CN106048295B - One kind is high to lead Lead free cutting copper alloys material and its preparation method and application - Google Patents
One kind is high to lead Lead free cutting copper alloys material and its preparation method and application Download PDFInfo
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- CN106048295B CN106048295B CN201610663323.8A CN201610663323A CN106048295B CN 106048295 B CN106048295 B CN 106048295B CN 201610663323 A CN201610663323 A CN 201610663323A CN 106048295 B CN106048295 B CN 106048295B
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- C22C9/00—Alloys based on copper
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Abstract
High Lead free cutting copper alloys material and its preparation method and application is led the invention discloses one kind, the chemical composition weight percentage for being characterized in the material is Te 0.10~0.30, P 0.003~0.009, Cu 99.70~99.90, impurity summation is less than 0.1.Using melting, extruding, drawing process, with reference to phosphorus lithium composite depth method of deoxidation, material oxygen content is less than 20ppm, reaches oxygen-free copper TU1 levels, and conductance is more than 95%IACS, hence it is evident that higher than C14500 conductances standard (being more than 85%IACS).The material has taken into account excellent cutting ability and splendid conduction, heat conductivility, anticorrosive and anti-electric ablation property is provided simultaneously with, can be widely applied to have the senior rifle mouth of the electric interface unit of high requirement, circuit lead frame, welding, motor and switch block etc. to electric conductivity.
Description
Technical field
The invention belongs to technical field of alloy material, and in particular to it is a kind of it is high lead Lead free cutting copper alloys material and its
Preparation method and application.
Background technology
Conduction red copper, although have good electric conductivity, but its intensity and heat resistance are relatively low.With power industry and
The development of electric equipment, in the urgent need to various middle high intensity, middle high rigidity and the good high-conductivity copper alloy material of combination property.
Tellurium copper C14500, one is kind of a high-conductivity free-cutting Cu alloy material, has taken into account excellent free cutting property, conduction, has led
Hot, anticorrosive, anti-electric ablation property, cold and hot working better performances.But it is due to that C14500 conductances only have 85~90%ICAS,
When for high pressure, high current electronics electrical connector, under long-time high load capacity condition of work, connector temperature liter is easily caused
Height, resistance increase finally results in electrical contact failure, influences its service life.
The country also has researcher to study high-strength, High-conduction copper alloy material, and intensifying method is mainly alloying
Method and composite method：Alloying improves mechanical property in the way of sacrificing conductance to a certain extent, it is impossible to real
The result that both take into account is reached, copper alloy conductance prepared by alloying is usually no more than 80%IACS, and needs addition valency
Lattice expensive Cr, Zr, Ni and rare earth metal, its complex process, industrial applications and production are difficult；Composite method processing technology
Very cumbersome, production cost is higher, at present still in the experimental study stage.
Therefore, develop that a kind of cost is relatively low, high intensity that industrialized production is easily realized, high conductive, free cutting copper are closed
Golden material, it will produce huge economic benefit and social benefit.
The content of the invention
The purpose of the present invention be in view of the shortcomings of the prior art there is provided one kind it is high lead Lead free cutting copper alloys material and
Its preparation method and application, are characterized in using copper as matrix, on the basis of a small amount of tellurium of addition, using phosphorus, lithium composite depth deoxidation skill
Art, prepares the Cu alloy material of highly conductive arc resistant scaling loss, meets the electronic apparatus connector market demand.
A kind of high chemical composition weight percentage for leading Lead free cutting copper alloys material that the present invention is provided
For：
Te 0.10~0.30%
P 0.003~0.009%
Cu 99.70~99.90%
Other impurity summations are less than 0.1%.
Scientific investigations showed that, when oxygen content is more than 80ppm in oxygen-free copper bar, 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 conductance to decline, and Cliver Peac were once
Propose computing formula：Copper conductance (%IACS)=102.14-0.001388 × ω【O】, it can be seen that oxygen content is influence material
Expect the major influence factors of conductance, oxygen content is higher, and conductance is lower, oxygen content height is also easy to cause " hydrogen disease " in addition.
