CN108315581B - High-strength high-softening-temperature low beryllium copper alloy and preparation method thereof - Google Patents
High-strength high-softening-temperature low beryllium copper alloy and preparation method thereof Download PDFInfo
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- 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 invention relates to a low beryllium copper alloy with high strength and high softening temperature and a preparation method thereof, wherein the low beryllium copper alloy comprises the following components in percentage by mass: 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%, less than or equal to 0.1% of inevitable impurities, and the balance of Cu. The low beryllium copper alloy prepared by the invention has the tensile strength of 850-1000MPa, the conductivity of 50-60% IACS, the softening temperature of over 600 ℃, and the comprehensive properties of excellent high elastic stability, low elastic aftereffect, no magnetism, wear resistance, corrosion resistance, plasticity and the like, and can be used in the industries of rail transit, aviation, automobiles, electric power, electronics, precise instruments and meters and the like.
Description
Technical Field
The invention relates to the field of alloy materials, in particular to a high-strength high-softening-temperature low beryllium copper alloy and a preparation method thereof.
Background
The annual demand of China for beryllium-containing copper alloy materials is about 4000t and is increased year by year, but the annual demand is limited by the technical level and the like, and more than 80% of the annual demand still depends on import. The low beryllium copper alloy has the advantages of high price of beryllium and high toxicity, has the beryllium content of 0.2-0.7 percent, has good conductive performance and certain strength and is widely applied, and has lower beryllium content than high-strength beryllium copper alloys such as TBe2, so the low beryllium copper alloy has the cost advantage and is beneficial to environmental protection. With the addition of low beryllium copper alloys such as TBe0.3-1.5, TBe0.4-1.8 and the like to the national standard, the low beryllium copper alloys are receiving more and more attention. At present, the tensile strength of domestic low beryllium copper alloy after aging is about 650-750 MPa, the conductivity is 45-60% IACS, and the conductivity is generally lower limit due to higher content of impurity elements and the like in the alloy. The tensile strength of a low beryllium copper alloy material produced by international known manufacturers such as NGK is 700-950 MPa, and the conductivity is 50-60% IACS; the beryllium content in the high-strength beryllium copper alloy is 1.6-2.1%, the tensile strength can be over 1400MPa at most after aging, but the conductivity is only 22% IACS. For the copper alloy itself, any method for improving the strength of the copper alloy will result in the reduction of the electrical conductivity, so that the high strength and the high electrical conductivity of the copper alloy are contradictory and cannot be obtained at the same time.
However, with the development of science and technology, the conductive materials used for some parts in the fields of rail transit, military industry, aviation, electronics and the like need to have both high conductivity and high strength. For example, the coil material of the high magnetic field magnet system must have a tensile strength of 1GPa or more to bear a strong Lorentz force, and must also have a relative conductivity of 60% to 75% IACS or more to avoid generating high Joule heat; the strength of the large-scale integrated circuit lead frame material is 600MPa, and the relative conductivity is more than 80% IACS (International Annealed copper standard), so that the long-term stability of the copper alloy during bearing is ensured; the power supply voltage of a contact line of a high-speed railway is 25-30 KV, the resistance is generally required to be reduced in order to improve the current-carrying capacity, the smaller the resistivity is, the smaller the sectional area of a lead per unit length of the contact line is, and the smaller the volume and the weight of the contact line are, so that the material is required to have excellent mechanical properties, and high conductivity, wear resistance, softening resistance, corrosion resistance and the like are required. In addition, the materials required by the resistance welding electrode, the lining of the continuous casting crystallizer, the contact bridge of the electrical engineering switch, the rotor lead of the large-sized high-speed turbine generator, the rotor of the high-power asynchronous traction motor and the like have high strength and high conductivity, and simultaneously have high-temperature softening resistance. The strength of the Cu-Ag in-situ fiber composite material developed at present reaches over 1200MPa, the conductivity can be kept between 60 and 85 percent, and the performance can meet the requirements of high strength and high conductivity, but the softening temperature of the composite material is lower than 350 ℃, the production cost is high, the flow is long, the process control is difficult, no report of commercial production application is seen in China, and the corrosion resistance and the wear resistance of the composite material are yet to be verified.
