CN108315581A - A kind of low beryllium content copper alloy and preparation method thereof of high intensity high softening temperature - Google Patents
A kind of low beryllium content copper alloy and preparation method thereof of high intensity high softening temperature Download PDFInfo
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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
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
Abstract
The present invention relates to a kind of low beryllium content copper alloy and preparation method thereof of high intensity high softening temperature, the mass percent of low beryllium content copper alloy each component is：Be：0.2 0.5%, Ni：1.0 1.8%, Co：0.15 0.4%, Ag：0.5 0.8%, Zr：0.05 0.1%, Mg：0.02 0.05%, inevitable impurity≤0.1%, surplus Cu.The tensile strength of low beryllium content copper alloy prepared by the present invention is up to 850~1000MPa, conductivity is 50~60%IACS, softening temperature is up to 600 DEG C or more, also there are the comprehensive performances such as excellent high resiliency stability, low elasticity aftereffect, nonmagnetic, wearability, corrosion resistance and plasticity simultaneously, can be used for the industries such as rail traffic, aviation, automobile, electric power, electronics, precision instrumentation.
Description
Technical field
The present invention relates to field of alloy material, and in particular to a kind of low beryllium content copper alloy and its system of high intensity high softening temperature
Preparation Method.
Background technology
China is about 4000t to the annual requirement of the material containing beallon and rises year by year, but by limitations such as technical merits,
80% or more still relies on import.Beryllium expensive and be extremely toxic substance, the beryllium content of low beryllium content copper alloy is 0.2%~0.7%,
Have good conductive property and certain intensity and be widely used, and beryllium content compared with the high intensity such as TBe2 contain beallon
It is low, there is cost advantage and be good for the environment.As the low beryllium content copper alloys such as TBe0.3-1.5, TBe0.4-1.8 increase national standard newly
In, low beryllium content copper alloy receives more and more attention.Currently, after the timeliness of domestic low beryllium content copper alloy tensile strength be about 650~
750MPa, conductivity is 45~60%IACS, since impurity element equal size is higher in alloy, conductivity limit generally on the lower side.State
The tensile strength of the produced low beryllium content copper alloy materials of the well-known manufacturer in border such as NGK is 700~950MPa, and conductivity is 50~60%
IACS；Beryllium content in high intensity beallon is 1.6%~2.1%, and tensile strength highest can be more than 1400MPa after timeliness,
But conductivity is only 22%IACS.For copper alloy itself, any method for improving its intensity can all cause conductivity to reduce, because
The high intensity and high conductivity of this copper alloy are conflicts, can not be got both.
But with development in science and technology, conductor material used in the certain components in the fields such as rail traffic, military project, aviation, electronics needs
There is high conductivity and high intensity simultaneously.For example, high-intensity magnetic field technology magnet system coil method must be with the anti-of 1GPa or more
Tensile strength must have the relative conductivity of 60%~75%IACS or more concurrently to avoid high coke is generated to bear strong Lorentz force
It has burning ears；The large-scale integrated circuit lead frame strength of materials is 600MPa, relative conductivity 80%IACS or more, to ensure to carry
When copper alloy long-time stability；High-speed railway contact line supply voltage is 25~30KV, is usually required to improve current-carrying capacity
Reduce resistance, resistivity is smaller, and contact line unit length wire cross-section area is smaller, contacts line volume and weight is smaller, this is removed
Material is needed to have outside excellent mechanical performance, it is also necessary to high conductivity, wearability, anti-softening ability and corrosion resistance etc..
In addition, resistance welding electrode, continuous cast mold liner, electrical engineering switch touch bridge, large high-speed turbine generator rotator conducting wire, big
While power asynchronous traction motor rotor etc. is required to material with high intensity and high conductivity, also there is high temperature resistance softening
Ability.While the Cu-Ag in-situ fiber composite material intensity having now been developed at present reaches 1200MPa or more, conductivity can also
Be maintained at 60%~85%, performance can meet the requirement of high-strength high-conductivity, but the softening temperature of this composite material compared with
Low about 350 DEG C, and its production cost is high, long flow path, technology controlling and process is more difficult, and the country yet there are no the report for commercially producing application
Road, and the corrosion resistance of this composite material and wearability are also to be verified.
