CN107858549A - A kind of fire-retardant high-strength height leads Cu Li In cupraliths - Google Patents

Abstract

The invention discloses one kind, fire-retardant high-strength height leads Cu Li In cupraliths and its processing technology between 1,200 1300 degree.By weight percentage, the chemical composition of alloy is：Li:0.5 1.5wt.%, In:2.0 4.0wt.%, Ca:1.0 2.0wt.%, Sr:2.0 3.0wt.%, Co:0.4 0.6wt.%, V:0.2 0.5wt.%, Ho:0.1 0.2wt.%, Er:0.1 0.2wt.%, B:0.5 1.2wt.%, surplus are copper.High-strength highly-conductive Cu Li In cupraliths have excellent conductance and tensile strength combination property.

Description

A kind of fire-retardant high-strength height leads Cu-Li-In cupraliths

Technical field

The present invention relates to technical field of alloy, specifically, is related to a kind of cupralith.

Background technology

With electronics, communication and automobile industry high speed development, the flexible members such as connector, connector are closed with copper-based elasticity The demand of gold increasingly increases.Simultaneously to the property such as the intensity of Copper-Nickel-Aluminium Alloy, conduction, stress relaxation resistance and fatigue strength More stringent requirement can be proposed.Elastic alloy also becomes in addition to good elastic performance with nonmagnetic, microplasticity The performances such as shape drag is high, hardness is high, resistivity is low, temperature coefficient of the elastic modulus is low and in-fighting is small.The former requires high bullet The property limit, low anelasticity effect, it is heat-resist, it can work at a higher temperature；The latter is required in certain temperature range Interior modulus of elasticity is little with temperature change.Copper-Nickel-Aluminium Alloy application is also very universal, is mainly used in the good bullet of electric conductivity Wear-resisting and diamagnetic flexible member in spring contact chip or other springs, precision instrument etc..For manufacturing important spring and elasticity Element, because its modulus of elasticity is low, and the height that elastic limit is relative, therefore in terms of diaphragm, bellows and microswitch is made, It is used widely.

The common Copper-Nickel-Aluminium Alloy system such as including beryllium-bronze.But because beryllium has seriously to the health and environment of people Detrimental effect, and the Technology for Heating Processing of beraloy is complicated big with actual production difficulty, it is only applied to special dimension.State Oneself conductance of the new no beryllium elastic copper alloy through exploitation is too low outside, could not exceed 80%IACS, it is impossible to meets modern first device Requirement of the part to conductance.Lithium is added in copper alloy as alloy element can greatly improve the elastic performance of copper alloy and resistance to Hot mastication performance.Exploitation novel high-strength, height are led, the cupralith of high abrasion, high softening temperature has turned into inevitable.

The characteristics of cupralith maximum is loose because of the easy oxidizing fire of cupralith melt, generation in smelting process Oxide-film and nitride film.This unsound bath surface compound film can not prevent the expansion of oxygen and nitrogen to bath surface Dissipate, result in continuous oxidation and consumption of the cupralith melt in fusion process.Therefore, at present in the smelting of cupralith Alloy preparation is typically carried out using the method for argon gas protection, and smelting temperature is at 1200 degree or so.In so high temperature Under, lithium causes to volatilize excessively in smelting process because vapour pressure is excessive, and remaining lithium content is too low in final alloy.It is general and Speech, using the cupralith of the method melting of argon gas protection, the recovery rate of final lithium only has 20-50wt.% or so.And the party There is casting to some extent to be also easy to produce the shortcomings of flux is mingled with, equipment is complicated and production cost is high for method.Therefore close copper lithium Development, the exploitation of gold are restricted with application.It is being badly in need of the industry of large-scale use cupralith and national defence, is depositing always Few in existing yield, technique is cumbersome, the present situation that the urgent need such as cost height overcomes.

Seek more preferable smelting process as one of key issue in cupralith application study and industrialization.Pass through conjunction The method of aurification reaches the oxidation for preventing the cupralith melt in smelting process, is to solve the development that cupralith smelts problem One of direction.Alloying ignition-proof and prevent that mechanism that lithium volatilizees in fusion process from being to add alloying element in the alloy to influence The thermodynamics and dynamics process of alloy oxidation.Dense oxidation film and nitride film with protective effect are formed in alloy surface, Reach the purpose for preventing alloy vigorous oxidation.Compared with argon gas is protected, alloying ignition-proof can eliminate flux and be mingled with, and reduce to big The pollution of gas.But as a kind of structural material, only have during melting it is fire-retardant with prevent lithium volatile performance in fusion process Requirement far can not be met, it is often more important that it is strong that final cupralith product will also possess gratifying mechanics simultaneously Degree, the mechanical property that can at least reach conventional cupralith are horizontal.Various alloy members thus how are balanced in cupralith The content of element, cupralith that is fire-retardant under atmospheric environment and preventing lithium from being volatilized in fusion process is prepared, and possessed excellent Mechanical property, be current cupralith a urgent problem to be solved.