In the case of high ambient temperature or a large amount of joule heat generated during operation, and when the strength of the material is required, the thermal stability of the performance of the conductor material must be considered. The softening temperature is a quantitative index for evaluating the high-temperature softening resistance of the material, and since the national standard GB/T33370-2016 copper and copper alloy softening temperature measuring method promulgated, the measurement of the softening temperature of the copper alloy has a unified execution standard, and the high-temperature softening resistance is more and more emphasized. Therefore, on the basis of the existing mature process technology, the content of impurity elements is further controlled, and the strength and the softening temperature of the alloy are further improved by multi-element microalloying under the condition of slightly reducing (even not reducing) the conductivity of the low beryllium copper alloy, so that the mode of realizing commercial production and further meeting the actual application requirements is provided.
In the related patents of the low beryllium copper alloy disclosed at present, for example, CN1616691A discloses a low beryllium copper alloy which has high hardness and good wear resistance, but the total content of Mn, Fe and Al exceeds 15%, and the conductivity is low, so that the alloy is only used as materials of dies and the like. CN101981211B discloses a beryllium copper forging block material, which improves the uniformity of material performance through plastic processing and heat treatment, has the strength of more than 1100MPa, and has smaller performance deviation in the center, surface and each direction, but has larger Be content control range and the upper limit of 2.0 percent, and does not mention conductivity, and the forging block is more suitable for the field of structural materials of bearings, boxes, dies and the like which have no or lower requirements on conductivity. CN102383078B discloses a high-strength high-conductivity low beryllium copper alloy, a certain amount of Nb is added to form reinforced particles, the tensile strength of the alloy is 1200-1400 MPa, CN102719699B discloses a high-elasticity low beryllium copper alloy, the tensile strength is 800-1010 MPa, the conductivity of the two alloy materials is 45-60% IACS, the strength and the conductivity of the two alloy materials basically meet the requirements of the field of high-strength high conductivity materials, but the thermal stability, particularly the high-temperature softening resistance, is not evaluated. The maximum softening temperature of beryllium copper alloys is currently about 520 ℃.
Disclosure of Invention
The invention aims to provide a low beryllium copper alloy with high strength and high softening temperature and a preparation method thereof, aiming at the defects of the prior art, the low beryllium copper alloy has the tensile strength of 850-1000MPa, the conductivity of 50-60% IACS, the softening temperature of over 600 ℃, and simultaneously has the comprehensive properties of excellent high elastic stability, low elastic after effect, no magnetism, wear resistance, corrosion resistance, plasticity and the like, and can be used in the industries of rail transit, aviation, automobiles, electric power, electronics, precise instruments and meters and the like.
The technical scheme of the invention is as follows:
a high-strength high-softening-temperature low beryllium copper alloy comprises the following components in percentage by mass: 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%, less than or equal to 0.1% of inevitable impurities, and the balance of Cu.
Preferably, the mass percentages of the components are as follows: 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% and the balance of Cu.
Preferably, Ni + Co is less than or equal to 2.0%, and 4.5 is less than or equal to (Ni + Co)/Be is less than or equal to 6.0.
The inevitable impurities in the low beryllium copper alloy comprise Fe, O, P and S, wherein the weight percent of Fe is less than or equal to 0.015 percent, and the weight percent of O is less than or equal to 0.005 percent.
The preparation method of the low beryllium copper alloy comprises the following steps:
1) melting
Proportioning raw materials according to the proportion of the alloy, carrying out vacuum melting at 1250-;
2) forging
Milling the surface of the ingot obtained in the step 1), heating to 850-;
3) hot rolling
Heating the forging stock obtained in the step 2) to 850-950 ℃, and preserving the heat for 1-2h, wherein the finish rolling temperature is not lower than 800 ℃, so as to obtain a wire;
4) solution treatment
Heating the wire obtained in the step 3) to 890-950 ℃, preserving the heat for 1-5h, quenching with water, and discharging the wire out of the furnace until the time of water entering is less than or equal to 5 s;
5) cold plastic working
Pickling and drying the wire rod subjected to the solution treatment in the step 4), and performing multi-pass cold drawing or cold rolling with the processing rate of each pass being more than 70% to obtain a wire rod;
6) aging treatment
Heating the wire subjected to cold plastic processing in the step 5) to 400-520 ℃, preserving the heat for 1-7h, and cooling in air or with a furnace.
