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CN111979435A - Smelting method for preparing copper-phosphorus alloy by using copper-phosphorus intermediate alloy - Google Patents

Smelting method for preparing copper-phosphorus alloy by using copper-phosphorus intermediate alloy Download PDF

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Publication number
CN111979435A
CN111979435A CN202010955038.XA CN202010955038A CN111979435A CN 111979435 A CN111979435 A CN 111979435A CN 202010955038 A CN202010955038 A CN 202010955038A CN 111979435 A CN111979435 A CN 111979435A
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phosphorus
copper
alloy
melting
standing
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CN111979435B (en
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易骛文
姚力军
潘杰
孙银祥
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Ningbo Weitai Vacuum Technology Co ltd
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Ningbo Weitai Vacuum Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/03Making non-ferrous alloys by melting using master alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention relates to a smelting method for preparing a copper-phosphorus alloy by using a copper-phosphorus intermediate alloy, which comprises the following steps: melting the copper raw material under the vacuum condition, carrying out first standing, then introducing protective gas, then adding the copper-phosphorus intermediate alloy, inclining a melting device, and then carrying out second standing and casting. The method provided by the invention solves the problem of phosphorus segregation in the preparation process of the copper-phosphorus alloy by specifically selecting the adding time and conditions of the copper-phosphorus intermediate alloy and simultaneously adopting an inclined mode in the follow-up process and utilizing the synergistic coupling effect between the copper-phosphorus intermediate alloy and the copper-phosphorus intermediate alloy, improves the uniformity of phosphorus in a copper-phosphorus ingot, controls the total phosphorus content, improves the quality of a copper-phosphorus anode and meets the production requirements of chips.

Description

Smelting method for preparing copper-phosphorus alloy by using copper-phosphorus intermediate alloy
Technical Field
The invention relates to the field of smelting, in particular to a smelting method for preparing a copper-phosphorus alloy by using a copper-phosphorus intermediate alloy.
Background
At present, high-purity 4N (99.99%) copper-phosphorus alloy (with phosphorus content of 400-700ppm) is a raw material for manufacturing copper-phosphorus alloy anodes for semiconductors, is mainly used for wiring of integrated circuit chips, and is an indispensable raw material in the production of high-quality chips.
CN102268567A discloses a preparation method of a copper-phosphorus alloy, aiming at the defects of complex production process, high energy consumption and environmental pollution existing in the existing preparation method of the copper-phosphorus alloy, the preparation method of the copper-phosphorus alloy is simple in process, uniform in product components, low in energy consumption and free of pollution in the production process. The preparation of the copper-phosphorus alloy comprises the following steps: weighing red phosphorus and pure copper; putting the weighed red phosphorus into a crucible; laying an interlayer material on the red phosphorus, and inserting a pure copper rod on the interlayer material; putting the weighed pure copper into a crucible, heating and smelting, smashing the interlayer material by using a rod after the red phosphorus completely reacts, removing the interlayer material from the melt after the interlayer material floats, continuously smelting until the alloy components are uniform, stopping smelting, and adding a covering agent in the smelting process; and removing the covering agent and the residual interlayer material on the surface of the smelted alloy melt, and discharging the alloy melt out of the crucible and cooling to obtain the copper-phosphorus alloy product.
CN106381410A discloses a method for preparing a phosphor-copper anode for an integrated circuit, a smelting furnace and a system thereof, wherein the method comprises the steps of adopting A-grade electrolytic copper with copper content of more than 99.99% and high-phosphor copper alloy with single impurity of not more than 0.003% as raw materials; vacuum melting and continuous casting: synthesizing and drawing copper and phosphorus of the A-grade electrolytic copper and the high-phosphorus copper alloy by using a vacuum smelting furnace to obtain a phosphorus copper alloy cast ingot; and (3) microcrystalline treatment: carrying out microcrystalline treatment on the phosphorus-copper alloy cast ingot in a vacuum state; cold-state processing and forming: and processing and forming the microcrystalline processed phosphorus-copper alloy cast ingot at normal temperature to obtain the phosphorus-copper anode for the integrated circuit. Through vacuum melting and continuous casting of raw materials, microcrystal treatment in a vacuum state and processing and forming at normal temperature, the manufacturing process is simple, and the prepared phosphor-copper anode for the integrated circuit has high filling capacity, higher ductility, high purity and small and uniform grain size.
