CN115679136A - Copper-chromium-zirconium alloy ingot and preparation method and application thereof - Google Patents
Copper-chromium-zirconium alloy ingot and preparation method and application thereof Download PDFInfo
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- CN115679136A CN115679136A CN202110833060.1A CN202110833060A CN115679136A CN 115679136 A CN115679136 A CN 115679136A CN 202110833060 A CN202110833060 A CN 202110833060A CN 115679136 A CN115679136 A CN 115679136A
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- QZLJNVMRJXHARQ-UHFFFAOYSA-N [Zr].[Cr].[Cu] Chemical compound [Zr].[Cr].[Cu] QZLJNVMRJXHARQ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910001093 Zr alloy Inorganic materials 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000956 alloy Substances 0.000 claims abstract description 66
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 63
- 239000010949 copper Substances 0.000 claims abstract description 61
- 238000005266 casting Methods 0.000 claims abstract description 56
- 229910052802 copper Inorganic materials 0.000 claims abstract description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000011651 chromium Substances 0.000 claims abstract description 47
- 238000003723 Smelting Methods 0.000 claims abstract description 41
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 26
- 239000012535 impurity Substances 0.000 claims abstract description 26
- 239000011261 inert gas Substances 0.000 claims abstract description 26
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 claims abstract description 22
- XTYUEDCPRIMJNG-UHFFFAOYSA-N copper zirconium Chemical compound [Cu].[Zr] XTYUEDCPRIMJNG-UHFFFAOYSA-N 0.000 claims abstract description 21
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 17
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000003280 down draw process Methods 0.000 claims abstract description 8
- 238000009749 continuous casting Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000007670 refining Methods 0.000 claims description 13
- 238000007872 degassing Methods 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical group [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000005070 sampling Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000000498 cooling water Substances 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 4
- 230000004907 flux Effects 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 230000007547 defect Effects 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 230000006698 induction Effects 0.000 description 5
- 238000005204 segregation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910017526 Cu-Cr-Zr Inorganic materials 0.000 description 1
- 229910017810 Cu—Cr—Zr Inorganic materials 0.000 description 1
- 206010039509 Scab Diseases 0.000 description 1
- QZKWFURVKCYMSP-UHFFFAOYSA-N [P].[Fe].[Cu] Chemical compound [P].[Fe].[Cu] QZKWFURVKCYMSP-UHFFFAOYSA-N 0.000 description 1
- ZUPBPXNOBDEWQT-UHFFFAOYSA-N [Si].[Ni].[Cu] Chemical compound [Si].[Ni].[Cu] ZUPBPXNOBDEWQT-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
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Abstract
The invention discloses a copper-chromium-zirconium alloy ingot and a preparation method and application thereof. The preparation method comprises the following steps: smelting, casting and cooling the raw materials to obtain the cast ingot; the raw materials comprise the following components in percentage by mass: 1.6 to 2.5 percent of chromium, 0.05 to 0.16 percent of zirconium, 0.05 to 0.1 percent of rare earth Re, and the balance of copper and inevitable impurities; chromium is added in a copper-chromium intermediate alloy mode, and zirconium is added in a copper-zirconium intermediate alloy mode; smelting copper at 1190-1360 ℃ to obtain molten copper, and sequentially adding chromium and rare earth Re into the molten copper under the protection of inert gas; the casting temperature is 1350-1370 ℃; in the casting step, non-vacuum down-drawing continuous casting is performed. The copper-chromium-zirconium alloy ingot prepared by the method has compact structure, low impurity content, high production efficiency and low cost.
Description
Technical Field
The invention relates to a copper-chromium-zirconium alloy ingot and a preparation method and application thereof.
Background
The ideal excellent lead frame material has the strength of more than 600MPa and the electric conductivity of more than 70% IACS, and the materials commonly used for the lead frame material at present, such as copper iron phosphorus, copper nickel silicon and the like, can not completely meet the requirements. The copper chromium zirconium series alloy is an important high-strength and high-conductivity copper alloy material, the strength of the copper chromium zirconium series alloy is 3 times of that of pure copper, the copper chromium zirconium series alloy has the good performances of 80% IACS conductivity, 550-degree resistance, no softening, wear resistance, corrosion resistance and the like, is the best high-strength and high-conductivity copper alloy material at present, and is widely applied to connectors, lead frames, conductive contact materials, welding materials and the like; particularly, with the development of 5G technology and electronic information technology, electronic information products are being miniaturized, ultra-thinned, lightweight, multifunctional, and intelligent, and the integrated circuit lead frame is required to have higher and more comprehensive performance requirements, and in addition, good thermal conductivity and electrical conductivity are required.
