature is to 1180 DEG C～1220 DEG C, and insulation stands
15min～20min；Being subsequently added the high purity tellurium (99.99% tellurium) of 0.12 part, control furnace temperature, to 1180 DEG C～1220 DEG C, is incubated
Stand 15min～20min；It is subsequently adding+0.002 part of lithium of 0.001 part of phosphor bronze alloy (1/3 times), after being completely melt, stirring
Molten bath, adjusting furnace temperature is 1200 DEG C～1240 DEG C, repeatedly implements traction after baking burner；
(2) extruding
Rod base composition and surface quality detection qualified after, put in induction furnace, be heated to 820 DEG C, insulation timeliness 30～
45min, makes crystal grain uniformly refine, and uses Ф 7.5 diplopore extrusion die, extrusion ratio 128, extrudes in inserting horizontal extruder
Processing；
(3) pickling and cold drawn processing
Above-mentioned extrusion process blank pickling, washes away oxide on surface, is drawn to Ф 6.6 intermediate products in machine drawing.
(4) annealing and drawing
Ф 6.6 intermediate products are placed in annealing furnace, anneal at a temperature of 600 DEG C, cool to room temperature with the furnace, then after insulation 3h
It is drawn into Ф 6.2 product in machine drawing.
(5) aligning sawing
After cold-drawn processing, material saw cutting is to designated length, then aligns on straightener, surface quality inspection and physical property
After energy detection is qualified, packaging warehouse-in.
Testing embodiment 1-4 gained alloy, its chemical composition and performance are as shown in Table 1 and Table 2.
1, chemical composition
Table 1: chemical composition testing result (unit wt%)
Note: detection method measures with reference to standard GB/T/T 5121-2008 " copper and copper alloy chemical analysis method "
2, physical property, cutting ability, electric conductivity
Physical property is pressed GB/T 228-2002 " metal material tensile testing at ambient temperature " and is measured, and cutting ability is according to GB/
T26306-2010 " free-cutting copper alloy rod " measures, and electric conductivity is according to GB/T351-1995 " metal material resistivity measurement
Method " measure.
Table 2: physical property and machinability testing result
Note: in table 2, cutting ability is compared with C36000 (100%).
Claims (10)
1. high lead Lead free cutting copper alloys material for one kind, it is characterised in that the chemical composition of this material percentage composition by weight
It is calculated as:
Te 0.10～0.30%
P 0.003～0.009%
Cu 99.70～99.90%
Other impurity summation is less than 0.1%.
2. prepare the preparation method of Cu alloy material as claimed in claim 1, it is characterised in that described method includes walking as follows
Rapid:
(1) melting: by weight, adds in D.C.casting stove by tough cathode 99.54～99.84 parts, at coverture covering protection
The lower fusing that heats up；After tough cathode is completely melt, add 0.002～0.006 part of phosphor bronze alloy deoxidation, control furnace temperature extremely
1180 DEG C～1220 DEG C, insulation adds the high purity tellurium of 0.10～0.30 part after standing, and control furnace temperature, to 1180 DEG C～1220 DEG C, is protected
Gentle and quiet postponing adds 0.001～0.003 part of phosphor bronze alloy and 0.002～0.005 part of lithium, after being completely melt, agitation molten pool,
Adjusting furnace temperature is 1200 DEG C～1240 DEG C, repeatedly implements traction after baking burner；
(2) extruding: put in induction furnace by step (1) gains, be heated to 760～820 DEG C, is incubated 30～45min, makes crystal grain
Uniformly refinement, then carries out extrusion process；
(3) pickling and cold drawn processing: step (2) gains are carried out pickling, washes away oxide on surface, then carry out cold drawn adding
Work.
Method the most according to claim 2, it is characterised in that described method is after step (3), and it is right to further comprise the steps of:
After cold drawn processing, material carries out aligning and sawing.
Method the most according to claim 2, it is characterised in that described phosphor bronze alloy is CuP14.
Method the most according to claim 2, it is characterised in that described lithium is to add with lithium copper intermediate alloy CuLi1.5 form
Entering, described high purity tellurium is 99.99% tellurium.
Method the most according to claim 2, it is characterised in that described coverture is Linesless charcoal, graphite flakes, graphite powder, rice
One in bran.
Method the most according to claim 2, it is characterised in that in step (2), described extrusion process is at horizontal extruder
In carry out.
Method the most according to claim 2, it is characterised in that in step (2), during extrusion process, Product processing is become 1/4
Hard state, half-hard state or hard state product.
Method the most according to claim 2, it is characterised in that in step (2), the time that described insulation stands is 15-20
Minute.
10. alloy material described in claim 1 or the alloy material for preparing according to method described in any one of claim 2-9
Material application in electrical or mechanical field, it is characterised in that described application is included in electric interface unit, integrated circuit
Application on lead frame, welding senior rifle mouth, motor or switch block.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110284024A (en) * | 2019-08-05 | 2019-09-27 | 成都云鑫有色金属有限公司 | A kind of preparation method of tellurium copper alloy material |
| CN110616353A (en) * | 2019-10-28 | 2019-12-27 | 河南科技大学 | High-purity high-conductivity copper and preparation method thereof |
| CN110983098A (en) * | 2019-12-18 | 2020-04-10 | 苏州金江铜业有限公司 | Easy-turning copper-titanium-tellurium alloy and manufacturing method thereof |
| CN111910100A (en) * | 2020-07-13 | 2020-11-10 | 苏州金江铜业有限公司 | Beryllium-copper alloy and method for manufacturing micro-wires by using same |
| CN112458321A (en) * | 2020-10-14 | 2021-03-09 | 陕西斯瑞新材料股份有限公司 | Metal processing technology of tellurium-copper alloy wire for high-current electric connector |
| CN111809074B (en) * | 2020-07-21 | 2022-03-08 | 四川科派新材料有限公司 | Lanthanum-carbon-magnesium composite material, tellurium-copper alloy material and preparation method thereof |
| CN115679146A (en) * | 2022-10-28 | 2023-02-03 | 宁波金田铜业(集团)股份有限公司 | Copper alloy and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110284024A (en) * | 2019-08-05 | 2019-09-27 | 成都云鑫有色金属有限公司 | A kind of preparation method of tellurium copper alloy material |
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| CN110616353B (en) * | 2019-10-28 | 2021-09-24 | 河南科技大学 | High-purity high-conductivity copper and preparation method thereof |
| CN110983098A (en) * | 2019-12-18 | 2020-04-10 | 苏州金江铜业有限公司 | Easy-turning copper-titanium-tellurium alloy and manufacturing method thereof |
| CN111910100A (en) * | 2020-07-13 | 2020-11-10 | 苏州金江铜业有限公司 | Beryllium-copper alloy and method for manufacturing micro-wires by using same |
| CN111809074B (en) * | 2020-07-21 | 2022-03-08 | 四川科派新材料有限公司 | Lanthanum-carbon-magnesium composite material, tellurium-copper alloy material and preparation method thereof |
| CN112458321A (en) * | 2020-10-14 | 2021-03-09 | 陕西斯瑞新材料股份有限公司 | Metal processing technology of tellurium-copper alloy wire for high-current electric connector |
| CN112458321B (en) * | 2020-10-14 | 2021-11-09 | 陕西斯瑞新材料股份有限公司 | Metal processing technology of tellurium-copper alloy wire for high-current electric connector |
| CN115679146A (en) * | 2022-10-28 | 2023-02-03 | 宁波金田铜业(集团)股份有限公司 | Copper alloy and preparation method thereof |
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| CN106048295B (en) | 2017-07-18 |
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