Step 1) the smelting comprises the following steps:
1) placing Cu, Ni and Co in a container, wherein the Ni and Co are positioned at the lower part of the container, small blocks are placed between large blocks, the lower part of the container is compact, and the upper part of the container is loose;
2) the vacuum degree of the vacuum furnace is less than 30Pa, and the temperature is raised to 1250-;
3) refining for the first time, when the vacuum degree is adjusted to Be less than 10Pa, filling argon to 7-10kPa, and sequentially adding Ag, Be and Zr at intervals, wherein the Zr is CuZr14Adding the intermediate alloy, increasing the power transmission and stirring for 2-5s to complete melting after adding one raw material, and repeatedly shaking the container during refining for 15-30 min;
4) refining for the second time, adjusting vacuum degree to be less than 5Pa, filling argon to 7-10kPa, adding Mg, MgNi20Adding the intermediate alloy in a form of refining for 10-15min, stirring, oscillating for 5-10s, standing, adjusting the temperature to 1170-1250 ℃, casting, solidifying and demolding to obtain the cast ingot.
The Cu added in the step 1) is copper oxide II, the Ni added is electrolytic nickel, and the Co added is electrolytic cobalt.
And 5) carrying out intermediate heat treatment and acid pickling during each cold drawing or cold rolling, wherein the intermediate heat treatment temperature is 890-950 ℃, and the heat preservation time is 20min-1 h.
The alloy of the invention has the following functions of elements:
ni, Be: ni and Be form NiBe and Ni5Be21Two intermediate compounds. Both Ni and Be have higher solubility in Cu at high temperature, the solubility of Ni is obviously reduced when the temperature is reduced,the addition of Ni can inhibit phase change in the alloy quenching process, delay the decomposition of the solid solution, inhibit the recrystallization process, improve the uniformity of the structure, refine grains, improve the equilibrium potential of the material and enhance the corrosion resistance, if the content of Ni is lower than 1%, a stronger aging strengthening effect cannot be generated, but if the content of Ni is higher than 1.8%, the conductivity of the material is obviously reduced.
Co: the crystal grain growth in the alloy heating process is hindered, and the solid solution decomposition is delayed. The intermediate BeCo compound is formed with Be, so that the crystal boundary reaction is inhibited, the nonuniformity caused by overaging is avoided, and the aging process of the aged alloy material is easier to control. If the content of Co is less than 0.15%, a strong aging strengthening effect cannot be generated, a crystal boundary reaction is easy to occur, and the aging process is not easy to control; however, if the content of Co is higher than 0.4%, the conductivity of the material is obviously reduced, and the cost is higher.
Ag: the influence on the electrical conductivity of the copper alloy is minimum, the strength of the alloy after aging can be improved, the high electrical conductivity is kept, and the recrystallization temperature, creep strength and high-temperature-resistant low-cycle fatigue stability of the alloy are obviously improved. If the Ag content is lower than 0.5%, the effects of strength, recrystallization temperature and the like of the material after aging are not obviously improved; however, if the content of Ag is higher than 0.8%, Ag atoms are gathered, grown, coarsened and spherical in the aging process, the strength and the conductivity of the material are reduced, and the cost is higher.
Zr: the influence on the conductivity of the copper alloy is small, a small amount of zirconium can form a fine dispersed precipitated phase, the hardness of the alloy material can be further improved, recrystallization can be delayed and delayed, the softening temperature of the copper alloy can be remarkably improved, and recrystallized grains can be refined. If the Zr content is lower than 0.05 percent, the softening temperature of the material cannot be increased or can be increased only by a small amount; however, if the Zr content is higher than 0.1%, the adverse effect on the electrical conductivity of the material begins to increase, and the cost is high.