Currently, enterprises at home and abroad mostly adopt a vacuum induction melting process to produce copper-phosphorus alloy ingots. Because the specific gravity of phosphorus is lighter than that of copper, some enterprises adopt a method of adding copper-phosphorus intermediate alloy. This improves the uniformity of the phosphorus, which is not yet fully satisfactory for chip production. In addition, since phosphorus is volatile during vacuum melting, the content of phosphorus is difficult to control. The uniformity of the phosphorus content in the copper anode has a direct influence on the quality of the product. However, during the smelting and casting of copper-phosphorus alloy, the specific gravity of phosphorus is lighter than that of copper, and phosphorus is volatile, so that the content of phosphorus is easy to segregate.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a smelting method for preparing a copper-phosphorus alloy by using a copper-phosphorus intermediate alloy, which solves the problem of phosphorus segregation in the preparation process of the copper-phosphorus alloy, further improves the uniformity of phosphorus in a copper-phosphorus ingot, controls the total phosphorus content, improves the quality of a copper-phosphorus anode, and meets the production requirements of chips.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a smelting method for preparing a copper-phosphorus alloy by using a copper-phosphorus intermediate alloy, which comprises the following steps: melting the copper raw material under the vacuum condition, carrying out first standing, then introducing protective gas, then adding the copper-phosphorus intermediate alloy, inclining a melting device, and then carrying out second standing and casting.
The method provided by the invention solves the problem of phosphorus segregation in the preparation process of the copper-phosphorus alloy by specifically selecting the adding time and conditions of the copper-phosphorus intermediate alloy and simultaneously adopting an inclined mode in the follow-up process and utilizing the synergistic coupling effect between the copper-phosphorus intermediate alloy and the copper-phosphorus intermediate alloy, improves the uniformity of phosphorus in a copper-phosphorus ingot, controls the total phosphorus content, improves the quality of a copper-phosphorus anode and meets the production requirements of chips.
In a preferred embodiment of the present invention, the melting is performed under a vacuum degree P of 0.005 Pa. ltoreq.P.ltoreq.0.015 Pa, and may be, for example, 0.005Pa, 0.006Pa, 0.007Pa, 0.008Pa, 0.009Pa, 0.01Pa, 0.011Pa, 0.012Pa, 0.013Pa, 0.014Pa, or 0.015Pa, but is not limited to the above-mentioned values, and other values not listed in the above range are also applicable.
In a preferred embodiment of the present invention, the first standing time is 20 to 40min, for example, 20min, 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min, 29min, 30min, 31min, 32min, 33min, 34min, 35min, 36min, 37min, 38min, 39min, or 40min, but is not limited to the above-mentioned values, and other values not listed in this range are also applicable.
As a preferred technical scheme of the invention, the protective gas comprises nitrogen and/or inert gas.
The inert gas in the present invention may be helium, neon, argon, or the like, but is not limited to the above-mentioned gases, and other gases may be used.
In a preferred embodiment of the present invention, the end point of introduction of the protective gas is a gauge pressure P in the melting apparatusTP is-0.07 MPa or lessTNot more than-0.04 MPa, for example, -0.07MPa, -0.065MPa, -0.06MPa, -0.055MPa, -0.05MPa, -0.045MPa or-0.04 MPa, etc., but not limited to the values listed, and other values not listed in the range are also applicable.
In a preferred embodiment of the present invention, the phosphorus content of the copper-phosphorus master alloy is 14 to 15% by mass, and may be, for example, 14%, 14.1%, 14.2%, 14.3%, 14.4%, 14.5%, 14.6%, 14.7%, 14.8%, 14.9%, or 15%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In the invention, the addition amount of the copper-phosphorus intermediate alloy is added according to the requirement of the phosphorus content in the final ingot. Typically, the phosphorus content in the final ingot is between 400ppm and 700 ppm.