The occasion of a large amount of Joule heats is will produce in environment temperature is higher or the course of work, and is had to the strength of materials higher
It is required that when, it must consider the thermal stability of conductor material property.Softening temperature is the amount for evaluating material high temperature resistance softening power
Change index, from national standard《The assay method of GB/T 33370-2016 copper and copper alloy softening temperature》Since promulgation, copper alloy softening
The measurement of temperature has the standard sought unity of action, high temperature resistance softening power also increasingly to draw attention.Therefore, in existing ripe work
In skill technical foundation, impurity content is further controlled, it is low in few reduction (or even not reducing) by multielement microalloying
Further increase the intensity of alloy in the case of beallon conductivity and softening temperature be one kind can be achieved to commercially produce into
And meet the mode of practical application request.
In current published low beryllium content copper alloy related patents, if CN1616691A discloses a kind of low beryllium content copper alloy, firmly
Degree is high, wearability is good, but its Mn, Fe, Al total content is more than 15%, and conductivity is low, is only used as the materials such as mold.
CN101981211B discloses a kind of beryllium copper forging block of material, and the uniform of material property is improved by plastic processing and heat treatment
Property, aberrations in property is smaller up to 1100MPa or more, and on center, surface and a direction for intensity, but its Be contents control range compared with
Greatly, the upper limit 2.0%, and do not refer to conductivity, this kind of forging block is relatively suitable for bearing, babinet, mold etc. to conductivity
No requirement (NR) requires lower structural material field.CN102383078B discloses a kind of low beryllium copper conjunction of high-strength high-conductivity
Gold is added a certain amount of Nb and forms enhanced particles, and tensile strength is 1200~1400MPa, and CN102719699B is disclosed with one
Kind high resiliency low beryllium content copper alloy, tensile strength are 800~1010MPa, and the conductivity of both alloy materials is 45~60%
IACS, intensity and conductivity all substantially meet the requirement of high-strength high-conductivity Material Field, but thermal stability is especially anti-
Hot mastication performance is not evaluated.The highest softening temperature of beallon is about 520 DEG C at present.
Invention content
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of low beryllium content copper alloys of high intensity high softening temperature
And preparation method, for the tensile strength of this low beryllium content copper alloy up to 850~1000MPa, conductivity is 50~60%IACS, softening
Temperature also has excellent high resiliency stability, low elasticity aftereffect, nonmagnetic, wearability, anti-corrosion up to 600 DEG C or more
The comprehensive performances such as property and plasticity, can be used for the industries such as rail traffic, aviation, automobile, electric power, electronics, precision instrumentation.
The technical scheme is that：
A kind of low beryllium content copper alloy of high intensity high softening temperature, the mass percent of each component are：Be：0.2-0.5%,
Ni：1.0-1.8%, Co：0.15-0.4%, Ag：0.5-0.8%, Zr：0.05-0.1%, Mg：0.02-0.05%, unavoidably
Impurity≤0.1%, surplus Cu.
Preferably, the mass percent of each component is：Be：0.3-0.4%, Ni：1.4-1.6%, Co：0.3-0.4%,
Ag：0.6-0.8%, Zr：0.05-0.09%, Mg：0.03-0.04%, surplus Cu.
Preferably, Ni+Co≤2.0%, 4.5≤(Ni+Co)/Be≤6.0.
Inevitable impurity includes Fe, O, P, S, Fe≤0.015wt%, O≤0.005wt% in low beryllium content copper alloy.
The preparation method of above-mentioned low beryllium content copper alloy, has steps of：
1) melting
By each material rate dispensing of alloy, vacuum melting, smelting temperature is 1250-1350 DEG C, and charging sequence is, Cu, Ni,
After Co fine melts, interval sequentially adds Ag, Be, Zr, Mg under protective atmosphere, and melting finishes, and is poured into a mould after standing, and cast temperature is
It 1170-1250 DEG C, is demoulded after cooling and obtains ingot casting；
2) it forges
Ingot casting obtained by step 1) is heated to 850-920 DEG C after face milling, keeps the temperature 1-3h, 850-920 DEG C of initial forging temperature,
Final forging temperature is not less than 780 DEG C, obtains forging stock；
3) hot rolling
Forging stock obtained by step 2) is heated to 850-950 DEG C, keeps the temperature 1-2h, finishing temperature is not less than 800 DEG C, obtains line
Material；
4) solution treatment
The wire rod that step 3) obtains is warming up to 890-950 DEG C and keeps the temperature 1-5h, water quenching, come out of the stove to enter time of water≤
5s；
5) cold plasticity is processed
It will be dried after wire acid cleaning after step 4) solution treatment, multi-pass cold drawing or cold rolling, every time working modulus
70% or more, obtain silk material；
6) ageing treatment
Silk material after step 5) cold plasticity is processed is warming up to 400-520 DEG C of heat preservation 1-7h, air-cooled or furnace cooling.