Mg: magnesium is the element with the largest surface activity in beryllium bronze, and a small amount of magnesium can refine grains, so that upsilon phase particles are distributed uniformly and finely and have certain desorptionThe oxygen action improves the mechanical property, corrosion resistance and high-temperature stability of the alloy, and has little influence on the conductivity. If the Mg content is lower than 0.02 percent, the effect on refining grains of the material is not obvious; however, if the Mg content is more than 0.05%, the material conductivity is lowered, and hard and brittle MgCu is easily formed2And the mechanical property of the material is not good.
Adverse effects of impurity elements in the low beryllium copper alloy material:
fe: although iron can delay recrystallization of the alloy to refine grains, excessive Fe can form a Fe-rich phase, so that the processing performance of the material is reduced, and the non-magnetic performance of the material is also reduced, which is extremely unfavorable for the material of a precision instrument, so that the content is strictly controlled to be less than or equal to 0.015 percent.
O: oxygen has a large influence on the conductivity of the copper alloy, and forms an eutectic phase with copper, the melting point of which is higher than the hot working temperature, and cold brittleness is easy to occur during cold working, so the content is strictly controlled to be less than or equal to 0.005 percent.
The preparation method of the invention has the following functions:
vacuum melting is one of the basic methods for producing refractory and rare active metals, the active metals have strong chemical activity (such as beryllium, zirconium and magnesium elements used in the application), can be rapidly oxidized and nitrided during melting and casting in the atmosphere to form a large amount of inclusions, and the high-purity and high-quality metal material can be obtained through vacuum melting.
The raw materials (Cu, Ni and Co) which have high melting points and are not easy to oxidize and burn are placed at the middle lower part of the crucible, small materials are placed between large materials, the crucible is tight at the bottom and loose at the top, and the bridging phenomenon during metal melting is effectively prevented. Easily oxidized and easily aspirated raw materials are added later, and the inert gas is pressurized to inhibit the oxidation or evaporation of the raw materials, so that the purity and quality of the smelted metal material are effectively ensured.
The deformation and recrystallization in the free forging and hot rolling process change the as-cast coarse structure into fine and uniform equiaxial grains, so that the defects of segregation, looseness, inclusion and the like in the cast ingot are improved or eliminated, the processing performance and the mechanical property of the material are improved, the section size is reduced, and the subsequent plastic processing is convenient.
The solution treatment can obtain a uniform supersaturated solid solution, and the solution treatment is also carried out for the intermediate softening of the press working, which is good for the organization preparation for aging strengthening. Ni and Be can form NiBe and Ni5Be21The two intermediate compounds, Ni and Be, have higher solubility in Cu at high temperature, and the solubility is obviously reduced when the temperature is reduced, so that a single supersaturated α solid solution can Be obtained by solution treatment, and then the precipitation strengthening effect can Be obtained by aging treatment.
The cold drawing and cold rolling process can obtain plates, strips, wires, bars and pipes with certain deformation degree, the size precision is high, the deformation strengthening degree can be controlled through the deformation quantity, and the comprehensive mechanical property of the material can be better by combining with the aging process.
Aging treatment can lead Be and Ni atoms dissolved in a matrix to form fine and uniformly distributed NiBe and Ni through phase change precipitation5Be21The particles inhibit movement of dislocations, grain boundaries, and the like, and cause dispersion strengthening.
The low beryllium copper alloy disclosed by the invention effectively improves the recrystallization temperature and the thermal stability of the copper alloy by adding trace elements of Ag, Zr and Mg, and the low beryllium copper alloy material obtained by cold plastic processing and solution aging treatment has high tensile strength (up to 850-1000MPa), high conductivity (50-60% IACS) and high softening temperature (up to over 600 ℃). Effectively solves the problems of the contradiction between high strength and high conductivity and the contradiction between high conductivity and high softening temperature of the traditional copper alloy.
The following further description is made with reference to the drawings and specific examples.
Drawings
FIG. 1 is a parameter diagram of the material preparation process of the present invention;
FIG. 2 is a graph showing the softening temperature characteristics of the copper alloy containing beryllium of each example and other copper alloy materials containing beryllium.
