CN117265281A - Preparation method of ultra-high purity copper-containing cast ingot - Google Patents
Preparation method of ultra-high purity copper-containing cast ingot Download PDFInfo
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- CN117265281A CN117265281A CN202311242585.3A CN202311242585A CN117265281A CN 117265281 A CN117265281 A CN 117265281A CN 202311242585 A CN202311242585 A CN 202311242585A CN 117265281 A CN117265281 A CN 117265281A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 111
- 239000010949 copper Substances 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 84
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 39
- 238000007670 refining Methods 0.000 claims abstract description 21
- 238000005266 casting Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000004321 preservation Methods 0.000 claims description 37
- 230000000630 rising effect Effects 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 11
- 239000000498 cooling water Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 14
- 238000007872 degassing Methods 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 238000003723 Smelting Methods 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000010943 off-gassing Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/006—Pyrometallurgy working up of molten copper, e.g. refining
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/04—Refining by applying a vacuum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/05—Refining by treating with gases, e.g. gas flushing also refining by means of a material generating gas in situ
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a preparation method of an ultra-high purity copper-containing cast ingot, which comprises the following steps: (1) Taking a round copper sheet as a raw material, and sequentially carrying out vacuumizing treatment, first-stage heat treatment, second-stage heat treatment and third-stage heat treatment to obtain copper liquid; (2) Refining the copper liquid obtained in the step (1) to obtain a purified liquid; (3) Casting the purifying liquid obtained in the step (2) to obtain the ultra-high purity copper-containing cast ingot. The preparation method provided by the invention can effectively solve the problems of deoxidation, degassing, impurity removal and the like in the smelting process, avoid shrinkage cavity, crack and oxidation of the cast ingot, effectively improve the purity of the cast ingot, and has higher yield.
Description
Technical Field
The invention relates to the technical field of metallurgical casting, in particular to a preparation method of an ultra-high purity copper-containing cast ingot.
Background
With the rapid development of very large scale integrated circuits, semiconductor chips are increasingly highly integrated, smaller in size and lower in power consumption, and therefore, higher requirements are being placed on materials used for the semiconductor chips. At present, the conventional aluminum and aluminum alloy materials cannot meet the requirements of the process of the very large scale integrated circuit. Compared with aluminum, the copper and copper alloy material can better meet the requirements of the process of the ultra-large scale integrated circuit, especially ultra-pure copper (purity is more than or equal to 6N), and has important significance for improving the conductivity and the operation speed of chip interconnection lines.
However, the smelting process of the ultra-high purity copper and the alloy thereof is complex, and defects such as shrinkage cavity, crack or oxidation of the cast ingot are easy to occur due to unreasonable casting process or pouring method, so that the cast ingot is scrapped or the yield is low.
For example, CN101199988A discloses a method for preparing an ultra-high purity copper ingot, which uses high purity graphite as crucible and mold materials, and sequentially performs cleaning, drying, charging, vacuumizing, vacuum smelting and vacuum casting to obtain the ultra-high purity copper ingot, but the method cannot further control gas impurities in the ingot, and is difficult to avoid the influence of the gas impurities on the purity of the ingot.
Therefore, the method for preparing the ultra-high purity copper-containing cast ingot has important significance by providing the method for effectively deoxidizing, degassing and removing impurities.
Disclosure of Invention
Aiming at the problems, the invention aims to provide the preparation method of the ultra-high purity copper-containing cast ingot, which can effectively solve the problems of deoxidation, degassing, impurity removal and the like in the smelting process, avoid shrinkage cavity, crack and oxidation of the cast ingot, effectively improve the purity of the cast ingot and has higher yield compared with the prior art.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the invention provides a preparation method of an ultra-high purity copper-containing cast ingot, which comprises the following steps:
(1) Taking a round copper sheet as a raw material, and sequentially carrying out vacuumizing treatment, first-stage heat treatment, second-stage heat treatment and third-stage heat treatment to obtain copper liquid;
(2) Refining the copper liquid obtained in the step (1) to obtain a purified liquid;
(3) Casting the purifying liquid obtained in the step (2) to obtain the ultra-high purity copper-containing cast ingot.