Step 1) the melting includes the following steps：
1) Cu, Ni, Co are placed in container, wherein Ni, Co is located at lower vessel portion, cobbing, container are placed between bulk material
Lower part consolidation, top are loose；
2) vacuum drying oven suction ＜ 30Pa, 1250-1350 DEG C of feeding temperature-raising to Cu, Ni, Co fine melt；
3) it refining for the first time, when adjusting vacuum degree ＜ 10Pa, argon filling to 7-10kPa is spaced Ag, Be, Zr is added successively,
In, Zr is with CuZr14Intermediate alloy form is added, and often plus after a kind of raw material increases power transmission power and stirring 2-5s is to fine melt, refine
Shi Fanfu shakes container, refining time 15-30min；
4) it refines for second, when adjusting vacuum degree ＜ 5Pa, Mg is added in argon filling to 7-10kPa, and Mg is with MgNi20Intermediate alloy shape
Formula is added, refining time 10-15min, and stirring, oscillation 5-10s are stood, and to 1170-1250 DEG C, casting solidification demoulds for temperature adjustment
To ingot casting.
Above-mentioned steps 1) Cu that is added is No. two copper oxide, the Ni of addition is electrolytic nickel, and the Co of addition is electrolytic cobalt.
Every time of step 5) cold drawing or cold rolling need intermediate heat-treatment, the pickling, wherein intermediate heat-treatment temperature to be
890-950 DEG C, keep the temperature 20min-1h.
The effect of alloy each element of the present invention is as follows：
Ni、Be：Ni and Be forms NiBe and Ni5Be21Two kinds of intermediate compounds.Have in Cu when Ni and Be high temperature higher
Solubility, when the temperature decreases the solubility of Ni be obviously reduced, first can obtain single supersaturated α through solution treatment and be dissolved
Body, then precipitation strength effect is obtained by ageing treatment and improves the strength of materials and wearability.The addition of Ni can not only inhibit alloy
Phase transformation in quenching process delays Solid solution decomposition, inhibits recrystallization process, improves the uniformity of tissue, crystal grain thinning, moreover it is possible to
The equilibrium potential of material is improved, corrosion resistance is enhanced.If Ni contents are less than 1%, stronger ageing strengthening effect cannot be generated；But
If Ni contents are higher than 1.8%, material electric conductivity has obvious reduction.
Co：It hinders crystal grain in alloy heating process to grow up, delays Solid solution decomposition.BeCo intermediate compounds are formed with Be,
Inhibit crystal boundary reaction, avoids inhomogeneities caused by overaging, the aging technique of aging alloy material is made to be more prone to control.Co
If content is less than 0.15%, stronger ageing strengthening effect cannot be generated, and crystal boundary reaction easily occurs, aging technique is not easily-controllable
System；But if Co contents are higher than 0.4%, and material electric conductivity has obvious reduction, and cost is higher.
Ag：Influence to copper alloy electric conductivity is minimum, the intensity after alloy aging can be improved, and keep high conductance
Rate significantly improves alloy recrystallization temperature, creep strength and the hot low-cycle fatigue stability of high temperature resistance.If Ag contents are less than
0.5%, then intensity and recrystallization temperature and other effects improve unobvious after material ages；If but Ag contents are higher than 0.8%, Ag atoms
The roughening of meeting agglomeration is in spherical, the reduction strength of materials and conductivity in ag(e)ing process, and cost is higher.
Zr：Influence to copper alloy electric conductivity is smaller, and a small amount of zirconium can form the precipitated phase of small and dispersed, not only can be into
One step improves the hardness of alloy material, delays and postpone recrystallization, is also remarkably improved the softening temperature of copper alloy, and refinement is tied again
Jingjing grain.If Zr contents are less than 0.05%, material softening temperature can not be improved or can only improved on a small quantity；If but Zr contents are higher than
0.1%, the adverse effect of material electric conductivity is started to increase, and cost is higher.