Detailed Description
Example 1
1. Ingredients
Taking No. two oxygen-free copper, electrolytic nickel, electrolytic cobalt, beryllium beads, high-purity silver and CuZr14、MgNi20Removing rust products on the surface of the raw material as the raw material, removing oil stains, floating liquid and the like, and drying for later use. According to the mass ratio Be: 0.3%, Ni: 1.4%, Co: 0.3%, Ag: 0.6, Zr: 0.07%, Mg: 0.04 percent of the raw materials are mixed.
2. Melting and casting
The second oxygen-free copper, the electrolytic nickel and the electrolytic cobalt are arranged in the crucible, wherein the electrolytic nickel and the electrolytic cobalt are arranged at the middle lower part of the crucible, the small material is arranged between the large blocks, and the lower part is tight and the upper part is loose, so that the bridging phenomenon when the metal is melted is prevented. Beryllium bead, high-purity silver and CuZr14And MgNi20The intermediate alloy is placed in the charging hopper. Vacuumizing, when the vacuum degree in the furnace is<And (3) starting to transmit electricity to melt materials at 30Pa, firstly transmitting electricity by about 30KW with medium power, gradually increasing the power until the temperature rises to 1250-1350 ℃, and reducing the transmitted electricity after the raw materials in the crucible are completely melted. After full melting, the first refining is carried out, the power is 25KW, the time is 20 minutes, and the vacuum degree is<The crucible was repeatedly tilted during 10 Pa. Filling argon to 7-10kPa, and sequentially adding high-purity silver, beryllium beads and CuZr14After adding one element, the master alloy should be stirred for 2-5 seconds with increased power to accelerate melting and make the distribution uniform. Then carrying out secondary refining with the power of 20KW for 10 minutes and the vacuum degree<2 Pa. Filling argon, adding MgNi20And (3) fully electromagnetically and mechanically stirring and vibrating the intermediate alloy for 5-10 seconds. Standing, adjusting the temperature to 1170-1250 ℃, continuously casting the trickle at a low speed, breaking vacuum after solidification, discharging, cooling and demoulding to obtain the cast ingot.
3. Milling surface
The surface scale of the ingot was milled off, and the ingot was sampled and subjected to chemical composition analysis, and the results are shown in table 1.
4. Forging
Heating the milled ingot to 890 ℃ along with the furnace, and preserving the temperature for 1.5 hours, wherein the initial forging temperature is 890 ℃ and the final forging temperature is not lower than 780 ℃. And (3) intermediate melting, heating again for heat preservation for not less than 15 minutes, finally forging into a straight strip with the cross section size of 30 multiplied by 30mm, chamfering to obtain a forging stock, and performing dye penetrant inspection and ultrasonic inspection.
5. Hot rolling
Heating the forging stock to 920 ℃ along with a furnace, preserving heat for 1 hour, wherein the final rolling temperature is not lower than 820 ℃, and the hot rolling pass is phi 28mm → phi 24mm → phi 22mm → phi 20mm → phi 18mm → phi 16mm → phi 14mm, thus obtaining the coiled wire.
6. Solution treatment
Heating the wire rod to 920 ℃, then placing the wire rod in a furnace at a temperature, preserving heat for 1 hour, and performing water quenching, wherein the time of the water feeding process is not more than 5 seconds.
7. Cold drawing
The wire rod after the solution treatment is pickled to remove surface oxide skin, and is dried and then subjected to cold drawing, wherein the processing pass is phi 14mm → phi 7mm → intermediate heat treatment (920 ℃ heat preservation for 30 minutes) → pickling passivation → phi 3mm → intermediate heat treatment (920 ℃ heat preservation for 20 minutes) → pickling passivation → phi 1 mm.
8. Aging treatment
And heating the cold drawn wire to 480 ℃, then placing the wire in a warm charging furnace, preserving the heat for 3 hours, and cooling in air.
After the processing of the working procedures, the phi 1mm wire is aged, the tensile strength is 920MPa, the conductivity is 57 percent IACS, and the softening temperature is 609 ℃.
Example 2
1. Ingredients
Taking second oxygen-free copper, electrolytic nickel, electrolytic cobalt, beryllium beads, high-purity silver and CuZr14、MgNi20Removing rust products on the surface of the raw material as the raw material, removing oil stains, floating liquid and the like, and drying for later use. According to the mass ratio Be: 0.4%, Ni: 1.5%, Co: 0.35%, Ag: 0.7, Zr: 0.08%, Mg: 0.04 percent of the raw materials are mixed.