The addition of suitable amounts of the elements chromium and zirconium to the copper alloy allows the achievement of the above desired novel copper alloy materials. However, because the Cr element and the Zr element are elements with strong air suction capacity, oxidation reaction and burning loss are easy to occur, the viscosity and the heat dissipation effect of the melt are greatly reduced due to the increased content of the Cr element, and meanwhile, the oxygen content in the melt is not easy to reduce, and the defects of inclusion, air holes and the like are easy to occur; zr element is not properly controlled and can be completely burnt, so that the Zr element is difficult to be effectively added into copper liquid, and the alloy yield is influenced; meanwhile, the high-temperature melt has large air suction amount and difficult degassing, and remains in the solid alloy to generate poor structure such as shrinkage cavity, air hole, segregation, high impurity content and the like.
At present, the preparation of copper-chromium-zirconium alloy at home and abroad mainly adopts a vacuum induction melting method, a copper block, a chromium block and metal zirconium in a certain proportion are put into a vacuum induction furnace for melting, and are poured into a mould after being completely melted, and the induction melting method and the deformation aging method are usually combined together to improve the performance of the alloy, but the induction melting method has low production efficiency and high cost, and can not produce large-scale cast ingots for rolled plates.
Disclosure of Invention
The invention aims to overcome the defects that the preparation of the copper-chromium-zirconium alloy in the prior art cannot realize low cost, high efficiency and good organization structure when the content of Cr is increased, and provides a copper-chromium-zirconium alloy ingot and a preparation method and application thereof. The copper-chromium-zirconium alloy ingot prepared by the method has the advantages of good structure, high production efficiency and low cost.
The invention solves the technical problems through the following technical scheme:
a preparation method of a copper-chromium-zirconium alloy ingot comprises the following steps:
smelting, casting and cooling the raw materials to obtain the cast ingot; wherein,
the raw materials comprise the following components in percentage by mass: 1.6-2.5% Cr, 0.05-0.16% Zr, 0.05-0.1% rare earth Re, the balance Cu and unavoidable impurities; the Cr is added in a copper-chromium intermediate alloy mode, and the Zr is added in a copper-zirconium intermediate alloy mode;
the smelting comprises the following steps: smelting copper at the smelting temperature of 1190-1360 ℃ to obtain molten copper liquid, and sequentially adding the Cr and the rare earth Re into the molten copper liquid under the protection of inert gas;
in the casting step, the casting temperature is 1350-1370 ℃;
the casting comprises the following steps: non-vacuum down-drawing continuous casting is carried out, and the flow rate of cooling water is set to be 6.0-8.0 m 3 H, casting speed is 60-80 mm/min, and simultaneously, addingZirconium.
In the present invention, the Cu may be added in the form of a copper source, which is a material containing copper element, such as an electrolytic copper plate, as is conventional in the art.
In the invention, the impurity content of the copper-chromium intermediate alloy is preferably less than or equal to 0.5%. The copper-chromium master alloy is preferably a copper-chromium 10 master alloy, and the copper-chromium 10 master alloy is more preferably available from West An Sirui advanced copper alloy technologies, inc.
In the present invention, the copper-zirconium master alloy is preferably a copper-zirconium 50 master alloy, and is more preferably added in the form of a copper-clad copper-zirconium 50 master alloy. The copper zirconium 50 master alloy is preferably available from west An Sirui advanced copper alloy technologies, ltd. The selection of the copper-zirconium intermediate alloy is beneficial to: 1) The burning loss during smelting is reduced; 2) Compared with metal Zr, the addition of the CuZr intermediate alloy improves the uniformity of the alloy components.
In the invention, the rare earth Re is preferably added in a form of copper sheet coated Re.