Mg：Magnesium is the maximum element of surface-active in beryllium-bronze, a small amount of magnesium can crystal grain thinning, keep Υ phase particles tiny
It is distributed evenly, there is certain deoxidation, the mechanical property and corrosion resisting property and high-temperature stability of alloy are improved, to electric conductivity shadow
Sound is smaller.If Mg contents are less than 0.02%, to material Grain refinement unobvious；But if Mg contents are higher than 0.05%,
Material conductivity reduces, and easily forms hard and crisp MgCu2Phase, it is unfavorable to material mechanical performance.
The adverse effect of impurity element in the low beryllium content copper alloy material：
Fe：Although iron can delay alloy recrystallization crystal grain thinning, excessive Fe can form rich Fe phases, to reduce material
Processing performance, can also reduce the nonmagnetic performance of material, this is totally unfavorable to precision instrument material, therefore strictly controls content
≤ 0.015%.
O：Oxygen is affected to copper alloy conductivity, and forms the eutectic phase that fusing point is higher than hot processing temperature with copper, cold to add
Working hour easily occur it is cold short, therefore strictly control content≤0.005%.
The effect of each technique of preparation method of the present invention is as follows：
Vacuum melting is to produce one of the basic skills of infusibility, rare active metal, and active metal chemistry activity is strong (such as
Beryllium used herein, zirconium, magnesium elements), under air when founding can abrupt oxidization and nitridation, formation is largely mingled with, and passes through vacuum
Melting can get the metal material of high-purity, high quality, and advantage is that air content is low, impurity is few, be mingled with that size is small, and defect is few, add
Work performance is good.
By the way that the high raw material (Cu, Ni, Co) for being not easy oxidization burning loss of fusing point is placed on crucible middle and lower part, placed between bulk material
Small powder, tightly upper pine under crucible, effectively prevent " bridge formation " phenomenon occur when metal molten.It is added after the raw material of oxidizable, easy air-breathing,
And its oxidation or evaporation are inhibited by inert gas pressurization, the purity and quality of smelting metal material is effectively ensured.
The tissue for keeping as cast condition coarse is deformed and recrystallized in open die forging and course of hot rolling becomes tiny and uniform equiax crystal
Grain, makes being improved or being eliminated the defects of being segregated, is loose, being mingled in ingot casting, improves the processing performance and mechanical property of material,
Its sectional dimension reduces, and is convenient for follow-up plastic processing.
Solution treatment can get uniform supersaturated solid solution, and performing tissue for ageing strengthening prepares, in pressure processing
Between soften also need carry out solution treatment.Ni and Be can form NiBe and Ni5Be21Two kinds of intermediate compounds, and when Ni and Be high temperature
There is higher solubility in Cu, its solubility is obviously reduced when the temperature decreases, therefore can first be obtained through solution treatment single
Supersaturated αsolidsolution, then precipitation strength effect is obtained by ageing treatment.
Cold drawing and cold-rolled process can get plank, band, wire rod, bar and the tubing of certain deformation extent, size essence
Exactness is high, can be by the degree of deformation amount controlling working hardening, and the comprehensive mechanical property of material can be made more by being combined with aging technique
It is good.
Ageing treatment can make Be, Ni atom being dissolved in matrix be precipitated through phase transformation to be formed NiBe that is tiny and being evenly distributed and
Ni5Be21Particle hinders the mobile generation dispersion-strengtherning of dislocation and crystal boundary etc..
Low beryllium content copper alloy of the present invention effectively improves copper alloy again by adding micro Ag, Zr, Mg element
Crystallization temperature and thermal stability, through cold plasticity processing, the low beryllium content copper alloy material obtained after fixation rates at the same have compared with
High tensile strength (up to 850-1000MPa), higher conductivity (50-60%IACS) and higher softening temperature (can
Up to 600 DEG C or more).Traditional copper alloy high strength and high conductivity is effectively solved to contradict and high conductivity and high softening temperature phase
The problem of contradiction.
It is further described in the following with reference to the drawings and specific embodiments.
Description of the drawings
Fig. 1 is material preparation process Parameter Map of the present invention；
Fig. 2 is the softening temperature performance diagram of each embodiment and other materials containing beallon.