2. Melting and casting
The second oxygen-free copper, the electrolytic nickel and the electrolytic cobalt are arranged in the crucible, the electrolytic nickel and the electrolytic cobalt are arranged at the middle lower part of the crucible, the small material is arranged between the large blocks, the lower part is tight and the upper part is loose, so as to prevent the bridging phenomenon when the metal is melted, and the beryllium bead, the high-purity silver and the CuZr are prevented14And MgNi20The intermediate alloy is placed in the charging hopper. Vacuumizing, when the vacuum degree in the furnace is<And (3) starting to transmit electricity and melt materials at 30Pa, gradually increasing the power to 1250-1350 ℃ when the medium power is about 30KW, and reducing the transmitted power after the raw materials in the crucible are completely melted. Crucible potThe first refining is carried out after the inner raw material is completely melted, the power is 25KW, the time is 25 minutes, and the vacuum degree is<The crucible was repeatedly tilted during 10 Pa. Filling argon to 7-10kPa, and sequentially adding high-purity silver, beryllium beads and CuZr14After adding one element, the master alloy should be stirred for 2-5 seconds with increased power to accelerate melting and make the distribution uniform. Then carrying out secondary refining with the power of 20KW for 15 minutes and the vacuum degree<2 Pa. Filling argon, adding MgNi20And (3) fully electromagnetically and mechanically stirring and vibrating the intermediate alloy for 5-10 seconds. Standing, adjusting the temperature to 1170-1250 ℃, continuously casting the trickle at a low speed, breaking vacuum after solidification, discharging, cooling and demoulding to obtain the cast ingot.
3. Milling surface
The surface scale of the ingot was milled off, and the ingot was sampled and subjected to chemical composition analysis, and the results are shown in table 1.
4. Forging
And heating the milled ingot to 900 ℃ along with the furnace, and preserving the heat for 2 hours, wherein the initial forging temperature is 900 ℃ and the final forging temperature is not lower than 780 ℃. And (3) intermediate reheating and heat preservation time is not less than 20 minutes, and finally forging the blank into a straight strip with the section size of 30 multiplied by 30mm and chamfering the straight strip to obtain a forged blank, and performing dye penetrant inspection and ultrasonic inspection.
5. Hot rolling
Heating the forging stock to 920 ℃ along with a furnace, preserving heat for 1.5 hours, wherein the final rolling temperature is not lower than 820 ℃, and the hot rolling pass is phi 28mm → phi 24mm → phi 22mm → phi 20mm → phi 18mm → phi 16mm → phi 14mm, thus obtaining the coiled wire.
6. Solution treatment
Heating the wire rod to 950 ℃, then charging into a furnace at a high temperature, preserving heat for 1 hour, and performing water quenching, wherein the time of the water charging process is not more than 5 seconds.
7. Cold drawing
The wire rod after the solution treatment is pickled to remove surface oxide skin, and is dried and then subjected to cold drawing, wherein the processing pass is phi 14mm → phi 7mm → intermediate heat treatment (heat preservation at 950 ℃ for 30 minutes) → pickling passivation → phi 3mm → intermediate heat treatment (heat preservation at 950 ℃ for 20 minutes) → pickling passivation → phi 1 mm.
8. Aging treatment
And heating the cold drawn wire to 480 ℃, then placing the wire in a warm charging furnace, preserving the heat for 3 hours, and cooling in air.
After the processing of the working procedures, the phi 1mm wire is aged to have the tensile strength of 954MPa, the conductivity of 55 percent IACS and the softening temperature of 623 ℃.
Example 3
1. Ingredients
Taking second oxygen-free copper, electrolytic nickel, electrolytic cobalt, beryllium beads, high-purity silver and CuZr14、MgNi20Removing rust products on the surface of the raw material as the raw material, removing oil stains, floating liquid and the like, and drying for later use. According to the mass ratio Be: 0.44%, Ni: 1.6%, Co: 0.4%, Ag: 0.8, Zr: 0.1%, Mg: 0.05 percent of the raw materials are mixed.