In a preferred embodiment of the present invention, the inclined melting device is performed at least 3 times, for example, 3 times, 4 times, 5 times, or 6 times, but the inclined melting device is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In a preferred embodiment of the present invention, the angle of inclination of the melting device is 45 to 55 °, for example, 45 °, 45.5 °, 46 °, 46.5 °, 47 °, 47.5 °, 48 °, 48.5 °, 49 °, 49.5 °, 50 °, 50.5 °, 51 °, 51.5 °, 52 °, 52.5 °, 53 °, 53.5 °, 54 °, 54.5 ° or 55 °, but not limited to the values listed, and other values not listed in this range are also applicable.
In a preferred embodiment of the present invention, the second standing time is 25 to 38min, for example, 25min, 26min, 27min, 28min, 29min, 30min, 31min, 32min, 33min, 34min, 35min, 36min, 37min, or 38min, but is not limited to the above-mentioned values, and other values not listed in this range are also applicable.
As a preferable embodiment of the present invention, the melting method includes: melting a copper raw material under a vacuum condition, carrying out first standing, introducing protective gas, adding a copper-phosphorus intermediate alloy, inclining a melting device, and carrying out second standing and casting;
the first standing time is 20-40 min; the mass percentage of phosphorus in the copper-phosphorus intermediate alloy is 14-15%; the tilting of the melting device is carried out at least 3 times; the inclination angle of the melting device is 45-55 degrees; and the second standing time is 25-38 min.
Compared with the prior art, the invention has the following beneficial effects:
the method provided by the invention solves the problem of phosphorus segregation in the preparation process of the copper-phosphorus alloy by specifically selecting the adding time and conditions of the copper-phosphorus intermediate alloy and simultaneously adopting an inclined mode in the follow-up process and utilizing the synergistic coupling effect between the copper-phosphorus intermediate alloy and the copper-phosphorus intermediate alloy, improves the uniformity of phosphorus in a copper-phosphorus ingot, controls the total phosphorus content, improves the quality of a copper-phosphorus anode and meets the production requirements of chips.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a smelting method for preparing a copper-phosphorus alloy by using a copper-phosphorus intermediate alloy, which comprises the following steps: melting a copper raw material under a vacuum condition, carrying out first standing, introducing nitrogen, adding a copper-phosphorus intermediate alloy, inclining a melting device, carrying out second standing and casting;
melting is carried out under the condition that the vacuum degree P is 0.01 Pa;
the first standing time is30 min; the introduction of the protective gas ends at the gauge pressure P in the melting apparatusTIs-0.055 MPa;
the mass percentage of phosphorus in the copper-phosphorus intermediate alloy is 14%; the tilting of the melting device was performed 3 times; the inclination angle of the melting device is 50 degrees;
the second standing time is 32 min.
The resulting copper phosphorus alloy had no phosphorus segregation and a phosphorus content of 522+/-40 ppm.
Example 2
The embodiment provides a smelting method for preparing a copper-phosphorus alloy by using a copper-phosphorus intermediate alloy, which comprises the following steps: melting a copper raw material under a vacuum condition, carrying out first standing, introducing argon, adding a copper-phosphorus intermediate alloy, inclining a melting device, carrying out second standing and casting;
melting is carried out under the condition that the vacuum degree P is 0.005 Pa;
the first standing time is 20 min; the introduction of the protective gas ends at the gauge pressure P in the melting apparatusTIs-0.07 MPa;
the mass percentage of phosphorus in the copper-phosphorus intermediate alloy is 14.3%; the tilting of the melting device was performed 4 times; the inclination angle of the melting device is 55 degrees;
the second standing time is 25 min.
The obtained copper-phosphorus alloy has no phosphorus segregation and the content of phosphorus is 545+/-50 ppm.