Specific implementation mode
Embodiment 1
1. dispensing
Take No. two oxygen-free coppers, electrolytic nickel, electrolytic cobalt, beryllium pearl, high purity silver, CuZr14、MgNi20As raw material, raw material is removed
Surface corrosion product, removes greasy dirt, supernatant liquid etc., and drying is for use.According to mass ratio Be：0.3%, Ni：1.4%, Co：0.3%,
Ag：0.6, Zr：0.07%, Mg：0.04% carries out dispensing.
2. melting and casting
No. two oxygen-free coppers, electrolytic nickel and electrolytic cobalt are placed in crucible, wherein electrolytic nickel and electrolytic cobalt are loaded under in crucible
Portion, small powder is placed between bulk material, and " bridge formation " phenomenon occurs in lower tight upper pine when preventing metal molten.Beryllium pearl, high purity silver, CuZr14
And MgNi20Intermediate alloy is placed in loading hopper.It vacuumizes, when vacuum degree in stove<Start power transmission melt when 30Pa, first with medium work(
Rate about 30KW or so power transmission is gradually increased power to temperature and is raised to 1250~1350 DEG C, and after raw material fine melt in crucible, reduction is sent
Electrical power.First time refining, power 25KW, 20 minutes time, vacuum degree are carried out after fine melt<10Pa, during which fascinate crucible repeatedly.
Argon filling sequentially adds high purity silver, beryllium pearl, CuZr to 7~10kPa14Intermediate alloy should all increase work(often plus after a kind of element
Rate stirs 2~5 seconds, is melted with accelerating and is allowed to be evenly distributed.It carries out refining for second later, power 20KW, the time 10 divides
Clock, vacuum degree<2Pa.MgNi is added in argon filling20Intermediate alloy, abundant electromagnetism and mechanical agitation, concussion 5~10 seconds.It stands, adjusts
Temperature to 1170~1250 DEG C, continuously cast at a slow speed by thread, and rear vacuum breaker to be solidified is come out of the stove, and is demoulded after cooling and is obtained ingot casting.
3. milling face
Ingot casting surface oxide skin etc. is milled, ingot casting is sampled and carries out chemical composition analysis, the results are shown in Table 1.
4. forging
The ingot casting in milling face is warming up to 890 DEG C with stove heat, keeps the temperature 1.5 hours, 890 DEG C of initial forging temperature, final forging temperature is not
Less than 780 DEG C.Centre is melted down heating and thermal insulation again and time and is not less than 15 minutes, finally forge as sectional dimension be 30 ×
The vertical bar and chamfering of 30mm, obtains forging stock, dye-penetrant inspection and ultrasonic examination.
5. hot rolling
Forging stock is warming up to 920 DEG C with stove heat, keeps the temperature 1 hour, finishing temperature is not less than 820 DEG C, hot rolling pass Φ
28mm → Φ 24mm → Φ 22mm → Φ 20mm → Φ 18mm → Φ 16mm → Φ 14mm, obtain disk round wires material.
6. solution treatment
To warm shove charge after disk round wires material is warming up to 920 DEG C, 1 hour is kept the temperature, water quenching enters water process time and is no more than 5 seconds
Clock.
7. cold drawing
Disk circle wire acid cleaning after solution treatment removes surface scale, and cold drawing processing is carried out after drying, processes passage
For Φ 14mm → Φ 7mm → intermediate heat-treatment (920 DEG C keep the temperature 30 minutes) → acid wash passivation → Φ 3mm → intermediate heat-treatment (920
DEG C heat preservation 20 minutes) → acid wash passivation → Φ 1mm.
8. ageing treatment
Silk material after cold drawing arrives warm shove charge after being warming up to 480 DEG C, keep the temperature 3 hours, air-cooled.
Through the above process processing after, Φ 1mm silk materials after timeliness tensile strength be 920MPa, conductivity 57%IACS,
Softening temperature is 609 DEG C.
Embodiment 2
1. dispensing
Take No. two oxygen-free coppers, electrolytic nickel, electrolytic cobalt, beryllium pearl, high purity silver, CuZr14、MgNi20As raw material, raw material is removed
Surface corrosion product, removes greasy dirt, supernatant liquid etc., and drying is for use.According to mass ratio Be：0.4%, Ni：1.5%, Co：
0.35%, Ag：0.7, Zr：0.08%, Mg：0.04% carries out dispensing.