The content of the invention

Present invention aims to overcome that the deficiencies in the prior art, there is provided one kind can be under 1200-1300 degree atmospheric conditions Carry out the high-strength highly-conductive Cu-Li-In cupraliths and its processing technology of melting.And finally produced in the alloy of this temperature range melting Product have the mechanical property of existing cupralith, and good temperature-room type plasticity and antioxygenic property.This method, which also has, to be produced into This is low, the characteristics of being easy to mass produce.

To achieve these goals, the present invention adopts the following technical scheme that：

A kind of high-strength highly-conductive Cu-Li-In cupraliths with the melting between 1200-1300 degree.By weight percentage, close Gold composition be：Li: 0.5-1.5wt.%,In:2.0-4.0wt.%,Ca:1.0-2.0wt.%,Sr:2.0-3.0wt.%,Co: 0.4-0.6wt.%, V: 0.2-0.5wt.%, Ho: 0.1-0.2wt.%, Er:0.1-0.2wt.%, B:0.5-1.2wt.%, Surplus is copper.The weight that the cupralith loses in fusion process because of the reason such as volatilization and formation clinker is in 2.0- 5.0wt.% or so.

The preparation method of above-mentioned cupralith, comprises the following steps：As above the raw material matched is added under atmosphere protection Electric induction furnace in, and use silicon carbide crucible.Sensing heating forms alloy solution to 1200-1300 degree, and is stirred using electromagnetism Effect is mixed to be sufficiently stirred 10 minutes or so.In the insulation of 1200-1300 degree alloy liquid is cast into heat top same level for 10 minutes to set Standby interior carry out semi-continuous casting, it is 7-10m/min that ingot casting, which moves down speed,.Ingot casting is subjected to deformation process at room temperature, every time Rolling under amount be 10-15%；Every 3 passes need to carry out an intermediate heat-treatment to eliminate processing hardening, and technique is：680 Degree, 2.6 hours；Final Heat Treatment Process after rolling is：Vacuum solid solution handles 790 degree, 4.2 hours；Vacuum aging processing 280 degree, 1.9 hours.

Compared with prior art, the present invention has the advantages that：

（1）Patent of the present invention is directed to cupralith under current high temperature needs the present situation for carrying out atmosphere protection melting to provide in melting A kind of novel protection solution.By the main and secondary addition element in preferred alloy, so as to effectively prevent Burning and excessive Evaporation Phenomenon occur for cupralith under melting state.By preferable alloying method, can not only drop significantly Low alloyed element usage amount, extraordinary flame retardant effect can also be obtained and improve lithium recovery rate.The content of lithium in final products Account for 80-90wt.% of initial lithium addition or so.

（2）During alloy melting, melt has static (insulation of melt and standing) and dynamic（The stirring of melt）Two kinds of shapes Formula.The Cu-Li-In cupraliths that this patent proposes have extremely excellent fire resistance in the quiescent state, can reach in 1200- 5 hours are stood without obvious burning under atmospheric environment in 1300 temperature ranges.In dynamic process, such as to liquid Alloy is stirred, blown etc. during melt treatment, after its skin covering of the surface is because being stirred vigorously destroyed, remains to rapid regeneration, Success hinders the burning of alloy.Gained alloy surface oxide-film and nitride film have extraordinary plasticity and viscosity, can be complete Alloy surface is sprawled and covered on ground, is effectively stopped in air intrusion aluminium alloy.

（3）High-strength highly-conductive Cu-Li-In cupraliths are after lithium is added, because lithium has excellent deoxidation getter action, So that crystal grain is refined.In addition, the alloy has low liquid-solid phase solidification temperature range, can solve casting when hot tearing incline Xiang great, the technical barriers such as the empty and loose substantially product yield rate of casting is low.