Rare earth is referred to as " vitamin " of metal material, in the research process of high-conductivity copper alloy is prepared, and is usually made
Used for comprehensive purifying agent, alterant, the mechanical property, processing characteristics, anti-wear performance of material can be improved, conduction copper can be made
Rod, copper bar, the conductance of copper bar bring up to 97~98%IACS from 95~97%IACS, but rare earth resources are limited, price is held high
It is expensive.Phosphorus is as conventional deoxidier, and deoxidation effect is good and cheap, but residual can excessively significantly reduce materials conductive rate；Lithium is made
, can not only deoxidation for deoxidier, moreover it is possible to play a part of removing Determination of Trace Sulfur, hydrogen, comprehensive removing impurities ability is strong, and lithium can also be played in addition
Refine the effect of column crystal.
The present invention can make C14500 conductances bring up to 95 from 85~90%IACS by the control to phosphorus and lithium addition
~97%IACS, while so that the residual quantity of lithium is denier.
As shown in the embodiment of the present invention, for C14500, the electric conductivity of present invention gained alloy is very excellent
Different, at least up to more than 95% under Y2 states, and C14500 conductance 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-electric ablation property, cold and hot working better performances, can be widely applied to have the electric of high requirement to electric conductivity
The senior rifle mouth of interface unit, circuit lead frame, welding, motor and switch block etc..
It is another object of the present invention to provide the method for preparing above-mentioned alloy, this method comprises the following steps：
(1) melting：By weight, by 99.54~99.84 parts of addition D.C.casting stoves of tough cathode, covered in coverture
The lower heating fusing of protection；After tough cathode is completely melt, 0.002~0.006 part of phosphor bronze alloy deoxidation is added, furnace temperature is controlled
To 1180 DEG C~1220 DEG C, insulation adds 0.10~0.30 part of high purity tellurium 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, after being completely melt, stirring is molten
Pond, adjustment furnace temperature is 1200 DEG C~1240 DEG C, repeatedly implements traction after baking burner；
(2) extrude：Step (1) gains are put into induction furnace, 760~820 DEG C are heated to, 30~45min is incubated, makes
Crystal grain is uniformly refined, and then carries out extrusion process；
(3) pickling and cold drawn processing：Pickling is carried out to step (2) gains, oxide on surface is washed away, then carries out cold drawn
Processing.
It is preferred that, methods described is after step (3), also including step：Material after cold drawn processing is aligned and sawed
Cut.Can be aligned on straightener, be sawed into designated length, surface quality inspection and physical property detection it is qualified after, packaging and storage.
It is preferred that, step (1) described phosphor bronze alloy is CuP14.CuP14 preparation method can be found in Chinese patent
ZL200810148006.8《A kind of preparation method of phosphor bronze alloy》.
It is preferred that, the lithium is added in lithium copper intermediate alloy CuLi1.5 forms, and the high purity tellurium is 99.99% tellurium, institute
It is one kind in charcoal, graphite flakes, graphite powder, rice bran to state coverture.
It is preferred that, step (2) described extrusion process is carried out in horizontal extruder, can be as requested during extrusion process
Product processing rate is set, by Product processing into 1/4 hard state, half-hard state or hard state product.
It is preferred that, the time that the insulation is stood is 15-20 minutes.
Present invention employs the material addition sequence of especial manufacture：Tough cathode --- coverture --- 2/3 times of phosphorus ---
Tellurium --- 1/3 times of phosphorus+lithium --- continuous casting.Wherein, " 2/3 times of phosphorus " sloughs most of oxygen, " 1/3 times of phosphorus+lithium " composite depth deoxidation,
Material oxygen content is less than 20ppm, reaches oxygen-free copper TU1 levels.Materials conductive rate is more than 95%IACS, hence it is evident that led higher than C14500
Electric rate standard (being more than 85%IACS), arc resistant scaling loss performance and physical property are suitable with C14500, meet highly conductive sub- electrical equipment
Connector market demands, long service life.
It is another object of the present invention to provide application of the above-mentioned alloy material in electrical or mechanical field.Such as in electricity
Application in terms of son electrical connection device, circuit lead frame, the senior rifle mouth of welding, motor or switch block.
Beneficial effects of the present invention：
1st, present invention gained alloy material oxygen content is less than 20ppm, reaches oxygen-free copper TU1 levels；
2nd, the arc resistant scaling loss performance and physical property of present invention gained alloy material are suitable with C14500, and conductance is more than
95%IACS, hence it is evident that higher than C14500 standards (being more than 85%IACS), meet highly conductive sub- electric coupler market demands, use
Long lifespan；
3rd, the tellurium content of present invention gained alloy material is only 0.10%~0.30%, but material cutting ability still reaches
More than the 80% of ledrite C36000.