In the present invention, preferably, before the smelting, a charging step is further included. Charging preferably includes charging the flux, the covering agent, the electrolytic copper plate. The flux is preferably 1:1 calcium fluoride: a composition of sodium fluoride (i.e., calcium fluoride: sodium fluoride = 1:1). The covering agent is preferably glass.
In the present invention, the smelting step preferably includes the steps of: after the copper is melted to obtain the copper liquid, sampling at 1200 +/-10 ℃ to detect the components of the copper liquid.
In the smelting step, the inert gas is introduced when the power is 850KW +/-10 KW.
In the present invention, in the step of smelting, the inert gas may be an inert gas conventional in the art, such as argon. The pressure under the protection of the inert gas is preferably 3 to 10Pa, more preferably 7Pa.
In the present invention, the step of melting preferably includes a step of stirring after the Cr is added. The stirring time is preferably 14-16min, for example 15min.
In the present invention, the step of smelting, after adding the Cr, preferably includes the steps of: sampling at 1350 +/-10 deg.C, and detecting and regulating the content of molten copper until the Cr content reaches target value.
In the present invention, the smelting step preferably further includes a refining step after the Cr is added, and the refining step includes the steps of: under the protection of inert gas, deoxidizing, and adding rare earth Re before discharging.
The inert gas can be used for degassing in a manner conventional in the art, and the degassing time is preferably 20-25min. The inert gas may be an inert gas conventional in the art, such as argon.
Wherein, the deoxidizer used for deoxidation can be an deoxidizer conventional in the field, such as CuMg alloy, and further such as CuMg 15-CuMg 50.
In the present invention, the step of casting preferably includes the steps of: before casting, when the melt flows into 75-85% of the square crystallizer, electromagnetic stirring is started. The frequency of the electromagnetic stirring is preferably 3 to 10Hz, and the current of the electromagnetic stirring is preferably 60 to 100A.
In the present invention, in the step of casting, the mechanical vibration is preferably set to 25 to 40 times/min, for example, 30 times/min.
In the present invention, in the step of casting, preferably, the Zr is added in portions, and the time interval of the portion addition is preferably 20 to 50s.
In the present invention, the ingot cooling may comprise the following steps as is conventional in the art: and spraying water to the material obtained after casting, and carrying out secondary cooling.
In a preferred embodiment of the present invention, the method for producing the copper chromium zirconium alloy ingot comprises the steps of:
1) Preparing materials: the raw materials comprise the following components in percentage by mass: 1.6 to 2.5 percent of chromium, 0.05 to 0.16 percent of zirconium, 0.05 to 0.1 percent of rare earth Re, and the balance of copper; wherein, chromium is added in the form of copper-chromium 10 intermediate alloy, the impurity content of the copper-chromium 10 intermediate alloy is less than or equal to 5 percent, zirconium is added in the form of copper-zirconium 50 intermediate alloy, and the impurity content of the copper-chromium 10 intermediate alloy is less than or equal to 5 percent;
2) Smelting: controlling the smelting temperature to 1350 +/-10 ℃, smelting copper to obtain molten copper, and adding chromium into the molten copper under the protection of inert gas; the chromium is uniformly distributed by fully stirring, the coverage is good in the smelting process, and the burning loss and the air suction are reduced;
3) Refining and degassing: degassing for 20 minutes by adopting inert gas, adding CuMg alloy for deoxidation, and adding rare earth Re wrapped by copper sheets before discharging;
4) Casting: starting casting when the temperature reaches 1350-1370 ℃;
5) Casting: when the melt flows into 75-85% of the square crystallizer, starting electromagnetic stirring, setting the frequency to be 3-10 Hz and the current to be 60-100A, starting a down-drawing speed button, adjusting the casting speed to be 60-80 mm/min, and mechanically vibrating for 30 times/min; the copper-zirconium 50 intermediate alloy is added in batches;
6) Cooling the cast ingot: and (4) cooling the crystallizer by water, spraying water to the material obtained after casting, and carrying out secondary cooling.
The invention also provides the copper-chromium-zirconium alloy ingot prepared by the preparation method.