（4）High-strength highly-conductive Cu-Li-In cupraliths have excellent conductance and tensile strength comprehensive after timeliness Energy.Its tensile strength is 800-900MPa, and conductance (%IACS) can maintain 94-96 (traditional copper alloy is less than 80).When Pass through 45% cold deformation after effect again, tensile strength rapidly rises to 950-980MPa, and electrical conductivity and elongation percentage can still maintain respectively In 85-89%IACS and 4-6%.Softening temperature test result shows that the alloy softening of aging state and the cold deformation state of timeliness+45% is warm Degree is respectively 600-650 degree and 720-740 degree.

（5）High-strength highly-conductive Cu-Li-In cupraliths are stirred between 1200-1300 degree, the melt treatment such as refining Without obvious burning phenomenon, and the weight that the cupralith loses in fusion process because of the reason such as volatilization and formation clinker occurs Amount is less than 5.0wt.% or so.Smelting processing method is simple, and production cost is reduced to equipment requirement than relatively low.Ensureing possess While anti-flammability, also make it that mechanical property is further improved under alloy service life and high temperature, be easy to industrialize big rule Mould application.

Embodiment

Embodiment 1

One kind has 1240 degree of smelting flame-proof high-strength highly-conductive Cu-Li-In cupraliths.By weight percentage, the chemistry of alloy Composition is：Li: 0.8wt.%,In:2.1wt.%,Ca:1.6wt.%,Sr:2.3wt.%,Co:0.5wt.%,V:0.3wt.%, Ho: 0.1wt.%, Er:0.1wt.%, B:0.6wt.%, surplus are copper.The preparation method of alloy：As above the raw material matched is added In electric induction furnace under to atmospheric environment, and use silicon carbide crucible.Sensing heating forms alloy solution, and profit to 1240 degree It is sufficiently stirred 10 minutes or so with galvanomagnetic-effect.Alloy liquid is cast to heat top same level equipment for 10 minutes in 1240 degree of insulations Interior carry out semi-continuous casting, it is 8m/min that ingot casting, which moves down speed,.Ingot casting is subjected to deformation process at room temperature, under every time rolling Measure as 12%.Every 3 passes need to carry out an intermediate heat-treatment to eliminate processing hardening, and technique is：It is 680 degree, 2.6 small When；Final Heat Treatment Process after rolling is：Vacuum solid solution handles 790 degree, 4.2 hours；Vacuum aging handles 280 degree, and 1.9 is small When.The alloy in 1240 degree and 5 hours between stirred under atmospheric environment, the melt treatment such as refining is obvious without occurring Burning phenomenon, and material raw material proportion of goods damageds caused by evaporating and being formed due to clinker can be controlled on a 2.6wt.% left sides It is right.High-strength highly-conductive Cu-Li-In cupraliths have excellent conductance and tensile strength combination property after timeliness.It is anti- Tensile strength is 820MPa, and conductance (%IACS) can maintain for 94 (traditional copper alloy is less than 80).Pass through 45% after timeliness again Cold deformation, tensile strength rapidly rises to 958MPa, and electrical conductivity and elongation percentage can still maintain 86%IACS and 4.5% respectively. Softening temperature test result shows that the alloy softening temperature of aging state and the cold deformation state of timeliness+45% is respectively 620 degree and 728 Degree.

Embodiment 2

One kind has 1250 degree of smelting flame-proof high-strength highly-conductive Cu-Li-In cupraliths.By weight percentage, the chemistry of alloy Composition is：Li: 1.2wt.%,In:2.7wt.%,Ca:1.8wt.%,Sr:2.6wt.%,Co:0.5wt.%,V:0.4wt.%, Ho: 0.1wt.%, Er:0.1wt.%, B:0.9wt.%, surplus are copper.The preparation method of alloy：As above the raw material matched is added In electric induction furnace under to atmospheric environment, and use silicon carbide crucible.Sensing heating forms alloy solution, and profit to 1250 degree It is sufficiently stirred 10 minutes or so with galvanomagnetic-effect.Alloy liquid is cast to heat top same level equipment for 10 minutes in 1250 degree of insulations Interior carry out semi-continuous casting, it is 9m/min that ingot casting, which moves down speed,.Ingot casting is subjected to deformation process at room temperature, under every time rolling Measure as 12%.Every 3 passes need to carry out an intermediate heat-treatment to eliminate processing hardening, and technique is：It is 680 degree, 2.6 small When；Final Heat Treatment Process after rolling is：Vacuum solid solution handles 790 degree, 4.2 hours；Vacuum aging handles 280 degree, and 1.9 is small When.The alloy in 1250 degree and 5 hours between stirred under atmospheric environment, the melt treatment such as refining is obvious without occurring Burning phenomenon, and material raw material proportion of goods damageds caused by evaporating and being formed due to clinker can be controlled on a 3.9wt.% left sides It is right.High-strength highly-conductive Cu-Li-In cupraliths have excellent conductance and tensile strength combination property after timeliness.It is anti- Tensile strength is 860MPa, and conductance (%IACS) can maintain for 95 (traditional copper alloy is less than 80).Pass through 45% after timeliness again Cold deformation, tensile strength rapidly rises to 972MPa, and electrical conductivity and elongation percentage can still maintain 86%IACS and 4.3% respectively. Softening temperature test result shows that the alloy softening temperature of aging state and the cold deformation state of timeliness+45% is respectively 614 degree and 729 Degree.