Embodiment
The present invention is specifically described below by embodiment, it is necessary to it is pointed out here that be following examples be use
It is further detailed in the present invention, it is impossible to be interpreted as limiting the scope of the invention, the field is skilled in technique
Some nonessential modifications and adaptations that personnel are made according to foregoing invention content, still fall within protection scope of the present invention.
In following examples, when adding raw material, unless otherwise specified, add by weight.
Embodiment 1
(1) melting
99.8 parts of tough cathode is added in D.C.casting stove, and heat up fusing under coverture charcoal covering protection；Treat that tough cathode is complete
After running down, 0.006 part of phosphor bronze alloy (2/3) times deoxidation is added, control furnace temperature is to 1180 DEG C~1220 DEG C, and insulation is stood
15min~20min；0.31 part of high purity tellurium (99.99% tellurium) is subsequently added, control furnace temperature is to 1180 DEG C~1220 DEG C, insulation
Stand 15min~20min；Then+0.005 part of lithium of 0.003 part of phosphor bronze alloy (1/3 times) is added, after being completely melt, stirring
Molten bath, adjustment furnace temperature is 1200 DEG C~1240 DEG C, repeatedly implements traction after baking burner；
(2) extrude
After bar stock composition and surface quality detection are qualified, it is put into induction furnace, is heated to 820 DEG C, insulation timeliness 30~
45min, makes crystal grain uniformly refine, and using the hole extrusion dies of Ф 7 five, extrusion ratio 58.7 is inserted and extruded in horizontal extruder
Processing；
(3) pickling and cold drawn processing
To above-mentioned extrusion process blank pickling, wash away and Ф 5.5 (Y) product is drawn on oxide on surface, drawbench.
(4) sawing is aligned
Then material saw cutting is aligned on straightener to designated length after cold-drawn processing, surface quality inspection and physical
After energy detection is qualified, packaging and storage.
Embodiment 2
(1) melting
99.7 parts of tough cathode is added in D.C.casting stove, and heat up fusing under coverture graphite flakes covering protection；Treat negative electrode
After copper is completely melt, 0.004 part of phosphor bronze alloy (2/3) times deoxidation is added, control furnace temperature is to 1180 DEG C~1220 DEG C, insulation
Stand 15min~20min；0.25 part of high purity tellurium (99.99% tellurium) is subsequently added, furnace temperature is controlled to 1180 DEG C~1220 DEG C,
Insulation stands 15min~20min；Then+0.004 part of lithium of 0.002 part of phosphor bronze alloy (1/3 times) is added, after being completely melt,
Agitation molten pool, adjustment furnace temperature is 1200 DEG C~1240 DEG C, repeatedly implements traction after baking burner；
(2) extrude
After bar stock composition and surface quality detection are qualified, it is put into induction furnace, is heated to 800 DEG C, insulation timeliness 30~
45min, makes crystal grain uniformly refine, and using the hole extrusion dies of Ф 11.2 5, extrusion ratio 38.3 is inserted and squeezed in horizontal extruder
Pressure processing；
(3) pickling and cold drawn processing
To above-mentioned extrusion process blank pickling, wash away and Ф 9.8 (Y2) product is drawn on oxide on surface, drawbench.
(4) sawing is aligned
Material is aligned on straightener after cold-drawn processing, is then sawn to designated length, surface quality inspection and physical
After energy detection is qualified, packaging and storage.
Embodiment 3
(1) 99.6 parts of tough cathode is added in D.C.casting stove, and heat up fusing under coverture graphite powder covering protection；Treat negative electrode
After copper is completely melt, 0.002 part of phosphor bronze alloy (2/3) times deoxidation is added, control furnace temperature is to 1180 DEG C~1220 DEG C, insulation
Stand 15min~20min；0.20 part of high purity tellurium (99.99% tellurium) is subsequently added, furnace temperature is controlled to 1180 DEG C~1220 DEG C,
Insulation stands 15min~20min；Then+0.003 part of lithium of 0.001 part of phosphor bronze alloy (1/3 times) is added, after being completely melt,
Agitation molten pool, adjustment furnace temperature is 1200 DEG C~1240 DEG C, repeatedly implements traction after baking burner；
(2) extrude
After bar stock composition and surface quality detection are qualified, it is put into induction furnace, is heated to 760 DEG C, insulation timeliness 30~
45min, makes crystal grain uniformly refine, and using the single hole extrusion dies of Ф 15.5, extrusion ratio 60 is inserted and extruded in horizontal extruder
Processing；
(3) pickling and cold drawn processing
To above-mentioned extrusion process blank pickling, wash away and Ф 14 (Y2) product is drawn on oxide on surface, drawbench.
