CN107815563A - A kind of Cu Li Sb cupraliths for substituting beryllium-bronze - Google Patents

Abstract

A kind of Cu Li Sb cupraliths for substituting beryllium-bronze, by weight percentage, the chemical composition of alloy is：Li:0.6‑1.9wt.%,Sb:1.0‑3.0wt.%,Sr:1.0‑2.6wt.%,Er:0.2‑0.5wt.%,Yb:0.1 0.2wt.%, Ni:0.2 0.6wt.%, B:0.4‑0.8wt.%,S:0.3 0.5wt.%, surplus are copper.The material has excellent mechanical property.Modulus of elasticity：125‑138GPa；Yield strength：950‑1080MPa；Tensile strength：1100‑1200MPa；Elongation percentage：4‑10%.And there is excellent decay resistance：Corrosion rate in the seawater is less than 1.1 × 10^{‑ 2}Mm/.

Description

A kind of Cu-Li-Sb cupraliths for substituting beryllium-bronze

Technical field

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

Background technology

Beryllium is steel grey metal, all lighter than conventional aluminium and titanium, but intensity is 4 times of steel.Fly now with many supersonic speed The brake apparatus of machine is manufactured with beryllium, because it has fabulous heat absorption, the performance of radiating, heat caused by brake is quickly It will scatter and disappear.Copper is much softer than steel, elastic and also not strong to erosion-resisting ability.But 1- is added in copper alloy After 3.5wt.% beryllium, there occurs significant change for the performance of copper alloy.Beryllium-bronze is the elasticity that best performance is good in copper alloy One of alloy, there is good heat conduction, conduction, nonmagnetic, elastic hysteresis is small.Beraloy is used to manufacture to work at high temperature Spring, such a spring still keeps good elasticity and toughness under red heat state, can compress more than several hundred million times.Beryllium-bronze can To make electronic connector contact, switch contact, key components and parts such as membranous disc, diaphragm, bellows, spring washer, micro machine electricity Brush and commutator, electrical connectors, clock and watch part, audio components etc., are widely used in instrument, instrument, computer, automobile, household electrical appliances Deng in industry.Beryllium-bronze is easy to welding and soldering, the high corrosion resistance in air, fresh water and seawater, is used to manufacture deep-sea Detector and submarine cable.Nickeliferous beryllium-bronze have one it is very valuable the characteristics of, exactly by hit when will not produce Spark.This feature instrument special to making military project, oil, mine is most important.

But because beryllium has serious detrimental effect to the health and environment of people, and the Technology for Heating Processing of beraloy is answered Miscellaneous and actual production difficulty is big, it is only applied to special dimension.Oneself external new no beryllium elastic copper alloy through exploitation is led Electric rate is too low, could not exceed 50%IACS, it is impossible to meet requirement of the modern component to conductance.Lithium is as alloy element The elastic performance and resistance to softening at high temperature energy of copper alloy can be greatly improved by adding in copper alloy.Exploitation novel high-strength, height are led, are high Wear-resisting, high softening temperature cupralith 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 10-30wt.% 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-Sb 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-Sb cupraliths with the melting between 1200-1300 degree.By weight percentage, close Gold composition be：Li: 0.6-1.9wt.%, Sb: 1.0-3.0wt.%,Sr:1.0-2.6wt.%, Er: 0.2-0.5wt.%, Yb:0.1-0.2wt.%, Ni:0.2-0.6wt.%, B:0.4-0.8wt.%, S:0.3-0.5wt.%, surplus are copper.The copper lithium The weight that alloy 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 8-12m/min that ingot casting, which moves down speed,.Ingot casting is subjected to deformation process at room temperature, every time Rolling under amount be 10-20%；Every 3 passes need to carry out an intermediate heat-treatment to eliminate processing hardening, and technique is：610 Degree, 3.9 hours；Final Heat Treatment Process after rolling is：Vacuum solid solution handles 720 degree, 5.8 hours；Vacuum aging processing 290 degree, 2.6 hours.