The preparation method provided by the invention comprises the steps of firstly carrying out vacuumizing treatment until reaching the required vacuum degree, and then carrying out first-stage heat treatment; rapidly pumping out water vapor in the furnace in the first-stage heat treatment to prevent oxidation of the feed liquid after the temperature exceeds 200 ℃ until the vacuum degree is stable, and performing the second-stage heat treatment; in the second stage heat treatment, the actual air release rate and the vacuum degree of the raw materials are adjusted, so that the fluctuation of the vacuum degree is prevented, the raw materials are easily deaerated and deoxidized, a large amount of gas impurities are released after the copper sheet is melted into a liquid state, and then the copper sheet enters the third stage heat treatment; deoxidizing and removing impurities in the third-stage heat treatment, so that the purity of the copper liquid is improved; and then refining to further improve the purity, and finally casting to obtain an ingot. The preparation method provided by the invention can effectively solve the problems of deoxidation, degassing, impurity removal and the like in the smelting process, avoid shrinkage cavity, crack and oxidation of the cast ingot, effectively improve the purity of the cast ingot, and has higher yield.
In the present invention, the purity of the ultra-high purity copper-containing ingot is not less than 5N, preferably not less than 6N, and may be, for example, 99.9999wt%, 99.99991wt%, 99.99992wt% or 99.99993wt%, but not limited to, the recited values, and other non-recited values within the numerical range are equally applicable.
Preferably, the diameter of the circular copper sheet in the step (1) is 250-350mm, for example, 250mm, 260mm, 270mm, 280mm, 290mm, 300mm, 310mm, 320mm, 340mm or 350mm, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the thickness of the circular copper sheet is 3-7mm, for example, 3mm, 4mm, 5mm, 6mm or 7mm, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, a circular copper gasket is placed between the circular copper sheet and the bottom of the crucible.
Preferably, the diameter of the circular copper gasket is 180-220mm, for example, 180mm, 190mm, 200mm, 210mm or 220mm, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the thickness of the circular copper pad is 40-60mm, for example 40mm, 45mm, 50mm, 55mm or 60mm, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the edges of the round copper gaskets are machined with R-shaped chamfers.
Preferably, the purity of the circular copper sheets and the circular copper gaskets is equal to or higher than 6N, for example, 99.9999wt%, 99.99991wt%, 99.99992wt% or 99.99993wt%, but the purity is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
According to the invention, by controlling the shape, the size and the purity of the round copper sheet and the round copper gasket, impurities can be prevented from being introduced into the crucible, scraping the inner wall of the crucible and introducing the impurities can be avoided.
Preferably, the final vacuum degree of the vacuuming treatment in the step (1) is (5-7). Times.10 -3 Pa, for example, may be 5×10 -3 Pa、5.5×10 -3 Pa、6×10 -3 Pa、6.5×10 -3 Pa or 7X 10 -3 Pa, but not limited to the recited values, other non-recited values within the range of values are equally applicable.
Preferably, the first-stage heat treatment of step (1) includes sequentially performing a first heat up and a first heat up.
The end temperature of the first temperature rise is preferably 145 to 155 ℃, and may be 145 ℃, 146 ℃, 147 ℃, 148 ℃, 149 ℃, 150 ℃, 151 ℃, 152 ℃, 153 ℃, 154 ℃, or 155 ℃, for example, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the time of the first heat preservation is 25-35min, for example, 25min, 26min, 27min, 28min, 29min, 30min, 31min, 32min, 34min or 35min, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
In the invention, the terminal temperature of the first temperature rise and the time of the first heat preservation are preferably controlled in a specific range, which is favorable for rapidly pumping out water vapor in the furnace and avoiding the oxidation of the cast ingot.
Preferably, the vacuum degree in the first heat preservation process is (5-7) multiplied by 10 -2 Pa, for example, may be 5×10 -2 Pa、5.5×10 -2 Pa、6×10 -2 Pa、6.5×10 -2 Pa or 7X 10 -2 Pa, but not limited to the recited values, other non-recited values within the range of values are equally applicable.
Preferably, the second stage heat treatment in the step (1) includes sequentially performing a second temperature rise, a third temperature rise, a second heat preservation, a fourth temperature rise and a third heat preservation.
The end temperature of the second temperature rise is preferably 780 to 800 ℃, and may be 780 ℃, 782 ℃, 784 ℃, 786 ℃, 788 ℃, 790 ℃, 792 ℃, 794 ℃, 796 ℃, 798 ℃, or 800 ℃, for example, but not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the temperature rising rate of the second temperature rising is 6-8 ℃/min, for example, 6 ℃/min, 6.2 ℃/min, 6.4 ℃/min, 6.6 ℃/min, 6.8 ℃/min, 7 ℃/min, 7.2 ℃/min, 7.4 ℃/min, 7.6 ℃/min, 7.8 ℃/min or 8 ℃/min, but the temperature rising rate is not limited to the recited value, and other non-recited values in the range of values are equally applicable.