In the invention, the shape of the copper chromium zirconium alloy ingot can be flat, round or square, and is preferably flat. When the copper chromium zirconium alloy cast ingot is in a flat shape, the prepared copper chromium zirconium alloy flat cast ingot is used as a rolling blank of an alloy strip, and compared with a conventional round ingot, the material loss can be reduced, and the production cost can be reduced.
In the invention, the copper chromium zirconium alloy ingot preferably comprises the following components in percentage by mass: 1.6-2.5% Cr, 0.05-0.15% Zr, an impurity content of not more than 0.1% by weight, the remainder being Cu, the total being 100%.
Wherein the mass percentage of Cr is preferably 2.3 to 2.4%, for example 2.32 to 2.34%, and further for example 2.33%.
The mass percentage of Zr is preferably 0.085 to 0.093%, for example, 0.089 or 0.091%.
Wherein the content of said impurities is preferably ≦ 0.055wt%, such as 0.045-0.055 wt%, further such as 0.047, 0.048 or 0.053wt%.
Wherein the impurities may include trace amounts of Re.
Wherein, the copper chromium zirconium alloy ingot preferably comprises the following components by mass percent: 2.32% of Cr,0.091% of Zr,0.045% of impurities, the remainder being Cu, the total amount being 100%.
Wherein, the copper chromium zirconium alloy ingot preferably comprises the following components by mass percent: 2.33% Cr,0.093% Zr,0.048% impurity, balance Cu, total 100%.
The copper chromium zirconium alloy ingot preferably comprises the following components in percentage by mass: 2.34% Cr,0.089% Zr,0.047% impurities, the remainder Cu, the total amount being 100%.
In the present invention, the specification (thickness × width × length) of the copper chromium zirconium alloy ingot may be 150 (t) × 370 (w) × L or 150 (t) × 420 (w) × L, where L denotes the length of the copper chromium zirconium alloy ingot.
The invention also provides application of the copper-chromium-zirconium alloy ingot in a lead frame material.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
1) The invention adopts a preparation method of non-vacuum induction melting, chromium and zirconium are added in a mode of intermediate alloy, a series of key parameters of non-vacuum melting and casting are determined according to different specifications through a large amount of process groceries, the uniformity of the alloy is realized, the alloy components and the oxygen content are effectively controlled, the chromium and zirconium burning loss is reduced, and the yield is improved.
2) In the preparation method, chromium is added in the form of a copper-chromium 10 alloy, zirconium is added in the form of a copper-zirconium 50 alloy, meanwhile, inert gas protection is adopted in the casting process, appropriate measures such as adjusting the contents of chromium and zirconium are added, a built-in crystallizer is used for electromagnetically stirring the molten copper liquid, and the like, so that the isometric crystal proportion can be increased, grains are refined, surface and subcutaneous air holes and inclusions are reduced, and the center porosity and segregation of the cast ingot are improved.
3) Compared with the traditional vacuum casting process, the non-vacuum down-drawing continuous casting process has the advantages of low equipment requirement, simple operation, stability and reliability. Low production cost and is suitable for industrial production.
4) The copper-chromium-zirconium alloy ingot prepared by the method has compact and uniform structure, low impurity content, few pores, few impurities, no defects of macro and micro segregation and the like.
Drawings
Fig. 1 is a process flow chart of the method for producing a copper-chromium-zirconium alloy ingot according to example 1 of the present invention.
FIG. 2 is a microscopic view of the as-cast structure (50X) of the ingot of copper chromium zirconium alloy prepared in example 1.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the invention thereto.
In the following examples, a copper chromium 10 master alloy and a copper zirconium 50 master alloy are available from west An Sirui advanced copper alloys, ltd.
Examples 1 to 5
A method for preparing a copper chromium zirconium alloy ingot, raw material ingredients were prepared according to table 1 below.