Example 3
The embodiment provides a smelting method for preparing a copper-phosphorus alloy by using a copper-phosphorus intermediate alloy, which comprises the following steps: melting a copper raw material under a vacuum condition, carrying out first standing, introducing nitrogen, adding a copper-phosphorus intermediate alloy, inclining a melting device, carrying out second standing and casting;
melting is carried out under the condition that the vacuum degree P is 0.015 Pa;
the first standing time is 40 min; the introduction of the protective gas ends at the gauge pressure P in the melting apparatusTIs-0.04 MPa;
the mass percentage of phosphorus in the copper-phosphorus intermediate alloy is 14.5%; the tilting of the melting device was performed 3 times; the inclination angle of the melting device is 45 degrees;
the time of the second standing is 38 min.
The resulting copper-phosphorus alloy had no phosphorus segregation and a phosphorus content of 535+/-30 ppm.
Example 4
The embodiment provides a smelting method for preparing a copper-phosphorus alloy by using a copper-phosphorus intermediate alloy, which comprises the following steps: melting a copper raw material under a vacuum condition, carrying out first standing, introducing nitrogen, adding a copper-phosphorus intermediate alloy, inclining a melting device, carrying out second standing and casting;
melting is carried out under the condition that the vacuum degree P is 0.013 Pa;
the first standing time is 25 min; the introduction of the protective gas ends at the gauge pressure P in the melting apparatusTIs-0.06 MPa;
the mass percentage of phosphorus in the copper-phosphorus intermediate alloy is 14.7%; the tilting of the melting device was performed 5 times; the inclination angle of the melting device is 47 degrees;
the time of the second standing is 27 min.
The resulting copper-phosphorus alloy had no phosphorus segregation and the phosphorus content was 511+/-40 ppm.
Example 5
The embodiment provides a smelting method for preparing a copper-phosphorus alloy by using a copper-phosphorus intermediate alloy, which comprises the following steps: melting a copper raw material under a vacuum condition, carrying out first standing, introducing nitrogen, adding a copper-phosphorus intermediate alloy, inclining a melting device, carrying out second standing and casting;
melting is carried out under the condition that the vacuum degree P is 0.008 Pa;
the first standing time is 33 min; the introduction of the protective gas ends at the gauge pressure P in the melting apparatusTIs-0.054 MPa;
the mass percentage of phosphorus in the copper-phosphorus intermediate alloy is 14.2%; the tilting of the melting device was performed 3 times; the inclination angle of the melting device is 53 degrees;
the second standing time is 36 min.
The resulting copper phosphorus alloy had no phosphorus segregation and a phosphorus content of 481+/-43 ppm.
Example 6
The embodiment provides a smelting method for preparing a copper-phosphorus alloy by using a copper-phosphorus intermediate alloy, which comprises the following steps: melting a copper raw material under a vacuum condition, carrying out first standing, introducing nitrogen, adding a copper-phosphorus intermediate alloy, inclining a melting device, carrying out second standing and casting;
melting is carried out under the condition that the vacuum degree P is 0.008 Pa;
the first standing time is 22 min; the introduction end point of the protective gas is the pressure P in the melting deviceTIs-0.066 MPa;
the mass percentage of phosphorus in the copper-phosphorus intermediate alloy is 14.6%; the tilting of the melting device was performed 3 times; the inclination angle of the melting device is 55 degrees;
the time of the second standing is 29 min.
The resulting copper phosphorus alloy had no phosphorus segregation and the phosphorus content was 565+/-35 ppm.
Example 7
The embodiment provides a smelting method for preparing a copper-phosphorus alloy by using a copper-phosphorus intermediate alloy, which comprises the following steps: melting a copper raw material under a vacuum condition, carrying out first standing, introducing helium, adding a copper-phosphorus intermediate alloy, inclining a melting device, carrying out second standing and casting;
melting is carried out under the condition that the vacuum degree P is 0.011 Pa;
the first standing time is 35 min; the introduction of the protective gas ends at the gauge pressure P in the melting apparatusTIs-0.044 MPa;
the mass percentage of phosphorus in the copper-phosphorus intermediate alloy is 15%; the tilting of the melting device was performed 3 times; the inclination angle of the melting device is 45 degrees;
the time of the second standing is 33 min.