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

（1）Patent of the present invention is directed to the present situation that cupralith needs to carry out atmosphere protection melting in melting under current high temperature and carried A kind of novel protection solution is supplied.By the main and secondary addition element in preferred alloy, so as to effectively prevent Burning occurs for cupralith under melting state and excessive Evaporation Phenomenon is entered., not only can be big by preferable alloying method Big the shortcomings that reducing alloying element usage amount, extraordinary flame retardant effect can also be obtained and improve lithium recovery rate, final products The content of middle lithium accounts 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-Sb 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-Sb cupraliths are after lithium is added, because there is lithium excellent deoxidation degasification to make With so that crystal grain is refined.In addition, the alloy has low liquid-solid phase solidification temperature range, can solve heat during casting It is big to split tendency, the technical barriers such as the empty and loose obvious product yield rate of casting is low.

（4）The Cu-Li-Sb cupraliths have excellent mechanical property after timeliness.Modulus of elasticity：125-138GPa； Yield strength：950-1080MPa；Tensile strength：1100-1200MPa；Elongation percentage：4-10%.Elastic hysteresis is small, and with excellent Decay resistance：Corrosion rate in the seawater is less than 1.1 × 10^-2Mm/.And seawater is to the intensity and elongation percentage of the alloy Have no significant effect, thus can be on active service in the seawater more than 40 years, be the irreplaceable material of submarine cable structure body.

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

Embodiment

Embodiment 1

One kind has 1240 degree of smelting flame-proof high-strength highly-conductive Cu-Li-Sb cupraliths.By weight percentage, the chemistry of alloy Composition is：Li:1.3wt.%,Sb:1.8wt.%,Sr: 1.6wt.%,Er:0.3wt.%,Yb:0.1wt.%, Ni:0.4wt.%, B: 0.6wt.%,S:0.4wt.%, surplus are copper.The preparation method of alloy：As above the raw material matched is added under atmospheric environment In electric induction furnace, and use silicon carbide crucible.Sensing heating forms alloy solution to 1240 degree, and abundant using galvanomagnetic-effect Stirring 10 minutes or so.Alloy liquid is cast in the same level equipment of heat top for 10 minutes in 1240 degree of insulations and carries out semicontinuous casting Make, it is 8m/min that ingot casting, which moves down speed,.Ingot casting is subjected to deformation process at room temperature, amount is 12% under every time rolling.Every 3 Secondary rolling needs to carry out an intermediate heat-treatment to eliminate processing hardening, and technique is：610 degree, 3.9 hours；After rolling most Whole Technology for Heating Processing is：Vacuum solid solution handles 720 degree, 5.8 hours；Vacuum aging handles 290 degree, 2.6 hours.The alloy exists Between in 1240 degree and 5 hours stir under atmospheric environment, the melt treatment such as refining without obvious burning phenomenon occurs, and Material raw material proportion of goods damageds caused by evaporating and being formed due to clinker can be controlled in 2.6wt.% or so.The Cu-Li- Sb cupraliths have excellent mechanical property after timeliness.Modulus of elasticity：129GPa；Yield strength：987MPa；Tension is strong Degree：1106MPa；Elongation percentage：4.9%.Elastic hysteresis is small, and has excellent decay resistance：Corrosion rate in the seawater is small In 1.1 × 10^-2Mm/.And seawater has no significant effect to the intensity and elongation percentage of the alloy, thus can be on active service in the seawater More than 40 years, be the irreplaceable material of submarine cable structure body.

Embodiment 2

One kind has 1250 degree of smelting flame-proof high-strength highly-conductive Cu-Li-Sb cupraliths.By weight percentage, the chemistry of alloy Composition is：Li:1.4wt.%,Sb: 2.3wt.%,Sr:1.8wt.%, Er:0.3wt.%,Yb:0.1wt.%, Ni:0.3wt.%, B:0.6wt.%, S:0.4wt.%, surplus are copper.The preparation method of alloy：As above the raw material matched is added to atmospheric environment Under electric induction furnace in, and use silicon carbide crucible.Sensing heating forms alloy solution, and utilize galvanomagnetic-effect to 1250 degree It is sufficiently stirred 10 minutes or so.Alloy liquid is cast in the same level equipment of heat top for 10 minutes in 1250 degree of insulations and partly connected Continuous casting, it is 9m/min that ingot casting, which moves down speed,.Ingot casting is subjected to deformation process at room temperature, amount is 12% under every time rolling.Often 3 passes need to carry out an intermediate heat-treatment to eliminate processing hardening, and technique is：610 degree, 3.9 hours；After rolling Final Heat Treatment Process is：Vacuum solid solution handles 720 degree, 5.8 hours；Vacuum aging handles 290 degree, 2.6 hours.The alloy exists Between in 1250 degree and 5 hours stir under atmospheric environment, the melt treatment such as refining without obvious burning phenomenon occurs, and Material raw material proportion of goods damageds caused by evaporating and being formed due to clinker can be controlled in 3.7wt.% or so.The Cu-Li- Sb cupraliths have excellent mechanical property after timeliness.Modulus of elasticity：132GPa；Yield strength：1020MPa；Tension is strong Degree：1168MPa；Elongation percentage：5.2%.Elastic hysteresis is small, and has excellent decay resistance：Corrosion rate in the seawater is small In 1.1 × 10^-2Mm/.And seawater has no significant effect to the intensity and elongation percentage of the alloy, thus can be on active service in the seawater More than 40 years, be the irreplaceable material of submarine cable structure body.