TABLE 1 formulation of raw materials copper, copper chromium 10 master alloy, copper zirconium 50 master alloy, rare earth Re master alloy for examples 1-5
The production process flow chart of the copper chromium zirconium alloy ingot is shown in figure 1, and the production process comprises the following specific steps:
step 1, proportioning: accurately weighing the required raw materials according to the ingredients in the table 1, and wrapping the weighed copper-chromium 10 intermediate alloy, copper-zirconium 50 intermediate alloy and rare earth Re with copper sheets;
step 2, charging: charging the prepared raw materials into a furnace, and sequentially charging a flux (calcium fluoride: sodium fluoride = 1:1), a covering agent (glass) and an electrolytic copper plate;
step 3, smelting: adding power, heating to melt, after the molten copper is molten and clear, sampling to detect the components of the original copper liquid when the measured temperature is about 1200 +/-10 ℃, keeping the power at 850KW +/-10 KW, introducing argon to remove gas for 15 minutes, and keeping the pressure of the argon at 7Pa; after the degassing is finished, adjusting the components according to the calculated addition amount of the copper-chromium 10 alloy, stirring for 15min at high power after the alloy is added, sampling when the temperature is raised to 1350 +/-10 ℃, detecting the adjusted copper liquid components, and adjusting the copper liquid components until the chromium content reaches a target value;
and 4, refining: the process is as follows in sequence: degassing for 20 minutes by argon, deoxidizing the CuMg15 alloy, and adding the rare earth Re wrapped by the copper sheet before discharging;
step 5, casting: continuously heating, and starting casting when the temperature reaches 1350-1370 ℃; if the casting temperature is too high, the internal gradient of the cast ingot is large, the thermal stress is increased, the crack tendency is increased, and meanwhile, the liquid cavity wall becomes thin, so that wide-surface cracks are easily generated; if the temperature is too low, the melt viscosity is high, the fluidity is reduced, and the defects of cold shut, slag inclusion and the like are easily generated;
step 6, casting: when the melt flows into 75-85% of the square crystallizer, starting electromagnetic stirring, setting the frequency to be 3-10 Hz and the current to be 60-100A, starting a pull-down speed button, slowly adjusting the casting speed from low to high to 60-80 mm/min, and mechanically vibrating for 30 times/min; meanwhile, adding the copper-clad copper-zirconium 50 alloy into the chute at a time interval of 20-50 s, and adjusting the adding time interval according to the detection result of the sampling components in front of the furnace; the casting speed determines the depth of the liquid cavity and is a key parameter in the casting process. For cast ingots, the casting speed is too high, the wall of the wide-surface liquid cavity becomes thin, the tensile stress of the surface layer of the wide surface originally in a tensile stress state is increased, and cracks are easily caused; if the casting speed is too low, side cracks can be caused, or defects such as cold shut and the like can be generated on a narrow surface; cooling water is added before castingThe flow rate is gradually adjusted to 6.0-8.0 m 3 H; the water flow parameter represents the amount of cooling water used in casting. The water flow is too high, the cooling degree is too large, stress concentration is easily caused, and cold shut is formed to cause cracks; the water flow is too low, the cooling rate of the cast ingot is too low, and the coarse structure and the performance reduction or other defects can be caused;
step 7, ingot casting cooling: cooling the crystallizer by water, and spraying water at a certain angle on the solidified ingot to carry out secondary cooling; the interior of the crystallizer can realize hot top casting, the solidification rate of the melt at the upper end is reduced, timely feeding is ensured, and floating removal of slag and gas is facilitated. When the amount of the melt in the crucible of the smelting furnace is small, adjusting the down-drawing speed to reduce until the down-drawing speed stops; and after the cast ingot is completely solidified, closing the cooling water.
Comparative example 1
A method for producing a copper-chromium-zirconium alloy ingot was carried out under the same conditions as in example 1 except that the casting temperature was changed to 1350 ℃ and the casting process was not carried out due to poor fluidity.
Comparative example 2
The preparation process of Cu-Cr-Zr alloy ingot includes the same steps as in example 1, the casting temperature is changed to 1380-1400 deg.c, and the chromium burning loss is increased to 85% to obtain the product.
Effects of the embodiment
The as-cast structure (50X) microscopic view of the copper chromium zirconium alloy ingot prepared in example 1 is shown in FIG. 2. The compositions of the copper chromium zirconium alloy ingots produced in examples 1 to 5 are shown in Table 2. The chemical components of the prepared cast ingot are uniform and consistent, and the impurity content is less than or equal to 0.1wt%; the surface has no defects of accretion, inclusion (slag), cold shut, scabbing, cracks, edge cracks and the like, and the internal structure of the cast ingot is compact and has no defects of pores, inclusion, looseness, shrinkage cavities, segregation, internal cracks and the like.