2. melting and casting
No. two oxygen-free coppers, electrolytic nickel and electrolytic cobalt are placed in crucible, and electrolytic nickel and electrolytic cobalt are mounted in crucible middle and lower part, bulk
Small powder is placed between material, lower tight upper pine prevents " bridge formation " phenomenon, beryllium pearl, high purity silver, CuZr occur when metal molten14And MgNi20
Intermediate alloy is placed in loading hopper.It vacuumizes, when vacuum degree in stove<Start power transmission material when 30Pa, first mid power about 30KW,
It is gradually increased power to temperature and is raised to 1250~1350 DEG C, after raw material fine melt in crucible, reduce power transmission power.Raw material in crucible
First time refining, power 25KW, 25 minutes time, vacuum degree are carried out after fine melt<10Pa, during which fascinate crucible repeatedly.Argon filling is to 7
~10kPa sequentially adds high purity silver, beryllium pearl, CuZr14Intermediate alloy often plus after a kind of element, should all increase power stirring 2
It~5 seconds, is melted with accelerating and is allowed to be evenly distributed.It carries out refining for second later, power 20KW, 15 minutes time, vacuum
Degree<2Pa.MgNi is added in argon filling20Intermediate alloy, abundant electromagnetism and mechanical agitation, concussion 5~10 seconds.It stands, temperature adjustment is extremely
1170~1250 DEG C, thread is continuously cast at a slow speed, and rear vacuum breaker to be solidified is come out of the stove, and is demoulded after cooling, is obtained ingot casting.
3. milling face
Ingot casting surface oxide skin etc. is milled, ingot casting is sampled and carries out chemical composition analysis, the results are shown in Table 1.
4. forging
Ingot casting behind milling face is warming up to 900 DEG C with stove heat, keeps the temperature 2 hours, 900 DEG C of initial forging temperature, final forging temperature is not low
In 780 DEG C.The heating and thermal insulation time again is melted down in centre, and not less than 20 minutes, it was 30 × 30mm's finally to forge as sectional dimension
Vertical bar and chamfering, obtain forging stock, dye-penetrant inspection and ultrasonic examination.
5. hot rolling
Forging stock is warming up to 920 DEG C with stove heat, keeps the temperature 1.5 hours, and finishing temperature is not less than 820 DEG C, hot rolling pass Φ
28mm → Φ 24mm → Φ 22mm → Φ 20mm → Φ 18mm → Φ 16mm → Φ 14mm, obtain disk round wires material.
6. solution treatment
Disk round wires material arrives warm shove charge after being warming up to 950 DEG C, keep the temperature 1 hour, water quenching, enters water process time and is no more than 5 seconds.
7. cold drawing
Disk circle wire acid cleaning after solution treatment removes surface scale, and cold drawing processing is carried out after drying, processes passage
For Φ 14mm → Φ 7mm → intermediate heat-treatment (950 DEG C keep the temperature 30 minutes) → acid wash passivation → Φ 3mm → intermediate heat-treatment (950
DEG C heat preservation 20 minutes) → acid wash passivation → Φ 1mm.
8. ageing treatment
Silk material after cold drawing arrives warm shove charge after being warming up to 480 DEG C, keep the temperature 3 hours, air-cooled.
Through the above process processing after, Φ 1mm silk materials after timeliness tensile strength be 954MPa, conductivity 55%IACS,
Softening temperature is 623 DEG C.
Embodiment 3
1. dispensing
Take No. two oxygen-free coppers, electrolytic nickel, electrolytic cobalt, beryllium pearl, high purity silver, CuZr14、MgNi20As raw material, raw material is removed
Surface corrosion product, removes greasy dirt, supernatant liquid etc., and drying is for use.According to mass ratio Be：0.44%, Ni：1.6%, Co：
0.4%, Ag：0.8, Zr：0.1%, Mg：0.05% carries out dispensing.