Embodiment 3

One kind has 1270 degree of smelting flame-proof high-strength highly-conductive Cu-Li-In cupraliths.By weight percentage, the chemistry of alloy Composition is：Li: 0.9wt.%,In:3.2wt.%,Ca:1.8wt.%,Sr:2.5wt.%,Co:0.5wt.%,V:0.3wt.%, Ho: 0.1wt.%, Er:0.1wt.%, B:0.6wt.%, surplus are copper.The preparation method of alloy：As above the raw material matched is added In electric induction furnace under to atmospheric environment, and use silicon carbide crucible.Sensing heating forms alloy solution, and profit to 1270 degree It is sufficiently stirred 10 minutes or so with galvanomagnetic-effect.Alloy liquid is cast to heat top same level equipment for 10 minutes in 1270 degree of insulations Interior carry out semi-continuous casting, it is 8m/min that ingot casting, which moves down speed,.Ingot casting is subjected to deformation process at room temperature, under every time rolling Measure as 12%.Every 3 passes need to carry out an intermediate heat-treatment to eliminate processing hardening, and technique is：It is 680 degree, 2.6 small When；Final Heat Treatment Process after rolling is：Vacuum solid solution handles 790 degree, 4.2 hours；Vacuum aging handles 280 degree, and 1.9 is small When.The alloy in 1270 degree and 5 hours between stirred under atmospheric environment, the melt treatment such as refining is obvious without occurring Burning phenomenon, and material raw material proportion of goods damageds caused by evaporating and being formed due to clinker can be controlled on a 4.2wt.% left sides It is right.High-strength highly-conductive Cu-Li-In cupraliths have excellent conductance and tensile strength combination property after timeliness.It is anti- Tensile strength is 892MPa, and conductance (%IACS) can maintain for 95 (traditional copper alloy is less than 80).Pass through 45% after timeliness again Cold deformation, tensile strength rapidly rises to 958MPa, and electrical conductivity and elongation percentage can still maintain 86%IACS and 5.2% respectively. Softening temperature test result shows that the alloy softening temperature of aging state and the cold deformation state of timeliness+45% is respectively 623 degree and 735 Degree.

Claims (3)

1. a kind of fire-retardant high-strength height leads Cu-Li-In cupraliths, it is characterised in that by weight percentage, alloy chemistry into It is divided into：Li:0.5-1.5wt.%,In:2.0-4.0wt.%,Ca:1.0-2.0wt.%,Sr:2.0-3.0wt.%,Co:0.4- 0.6wt.%,V:0.2-0.5wt.%,Ho:0.1-0.2wt.%, Er:0.1-0.2wt.%, B:0.5-1.2wt.%, surplus are Copper.

2. fire-retardant high-strength height leads Cu-Li-In cupraliths according to claim 1, it is characterised in that the preparation method of alloy Comprise the following steps：As above the raw material matched is added in the electric induction furnace under atmospheric environment, and uses silicon carbide crucible；Sense 1200-1300 degree should be heated to, forms alloy solution, and be sufficiently stirred 10 minutes or so using galvanomagnetic-effect；By alloy liquid It is cast within 10 minutes in the same level equipment of heat top in the insulation of 1200-1300 degree and carries out semi-continuous casting, it is 7- that ingot casting, which moves down speed, 10m/min。

3. fire-retardant high-strength height leads Cu-Li-In cupraliths according to claim 1, it is characterised in that includes following processing step Suddenly：Ingot casting is subjected to deformation process at room temperature, amount is 10-15% under every time rolling；Every 3 passes need to carry out once Intermediate heat-treatment is hardened to eliminate processing, and technique is：680 degree, 2.6 hours；Final Heat Treatment Process after rolling is：Vacuum 790 degree, 4.2 hours of solution treatment；Vacuum aging handles 280 degree, 1.9 hours.