Embodiment 3

One kind has 1270 degree of smelting flame-proof high-strength highly-conductive Cu-Li-Sb cupraliths.By weight percentage, the chemistry of alloy Composition is：Li:1.5wt.%,Sb: 2.1wt.%,Sr:2.1wt.%, Er: 0.3wt.%,Yb:0.1wt.%, Ni:0.4wt.%, B:0.6wt.%,S:0.3wt.%, surplus are copper.The preparation method of alloy：As above the raw material matched is added under atmospheric environment Electric induction furnace in, and use silicon carbide crucible.Sensing heating forms alloy solution, and fill using galvanomagnetic-effect to 1270 degree Divide stirring 10 minutes or so.By alloy liquid 1270 degree of insulations be cast within 10 minutes in the same level equipment of heat top carry out it is semicontinuous Casting, it is 8m/min that ingot casting, which moves down speed,.Ingot casting is subjected to deformation process at room temperature, amount is 12% under every time rolling.Every 3 Passes need to carry out an intermediate heat-treatment to eliminate processing hardening, and technique is：610 degree, 3.9 hours；After rolling Final Heat Treatment Process is：Vacuum solid solution handles 720 degree, 5.8 hours；Vacuum aging handles 290 degree, 2.6 hours.The alloy exists Between in 1270 degree and 5 hours stir under atmospheric environment, the melt treatment such as refining without obvious burning phenomenon occurs, and Material raw material proportion of goods damageds caused by evaporating and being formed due to clinker can be controlled in 4.2wt.% or so.The Cu-Li- Sb cupraliths have excellent mechanical property after timeliness.Modulus of elasticity：130GPa；Yield strength：1020MPa；Tension is strong Degree：1164MPa；Elongation percentage：6.2%.Elastic hysteresis is small, and has excellent decay resistance：Corrosion rate in the seawater is small In 1.1 × 10^-2Mm/.And seawater has no significant effect to the intensity and elongation percentage of the alloy, thus can be on active service in the seawater More than 40 years, be the irreplaceable material of submarine cable structure body.

Claims (3)

1. it is a kind of substitute beryllium-bronze Cu-Li-Sb cupraliths, it is characterised in that by weight percentage, alloy chemistry into It is divided into：Li: 0.6-1.9wt.%, Sb: 1.0-3.0wt.%,Sr: 1.0-2.6wt.%, Er: 0.2-0.5wt.%, Yb: 0.1-0.2wt.%, Ni:0.2-0.6wt.%, B:0.4-0.8wt.%, S:0.3-0.5wt.%, surplus are copper.

2. the Cu-Li-Sb cupraliths of beryllium-bronze are substituted 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 poured onto 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 8- that ingot casting, which moves down speed, 12m/min。

3. the Cu-Li-Sb cupraliths of beryllium-bronze are substituted according to claim 1, it is characterised in that include following processing step Suddenly：Ingot casting is subjected to deformation process at room temperature, amount is 10-20% under every time rolling；Every 3 passes need to carry out once Intermediate heat-treatment is hardened to eliminate processing, and technique is：610 degree, 3.9 hours；Final Heat Treatment Process after rolling is：Vacuum 720 degree, 5.8 hours of solution treatment；Vacuum aging handles 290 degree, 2.6 hours.