2. Melting and casting
The second oxygen-free copper, the electrolytic nickel and the electrolytic cobalt are arranged in the crucible, the electrolytic nickel and the electrolytic cobalt are arranged at the middle lower part of the crucible, the small material is arranged between the large blocks, the lower part is tight and the upper part is loose, so as to prevent the bridging phenomenon when the metal is melted, and the beryllium bead, the high-purity silver and the CuZr are prevented14And MgNi20The intermediate alloy is placed in the charging hopper. Vacuumizing, when the vacuum degree in the furnace is<And (3) starting to transmit the materials at 30Pa, transmitting the materials by using medium power about 30KW, gradually increasing the power until the temperature rises to 1250-1350 ℃, and reducing the transmitted power after the materials are completely melted. After full melting, the first refining is carried out, the power is 30KW, the time is 20 minutes, and the vacuum degree is<The crucible was repeatedly tilted during 10 Pa. Filling argon to 7-10kPa, and sequentially adding high-purity silver, beryllium beads and CuZr14After adding one element, the master alloy should be stirred for 2-5 seconds with increased power to accelerate melting and make the distribution uniform. Then carrying out secondary refining with the power of 25KW for 10 minutes and the vacuum degree<2 Pa. Filling argon, adding MgNi20And (3) fully electromagnetically and mechanically stirring and vibrating the intermediate alloy for 5-10 seconds. Standing, adjusting the temperature to 1170-1250 ℃, continuously casting the trickle at a low speed, breaking vacuum after solidification, discharging, cooling and demoulding to obtain the cast ingot.
3. Milling surface
The surface scale of the ingot was milled off, and the ingot was sampled and subjected to chemical composition analysis, and the results are shown in table 1.
4. Forging
Heating to 920 ℃ along with the furnace, and preserving heat for 2 hours, wherein the initial forging temperature is 920 ℃ and the final forging temperature is not lower than 800 ℃. And (3) intermediate reheating and heat preservation time is not less than 20 minutes, and finally forging the blank into a straight strip with the section size of 30 multiplied by 30mm and chamfering the straight strip to obtain a forged blank, and performing dye penetrant inspection and ultrasonic inspection.
5. Hot rolling
Heating the forging stock to 920 ℃ along with a furnace, preserving heat for 2 hours, wherein the final rolling temperature is not lower than 820 ℃, and the hot rolling pass is phi 28mm → phi 24mm → phi 22mm → phi 20mm → phi 18mm → phi 16mm → phi 14mm, thus obtaining the coiled wire.
6. Solution treatment
Heating the wire rod to 920 ℃, then placing in a furnace at a warm temperature, keeping the temperature for 1.5 hours, and performing water quenching, wherein the time of the water entering process is not more than 5 seconds.
7. Cold drawing
The wire rod after the solution treatment is pickled to remove surface oxide skin, and is dried and then subjected to cold drawing, wherein the processing pass is phi 14mm → phi 7mm → intermediate heat treatment (920 ℃ for 30 minutes) → pickling passivation → phi 3mm → intermediate heat treatment (890 ℃ for 30 minutes) → pickling passivation → phi 1 mm.
8. Aging treatment
And heating the cold drawn wire to 480 ℃, then placing the wire in a warm furnace, preserving the heat for 3 hours, and cooling in air.
After the processing of the procedures, the phi 1mm wire is aged, the tensile strength is 989MPa, the conductivity is 51% IACS, and the softening temperature is 642 ℃.
TABLE 1 examples Low beryllium copper alloy chemistry (wt%)
| Element(s) | Be | Ni | Co | Ag | Zr | Mg | Fe | O | S | P | Cu |
| Example 1 | 0.28 | 1.4 | 0.29 | 0.58 | 0.056 | 0.025 | 0.012 | 0.004 | <0.004 | <0.002 | Balance of |
| Example 2 | 0.36 | 1.5 | 0.32 | 0.66 | 0.078 | 0.035 | 0.010 | 0.003 | <0.004 | <0.002 | Balance of |
| Example 3 | 0.42 | 1.58 | 0.39 | 0.77 | 0.092 | 0.044 | 0.012 | 0.005 | <0.004 | <0.002 | Balance of |
The performance profiles of each example are shown in Table 2 with commercially available TBe2, TBe0.3-1.5, and import C17510.