The obtained copper-phosphorus alloy has no phosphorus segregation and the content of phosphorus is 466+/-32 ppm.
Comparative example 1
The only difference from example 1 is that the copper phosphorus master alloy was added between melting and the first standing and the resulting copper phosphorus alloy had phosphorus segregation with a phosphorus content of 482+/-100 ppm.
Comparative example 2
The only difference from example 1 is that the copper-phosphorus master alloy was added between the second standing and casting, and the resulting copper-phosphorus alloy had phosphorus segregation with a phosphorus content of 502+/-120 ppm.
Comparative example 3
The only difference from example 1 is that no nitrogen gas was introduced before the addition of the copper-phosphorus master alloy, and the resulting copper-phosphorus alloy had phosphorus segregation with a phosphorus content of 522+/-110 ppm.
Comparative example 4
The only difference from example 1 is that without tilting the melting apparatus before the second standing, the resulting copper-phosphorus alloy had phosphorus segregation with a phosphorus content of 477+/-130 ppm.
According to the results of the above examples and comparative examples, the method provided by the invention solves the problem of phosphorus segregation in the copper-phosphorus alloy preparation process by specifically selecting the adding time and conditions of the copper-phosphorus intermediate alloy and adopting an inclined mode subsequently and utilizing the synergistic coupling effect between the copper-phosphorus intermediate alloy and the copper-phosphorus intermediate alloy, and simultaneously improves the uniformity of phosphorus in a copper-phosphorus ingot, controls the total phosphorus content, improves the quality of a copper-phosphorus anode and meets the production requirements of chips.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (10)

1. A smelting method for preparing a copper-phosphorus alloy by using a copper-phosphorus intermediate alloy is characterized by comprising the following steps: melting the copper raw material under the vacuum condition, carrying out first standing, then introducing protective gas, then adding the copper-phosphorus intermediate alloy, inclining a melting device, and then carrying out second standing and casting.
2. Smelting process according to claim 1, wherein the melting is carried out under a vacuum level P of 0.005 Pa. ltoreq.P.ltoreq.0.015 Pa.
3. Smelting process as claimed in claim 1 or 2, wherein the time of the first rest is 20-40 min.
4. Smelting process as claimed in any one of claims 1 to 3, wherein said protective gas comprises nitrogen and/or inert gas.
5. Smelting process as claimed in any one of claims 1 to 4, wherein the introduction of the protective gas is terminated at the gauge pressure P in the smelting unitTP is-0.07 MPa or lessT≤-0.04MPa。
6. Smelting method according to any one of claims 1 to 5, wherein the mass percentage of phosphorus in the copper-phosphorus master alloy is 14-15%.
7. Smelting process as claimed in any one of claims 1 to 6, wherein said inclined melting means is carried out at least 3 times.
8. Smelting process as claimed in any one of claims 1 to 7, wherein the angle of inclination of the melting apparatus is in the range 45 to 55 °.
9. Smelting process as claimed in any one of claims 1 to 8, wherein the time of said second rest is from 25 to 38 min.
10. Smelting process as claimed in any one of claims 1 to 9, wherein the smelting process comprises: melting a copper raw material under a vacuum condition, carrying out first standing, introducing protective gas, adding a copper-phosphorus intermediate alloy, inclining a melting device, and carrying out second standing and casting;
the first standing time is 20-40 min; the mass percentage of phosphorus in the copper-phosphorus intermediate alloy is 14-15%; the tilting of the melting device is carried out at least 3 times; the inclination angle of the melting device is 45-55 degrees; and the second standing time is 25-38 min.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115612872A (en) * 2022-09-27 2023-01-17 同创普润(上海)机电高科技有限公司 Smelting process of ultra-pure copper-manganese alloy

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Publication number Priority date Publication date Assignee Title
CN115612872A (en) * 2022-09-27 2023-01-17 同创普润(上海)机电高科技有限公司 Smelting process of ultra-pure copper-manganese alloy
CN115612872B (en) * 2022-09-27 2023-12-29 同创普润(上海)机电高科技有限公司 Smelting process of ultra-high purity copper-manganese alloy

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