Table 2 examples 1-5 ingots were prepared with the following composition:
while specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and that the scope of the invention is defined by the appended claims. Various changes or modifications to these embodiments may be made by those skilled in the art without departing from the principle and spirit of this invention, and these changes and modifications are within the scope of this invention.
Claims (10)
1. The preparation method of the copper-chromium-zirconium alloy ingot is characterized by comprising the following steps of:
smelting, casting and cooling the raw materials to obtain the cast ingot; wherein,
the raw materials comprise the following components in percentage by mass: 1.6 to 2.5% of Cr,0.05 to 0.16% of Zr,0.05 to 0.1% of rare earth Re, and the balance of Cu and inevitable impurities; the Cr is added in a copper-chromium intermediate alloy mode, and the Zr is added in a copper-zirconium intermediate alloy mode;
the smelting comprises the following steps: smelting copper at the smelting temperature of 1190-1360 ℃ to obtain molten copper liquid, and sequentially adding the Cr and the rare earth Re into the molten copper liquid under the protection of inert gas;
in the casting step, the casting temperature is 1350-1370 ℃;
the casting comprises the following steps: performing non-vacuum down-drawing continuous casting, wherein the flow rate of cooling water is set to be 6.0-8.0 m 3 The casting speed is 60-80 mm/min, and zirconium is added at the same time.
2. The method for producing a copper chromium zirconium alloy ingot according to claim 1, wherein the Cu is added in the form of an electrolytic copper plate;
and/or the impurity content of the copper-chromium intermediate alloy is less than or equal to 0.5 percent;
and/or the copper-chromium intermediate alloy is a copper-chromium 10 intermediate alloy;
and/or the copper-zirconium intermediate alloy is a copper-zirconium 50 intermediate alloy;
and/or the rare earth Re is added in a form that Re is wrapped by copper sheets;
and/or, before the smelting, the method also comprises the step of charging;
and/or the smelting step comprises the following steps: after the copper is melted to obtain copper liquid, sampling at 1200 +/-10 ℃ to detect the components of the copper liquid;
and/or in the smelting step, the inert gas is introduced when the power is 850KW +/-10 KW;
and/or, in the smelting step, the inert gas is argon;
and/or in the smelting step, the pressure under the protection of the inert gas is 3-10Pa;
and/or in the step of smelting, after the Cr is added, a step of stirring is included; the stirring time is 14-16min;
and/or in the smelting step, after the Cr is added, the smelting step comprises the following steps: sampling at 1350 +/-10 deg.c, detecting and regulating the components of molten copper until the chromium content reaches the target value;
and/or in the smelting step, after the Cr is added, the smelting step further comprises a refining step, wherein the refining step comprises the following steps: deoxidizing under the protection of inert gas, and adding rare earth Re before discharging;
wherein in the refining step, the inert gas protection mode is a mode of degassing by using inert gas;
in the refining step, a deoxidizer used for deoxidation is a CuMg alloy;
and/or the step of casting comprises the following steps: before casting, when the melt flows into 75-85% of a square crystallizer, starting electromagnetic stirring;
and/or, in the step of casting, the mechanical vibration is set to be 25 to 40 times/min;
and/or in the step of casting, the Zr is added in batches;
and/or, the ingot casting cooling comprises the following steps: and spraying water to the material obtained after casting, and carrying out secondary cooling.
3. The method for preparing the copper-chromium-zirconium alloy ingot according to claim 2, wherein the copper-chromium 10 intermediate alloy is obtained from An Sirui advanced copper alloy technology ltd;
and/or the copper-zirconium intermediate alloy is added in the form of copper sheet wrapped copper-zirconium 50 intermediate alloy;
and/or the charging comprises charging a fusing agent, a covering agent and an electrolytic copper plate; the flux is prepared from the following components in percentage by mass: 1 calcium fluoride: a composition of sodium fluoride; the covering agent is glass;
and/or in the smelting step, the pressure under the protection of inert gas is 7Pa;
and/or in the step of smelting, after the Cr is added, a step of stirring is included; the stirring time is 15min;
and/or when the smelting step further comprises a refining step, the inert gas is protected in a degassing mode by using inert gas in the refining step, and the degassing time is 20-25min; the inert gas is argon;
and/or when the smelting step further comprises a refining step, in the refining step, the deoxidizer used for deoxidation is CuMg 15-CuMg 50;
and/or the step of casting comprises the following steps: before casting, when the melt flows into 75-85% of a square crystallizer, starting electromagnetic stirring; the frequency of the electromagnetic stirring is 3-10 Hz, and the current of the electromagnetic stirring is 60-100A;
and/or, in the step of casting, the mechanical vibration is set to 30 times/min;
and/or in the step of casting, the Zr is added in batches, and the time interval of the batch addition is 20-50 s.