Table 2 comparison of the properties of the examples with other beryllium copper materials
| Material | Tensile strength/MPa | Conductivity/% IACS | Softening temperature/. degree.C |
| Example 1 | 920 | 57 | 609 |
| Example 2 | 954 | 55 | 623 |
| Example 3 | 989 | 51 | 642 |
| Domestic TBe2 | 1342 | 26 | 442 |
| Domestic TBe0.3-1.5 | 467 | 51 | 350 |
| Inlet C17510 | 783 | 58 | 524 |
Claims (8)
1. The high-strength high-softening-temperature low beryllium copper alloy is characterized by comprising the following components in percentage by mass: 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%, wherein Ni + Co is less than or equal to 2.0%, unavoidable impurities are less than or equal to 0.1%, and the balance is Cu.
2. The low beryllium copper alloy of claim 1, wherein the weight percentages of the components are as follows: 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% and the balance of Cu.
3. The low beryllium copper alloy of claim 1 or 2, wherein: (Ni + Co)/Be is more than or equal to 4.5 and less than or equal to 6.0.
4. The low beryllium copper alloy of claim 1, wherein: the inevitable impurities Fe are less than or equal to 0.015wt percent and O is less than or equal to 0.005wt percent.
5. A method for preparing a low beryllium copper alloy as claimed in any one of claims 1 to 3, comprising the steps of:
1) melting
The ingredients according to claim 1, 2 or 3 are mixed and vacuum smelted, the smelting temperature is 1250-;
2) forging
Milling the surface of the ingot obtained in the step 1), heating to 850-;
3) hot rolling
Heating the forging stock obtained in the step 2) to 850-950 ℃, and preserving the heat for 1-2h, wherein the finish rolling temperature is not lower than 800 ℃, so as to obtain a wire;
4) solution treatment
Heating the wire obtained in the step 3) to 890-950 ℃, preserving the heat for 1-5h, quenching with water, and discharging the wire out of the furnace until the time of water entering is less than or equal to 5 s;
5) cold plastic working
Pickling and drying the wire rod subjected to the solution treatment in the step 4), and performing multi-pass cold drawing or cold rolling with the processing rate of each pass being more than 70% to obtain a wire rod;
6) aging treatment
Heating the wire subjected to cold plastic processing in the step 5) to 400-520 ℃, preserving the heat for 1-7h, and cooling in air or with a furnace.
6. The method of claim 5, wherein the smelting of step 1) comprises the steps of:
1) placing Cu, Ni and Co in a container, wherein the Ni and Co are positioned at the lower part of the container, small blocks are placed between large blocks, the lower part of the container is compact, and the upper part of the container is loose;
2) the vacuum degree of the vacuum furnace is less than 30Pa, and the temperature is raised to 1250-;
3) refining for the first time, when the vacuum degree is adjusted to Be less than 10Pa, filling argon to 7-10kPa, and sequentially adding Ag, Be and Zr at intervals, wherein the Zr is CuZr14Adding the intermediate alloy, increasing the power transmission and stirring for 2-5s to complete melting after adding one raw material, and repeatedly shaking the container during refining for 15-30 min;
4) refining for the second time, adjusting vacuum degree to be less than 5Pa, filling argon to 7-10kPa, adding Mg, MgNi20Adding the intermediate alloy in a form of refining for 10-15min, stirring, oscillating for 5-10s, standing, adjusting the temperature to 1170-1250 ℃, casting, solidifying and demolding to obtain the cast ingot.
7. The method according to claim 5, wherein the Cu added in step 1) is copper oxide II, the Ni added is electrolytic nickel, and the Co added is electrolytic cobalt.
8. The method as claimed in claim 5, wherein the step 5) of cold drawing or cold rolling requires intermediate heat treatment and acid pickling during each pass, wherein the intermediate heat treatment temperature is 890-950 ℃, and the temperature is maintained for 20min-1 h.
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