(4) sawing is aligned
Material is aligned on straightener after cold-drawn processing, is then sawn to designated length, surface quality inspection and physical
After energy detection is qualified, packaging and storage.
Embodiment 4
(1) melting
99.50 parts of tough cathode is added in D.C.casting stove, and heat up fusing under coverture rice bran covering protection；Treat that tough cathode is complete
After running down, 0.002 part of phosphor bronze alloy (2/3) times deoxidation is added, control furnace temperature is to 1180 DEG C~1220 DEG C, and insulation is stood
15min~20min；0.12 part of high purity tellurium (99.99% tellurium) is subsequently added, control furnace temperature is to 1180 DEG C~1220 DEG C, insulation
Stand 15min~20min；Then+0.002 part of lithium of 0.001 part of phosphor bronze alloy (1/3 times) is added, after being completely melt, stirring
Molten bath, adjustment furnace temperature is 1200 DEG C~1240 DEG C, repeatedly implements traction after baking burner；
(2) extrude
After bar stock composition and surface quality detection are qualified, it is put into induction furnace, is heated to 820 DEG C, insulation timeliness 30~
45min, makes crystal grain uniformly refine, and using the diplopore extrusion dies of Ф 7.5, extrusion ratio 128 is inserted and extruded in horizontal extruder
Processing；
(3) pickling and cold drawn processing
Above-mentioned extrusion process blank pickling, washes away oxide on surface, and the intermediate products of Ф 6.6 are drawn in machine drawing.
(4) annealing and drawing
The intermediate products of Ф 6.6 are placed in annealing furnace, are annealed at a temperature of 600 DEG C, cool to normal temperature with the furnace after insulation 3h, then
The products of Ф 6.2 are drawn into machine drawing.
(5) sawing is aligned
Then material saw cutting is aligned on straightener to designated length after cold-drawn processing, surface quality inspection and physical
After energy detection is qualified, packaging and storage.
Alloy obtained by embodiment 1-4 is tested, its chemical composition and performance are as shown in Table 1 and Table 2.
1st, chemical composition
Table 1：Chemical composition testing result (unit wt%)
Note：Detection method is with reference to standard GB/T/T 5121-2008《Copper and copper alloy chemical analysis method》Determine
2nd, physical property, cutting ability, electric conductivity
Physical property presses GB/T 228-2002《Metal material tensile testing at ambient temperature》Determine, cutting ability is according to GB/
T26306-2010《Free-cutting copper alloy rod》Determine, electric conductivity is according to GB/T351-1995《Metal material resistivity measurement
Method》Determine.
Table 2：Physical property and machinability testing result
Note：Cutting ability is compared with C36000 (100%) in table 2.
Claims (9)
1. a kind of high preparation method for leading Lead free cutting copper alloys material, it is characterised in that methods described includes following step
Suddenly：
（1）Melting：By weight, by the addition D.C.casting stove of .84 parts of the .54 of tough cathode 99~99, cover and protect in coverture
The lower heating fusing of shield；After tough cathode is completely melt, the phosphor bronze alloy deoxidation of .006 parts of 0 .002~0 is added, furnace temperature is controlled
To 1180 DEG C~1220 DEG C, insulation adds the high purity tellurium of .30 part of 0 .10~0 after standing, control furnace temperature to 1180 DEG C~
1220 DEG C, insulation adds .003 parts of 0 .001~0 phosphor bronze alloy and .005 parts of 0 .002~0 lithium after standing, and melts completely
After change, agitation molten pool, adjustment furnace temperature is 1200 DEG C~1240 DEG C, repeatedly implements traction after baking burner；
（2）Extruding：By step（1）Gains are put into induction furnace, are heated to 760~820 DEG C, are incubated 30~45 min, are made crystalline substance
The uniform refinement of grain, then carries out extrusion process；
（3）Pickling and cold drawn processing：To step（2）Gains carry out pickling, wash away oxide on surface, then carry out cold drawn add
Work；
Wherein, the chemical composition weight percentage of the Cu alloy material is：
The .30 % of .10 of Te 0~0
The .009 % of .003 of P 0~0
The % of Cu 99.70~99.90
Other impurity summations are less than 0 .1 %.