4. The method of manufacturing a copper chromium zirconium alloy ingot according to claim 1, comprising the steps of:
1) Preparing materials: the raw materials comprise the following components in percentage by mass: 1.6-2.5% of Cr, 0.05-0.16% of Zr, 0.05-0.1% of rare earth Re, and the balance of Cu; wherein, chromium is added in the form of copper-chromium 10 intermediate alloy, the impurity content of the copper-chromium 10 intermediate alloy is less than or equal to 5 percent, zirconium is added in the form of copper-zirconium 50 intermediate alloy, and the impurity content of the copper-chromium 10 intermediate alloy is less than or equal to 5 percent;
2) Smelting: controlling the smelting temperature to 1350 +/-10 ℃, smelting copper to obtain molten copper, and adding chromium into the molten copper under the protection of inert gas; the chromium is uniformly distributed by fully stirring, the coverage is good in the smelting process, and the burning loss and the air suction are reduced;
3) Refining and degassing: degassing for 20 minutes by adopting inert gas, adding CuMg alloy for deoxidation, and adding copper sheet coated rare earth Re before discharging;
4) Casting: starting casting when the temperature reaches 1350-1370 ℃;
5) Casting: when the melt flows into 75-85% of the square crystallizer, starting electromagnetic stirring, setting the frequency to be 3-10 Hz and the current to be 60-100A, starting a down-drawing speed button, adjusting the casting speed to be 60-80 mm/min, and mechanically vibrating for 30 times/min; the copper-zirconium 50 intermediate alloy is added in batches;
6) Cooling the cast ingot: and (4) cooling the crystallizer by water, spraying water to the material obtained after casting, and cooling for the second time.
5. A copper chromium zirconium alloy ingot produced by the method for producing a copper chromium zirconium alloy ingot according to any one of claims 1 to 4.
6. The copper chromium zirconium alloy ingot of claim 5, wherein the copper chromium zirconium alloy ingot comprises the following composition in mass percent: 1.6 to 2.5% by weight of Cr,0.05 to 0.15% by weight of Zr, the content of impurities is not more than 0.1% by weight, and the balance is Cu, the total amount being 100%.
7. The copper chromium zirconium alloy ingot of claim 6, wherein the mass percent of Cr is 2.3-2.4%;
and/or the mass percent of Zr is 0.085-0.093%;
and/or, the content of the impurities is less than or equal to 0.055wt%;
and/or, the impurities include trace amounts of Re;
and/or the copper chromium zirconium alloy ingot is flat, round or square.
8. The copper chromium zirconium alloy ingot of claim 6, wherein the copper chromium zirconium alloy ingot comprises the following composition in mass percent: 2.32% of Cr,0.091% of Zr,0.045% of impurities, the remainder being Cu, the total amount being 100%;
or the copper-chromium-zirconium alloy ingot comprises the following components in percentage by mass: 2.33% Cr,0.093% Zr,0.048% impurities, balance Cu, total 100%;
or the copper-chromium-zirconium alloy ingot comprises the following components in percentage by mass: 2.34% Cr,0.089% Zr,0.047% impurities, balance Cu, total 100%.
9. The copper chromium zirconium alloy ingot of claim 5, wherein the copper chromium zirconium alloy ingot has a gauge of thickness x width x length of 150 x 370 x L or 150 x 420 x L, where L refers to the length of the copper chromium zirconium alloy ingot.
10. Use of a copper chromium zirconium alloy ingot according to any one of claims 5 to 9 in a lead frame material.
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