2. melting and casting
No. two oxygen-free coppers, electrolytic nickel and electrolytic cobalt are placed in crucible, and electrolytic nickel and electrolytic cobalt are mounted in crucible middle and lower part, bulk
Small powder is placed between material, lower tight upper pine prevents " bridge formation " phenomenon, beryllium pearl, high purity silver, CuZr occur when metal molten14And MgNi20
Intermediate alloy is placed in loading hopper.It vacuumizes, when vacuum degree in stove<Start power transmission material when 30Pa, first about with mid power
30KW or so power transmissions are gradually increased power to temperature and are raised to 1250~1350 DEG C, after fine melt, reduce power transmission power.After fine melt
Carry out first time refining, power 30KW, 20 minutes time, vacuum degree<10Pa, during which fascinate crucible repeatedly.Argon filling to 7~
10kPa sequentially adds high purity silver, beryllium pearl, CuZr14Intermediate alloy often plus after a kind of element, should all increase power stirring 2~5
Second, it is melted with accelerating and is allowed to be evenly distributed.It carries out refining for second later, power 25KW, 10 minutes time, vacuum degree<
2Pa.MgNi is added in argon filling20Intermediate alloy, abundant electromagnetism and mechanical agitation, concussion 5~10 seconds.It stands, temperature adjustment to 1170~
1250 DEG C, thread is continuously cast at a slow speed, and rear vacuum breaker to be solidified is come out of the stove, and is demoulded after cooling and is obtained ingot casting.
3. milling face
Ingot casting surface oxide skin etc. is milled, ingot casting is sampled and carries out chemical composition analysis, the results are shown in Table 1.
4. forging
920 DEG C are warming up to stove heat, keeps the temperature 2 hours, 920 DEG C of initial forging temperature, final forging temperature is not less than 800 DEG C.It is intermediate
Melt down again the heating and thermal insulation time be not less than 20 minutes, finally forge as sectional dimension be 30 × 30mm vertical bar and chamfering,
Obtain forging stock, dye-penetrant inspection and ultrasonic examination.
5. hot rolling
Forging stock is warming up to 920 DEG C with stove heat, keeps the temperature 2 hours, and finishing temperature is not less than 820 DEG C, hot rolling pass Φ
28mm → Φ 24mm → Φ 22mm → Φ 20mm → Φ 18mm → Φ 16mm → Φ 14mm, obtain disk round wires material.
6. solution treatment
Disk round wires material arrives warm shove charge after being warming up to 920 DEG C, keep the temperature 1.5 hours, water quenching, enters water process time and is no more than 5 seconds
Clock.
7. cold drawing
Disk circle wire acid cleaning after solution treatment removes surface scale, and cold drawing processing is carried out after drying, processes passage
For Φ 14mm → Φ 7mm → intermediate heat-treatment (920 DEG C keep the temperature 30 minutes) → acid wash passivation → Φ 3mm → intermediate heat-treatment (890
DEG C heat preservation 30 minutes) → acid wash passivation → Φ 1mm.
8. ageing treatment
To warm shove charge after the silk material after cold drawing is warming up to 480 DEG C, 3 hours are kept the temperature, it is air-cooled.
Through the above process processing after, Φ 1mm silk materials after timeliness tensile strength be 989MPa, conductivity 51%IACS,
Softening temperature is 642 DEG C.
1 each embodiment low beryllium content copper alloy chemical composition (wt%) of table
| Element | Be | Ni | Co | Ag | Zr | Mg | Fe | O | S | P | Cu |
| Embodiment 1 | 0.28 | 1.4 | 0.29 | 0.58 | 0.056 | 0.025 | 0.012 | 0.004 | <0.004 | <0.002 | Surplus |
| Embodiment 2 | 0.36 | 1.5 | 0.32 | 0.66 | 0.078 | 0.035 | 0.010 | 0.003 | <0.004 | <0.002 | Surplus |
| Embodiment 3 | 0.42 | 1.58 | 0.39 | 0.77 | 0.092 | 0.044 | 0.012 | 0.005 | <0.004 | <0.002 | Surplus |
Each embodiment and the performance comparison of commercially available TBe2, TBe0.3-1.5 and import C17510 are as shown in table 2.