2. according to the method described in claim 1, it is characterised in that methods described is in step（3）Afterwards, also including step：It is right
Material is aligned and sawing after cold drawn processing.
3. according to the method described in claim 1, it is characterised in that the phosphor bronze alloy is CuP14.
4. according to the method described in claim 1, it is characterised in that the lithium is added in lithium copper intermediate alloy CuLi1 .5 forms
Enter, the high purity tellurium is 99.99 % telluriums.
5. according to the method described in claim 1, it is characterised in that the coverture is charcoal, graphite flakes, graphite powder, rice
One kind in chaff.
6. according to the method described in claim 1, it is characterised in that step（2）In, the extrusion process is in horizontal extruder
It is middle to carry out.
7. according to the method described in claim 1, it is characterised in that step（2）In, during extrusion process, by Product processing into 1/4
Hard state, half-hard state or hard state product.
8. according to the method described in claim 1, it is characterised in that step（1）In, the time that standing is incubated twice is
15-20 minutes.
9. the Cu alloy material prepared according to any one of claim 1-8 methods described answering in electrical or mechanical field
It is in electric interface unit, circuit lead frame, the senior rifle mouth of welding, electronic with, it is characterised in that the application
Application on machine or switch block.
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| CN111809074A (en) * | 2020-07-21 | 2020-10-23 | 四川科派新材料有限公司 | Lanthanum-carbon-magnesium composite material, tellurium-copper alloy material and preparation method thereof |
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| CN110284024B (en) * | 2019-08-05 | 2021-04-13 | 成都云鑫有色金属有限公司 | Preparation method of tellurium-copper alloy material |
| CN110616353B (en) * | 2019-10-28 | 2021-09-24 | 河南科技大学 | High-purity high-conductivity copper and preparation method thereof |
| CN110983098B (en) * | 2019-12-18 | 2021-12-10 | 苏州金江铜业有限公司 | Easy-turning copper-titanium-tellurium alloy and manufacturing method thereof |
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| JPS59166645A (en) * | 1983-03-10 | 1984-09-20 | Sumitomo Metal Mining Co Ltd | Copper alloy for radiator fin |
| JPH06184673A (en) * | 1992-12-22 | 1994-07-05 | Mitsubishi Materials Corp | Pitting corrosion resistant copper alloy piping for feeding water and hot water |
| JPH0790427A (en) * | 1993-09-20 | 1995-04-04 | Mitsubishi Materials Corp | Copper alloy excellent in resistance to ant's lair-form corrosion |
| CN1266294C (en) * | 2004-05-14 | 2006-07-26 | 四川大学 | Anti-electric-arc copper-tellurium-chromium multi-element alloy material |
| CN101429601B (en) * | 2008-12-16 | 2010-09-22 | 四川鑫炬矿业资源开发股份有限公司 | Tellurium copper alloy material for electric power industry and method for producing the same |
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| CN111809074A (en) * | 2020-07-21 | 2020-10-23 | 四川科派新材料有限公司 | Lanthanum-carbon-magnesium composite material, tellurium-copper alloy material and preparation method thereof |
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Effective date of registration: 20171120 Address after: Room 2, room 3, building No. 3, courtyard 30, Shixing Avenue, Shijingshan District, Beijing, Beijing Co-patentee after: Sichuan Xin Ju Xinxing new Mstar Technology Ltd Patentee after: Middle energy-saving industrial Power Conservation, Ltd. Address before: He becomes an industrial park in Jintang County of Chengdu City, Sichuan province 610000 Jin Road No. 1 Patentee before: Sichuan Xin Ju Xinxing new Mstar Technology Ltd |
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Application publication date: 20161026 Assignee: Sichuan Xinju Mineral Industry Resource Development Co., Ltd. Assignor: Sichuan Xin Ju Xinxing new Mstar Technology Ltd|Middle energy-saving industrial Power Conservation, Ltd. Contract record no.: 2018510000021 Denomination of invention: Ultrahigh-conductivity leadless free-cutting copper alloy material, and preparation method and application thereof Granted publication date: 20170718 License type: Common License Record date: 20180518 |
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