2 each embodiment of table and other beryllium copper material performance comparisons
| Material | Tensile strength/MPa | Conductivity/%IACS | Softening temperature/DEG C |
| Embodiment 1 | 920 | 57 | 609 |
| Embodiment 2 | 954 | 55 | 623 |
| Embodiment 3 | 989 | 51 | 642 |
| Domestic TBe2 | 1342 | 26 | 442 |
| Domestic TBe0.3-1.5 | 467 | 51 | 350 |
| Import C17510 | 783 | 58 | 524 |
Claims (8)
1. a kind of low beryllium content copper alloy of high intensity high softening temperature, which is characterized in that the mass percent of each component is：Be：
0.2-0.5%, Ni：1.0-1.8%, Co：0.15-0.4%, Ag：0.5-0.8%, Zr：0.05-0.1%, Mg：0.02-
0.05%, inevitable impurity≤0.1%, surplus Cu.
2. low beryllium content copper alloy according to claim 1, which is characterized in that the mass percent of each component is：Be：0.3-
0.4%, Ni：1.4-1.6%, Co：0.3-0.4%, Ag：0.6-0.8%, Zr：0.05-0.09%, Mg：0.03-0.04%, it is remaining
Amount is Cu.
3. low beryllium content copper alloy according to claim 1 or 2, it is characterised in that：Ni+Co≤2.0%, 4.5≤(Ni+Co)/
Be≤6.0。
4. low beryllium content copper alloy according to claim 1, it is characterised in that：Inevitable impurity F e≤0.015wt%, O
≤ 0.005wt%.
5. the preparation method of any low beryllium content copper alloy of claims 1 to 3, which is characterized in that have steps of：
1) melting
By claims 1 or 2 or 3 dispensings, vacuum melting, smelting temperature is 1250-1350 DEG C, and charging sequence is Cu, Ni, Co
After fine melt, interval sequentially adds Ag, Be, Zr, Mg under protective atmosphere, and melting finishes, and is poured into a mould after standing, and cast temperature is
It 1170-1250 DEG C, is demoulded after cooling and obtains ingot casting；
2) it forges
Ingot casting obtained by step 1) is heated to 850-920 DEG C after face milling, keeps the temperature 1-3h, 850-920 DEG C of initial forging temperature, finish-forging
Temperature is not less than 780 DEG C, obtains forging stock；
3) hot rolling
Forging stock obtained by step 2) is heated to 850-950 DEG C, keeps the temperature 1-2h, finishing temperature is not less than 800 DEG C, obtains wire rod；
4) solution treatment
The wire rod that step 3) obtains is warming up to 890-950 DEG C and keeps the temperature 1-5h, water quenching is come out of the stove to the time≤5s for entering water；
5) cold plasticity is processed
To be dried after wire acid cleaning after step 4) solution treatment, multi-pass cold drawing or cold rolling, every time working modulus 70% with
On, obtain silk material；
6) ageing treatment
Silk material after step 5) cold plasticity is processed is warming up to 400-520 DEG C of heat preservation 1-7h, air-cooled or furnace cooling.
6. preparation method according to claim 5, which is characterized in that the step 1) melting includes the following steps：
1) Cu, Ni, Co are placed in container, wherein Ni, Co is located at lower vessel portion, cobbing, lower vessel portion are placed between bulk material
Consolidation, top are loose；
2) vacuum drying oven suction ＜ 30Pa, 1250-1350 DEG C of feeding temperature-raising to Cu, Ni, Co fine melt；
3) it refines for the first time, when adjusting vacuum degree ＜ 10Pa, argon filling to 7-10kPa is spaced Ag, Be, Zr is added successively, wherein Zr
With CuZr14Intermediate alloy form is added, and often plus after a kind of raw material increases power transmission power and stirring 2-5s is to fine melt, when refining repeatedly
Shake container, refining time 15-30min；
4) it refines for second, when adjusting vacuum degree ＜ 5Pa, Mg is added in argon filling to 7-10kPa, and Mg is with MgNi20Intermediate alloy form adds
Enter, refining time 10-15min, stirring, oscillation 5-10s are stood, and to 1170-1250 DEG C, casting solidification demoulding is cast for temperature adjustment
Ingot.
7. preparation method according to claim 5, which is characterized in that the Cu that step 1) is added is No. two copper oxide, is added
Ni be electrolytic nickel, the Co of addition is electrolytic cobalt.
8. preparation method according to claim 5, which is characterized in that in every time need of step 5) cold drawing or cold rolling
Between heat treatment, pickling, wherein intermediate heat-treatment temperature be 890-950 DEG C, keep the temperature 20min-1h.
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