In the invention, the heating rate of the second heating is preferably controlled within a specific range, so that the air release rate of the raw material can be further controlled, the excessive vacuum degree in the furnace is avoided, and the degassing of the raw material is facilitated.
The end temperature of the third temperature rise is preferably 1180 to 1200 ℃, and may be 1180 ℃, 1182 ℃, 1184 ℃, 1186 ℃, 1188 ℃, 1190 ℃, 1192 ℃, 1194 ℃, 1196 ℃, 1198 ℃, or 1200 ℃, for example, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the temperature rising rate of the third temperature rising is 3-5 ℃/min, for example, 3 ℃/min, 3.2 ℃/min, 3.4 ℃/min, 3.6 ℃/min, 3.8 ℃/min, 4 ℃/min, 4.2 ℃/min, 4.4 ℃/min, 4.6 ℃/min, 4.8 ℃/min or 5 ℃/min, but the temperature rising rate is not limited to the recited value, and other non-recited values in the numerical range are equally applicable.
In the invention, the heating rate of the third heating is preferably controlled within a specific range, so that the air release rate of the raw material can be further controlled, the excessive vacuum degree in the furnace is avoided, and the degassing of the raw material is facilitated.
Preferably, the temperature of the second insulation is 1100-1150 ℃, for example 1100 ℃, 1110 ℃, 1120 ℃, 1130 ℃, 1140 ℃ or 1150 ℃, but not limited to the values listed, and other values not listed in the numerical range are equally applicable.
In the invention, the copper sheet is continuously melted into liquid after the third temperature rise, the melting is an endothermic process, the temperature is slightly reduced after the third temperature rise, at the moment, the solid raw material is just melted into liquid, and a large amount of gas impurities are released, so the second heat preservation is carried out until the gas release is complete, namely, the liquid level is not in a boiling state, and the vacuum degree is kept at 2 multiplied by 10 -1 Pa or below.
Preferably, the end temperature of the fourth temperature rise is 1180-1220 ℃, for example 1180 ℃, 1190 ℃, 1200 ℃, 1210 ℃ or 1220 ℃, but not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the time of the third incubation is 25-35min, for example, 25min, 26min, 28min, 30min, 32min, 34min or 35min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
In the invention, the raw materials are fully melted into liquid in the third heat preservation process, and volatile impurities in the melt can be fully released and removed through the third heat preservation.
Preferably, the third stage heat treatment of step (1) comprises a fifth elevated temperature.
Preferably, the final temperature of the fifth temperature rise is 1240-1260 ℃, such as 1240 ℃, 1245 ℃, 1250 ℃, 1255 ℃ or 1260 ℃, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the temperature rising rate of the fifth temperature rising is 3-4 ℃/min, for example, 3 ℃/min, 3.2 ℃/min, 3.4 ℃/min, 3.6 ℃/min, 3.8 ℃/min or 4 ℃/min, but the temperature rising rate is not limited to the recited value, and other non-recited values in the numerical range are equally applicable.
Preferably, the inert gas substitution is performed before the refining in the step (2).
Preferably, the inert gas comprises argon.
Preferably, the number of inert gas substitutions is at least 2, for example, 2, 3 or 4, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the inert gas is continuously introduced after the inert gas is replaced until the vacuum degree is (0.8-1.2) multiplied by 10 2 Pa may be, for example, 0.8X10 2 Pa、0.85×10 2 Pa、0.9×10 2 Pa、0.95×10 2 Pa、1×10 2 Pa、1.1×10 2 Pa or 1.2X10 2 Pa, but not limited to the recited values, other non-recited values within the range of values are equally applicable.
Preferably, the temperature of the refining in step (2) is 1300-1350 ℃, such as 1300 ℃, 1310 ℃, 1320 ℃, 1340 ℃ or 1350 ℃, but not limited to the values recited, and other values not recited in the range of values are equally applicable.
Preferably, the refining time is 50-70min, for example, 50min, 52min, 54min, 56min, 58min, 60min, 62min, 64min, 66min, 68min or 70min, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
In the invention, the refining temperature and time are preferably controlled within a specific range, which is favorable for further finishing the deoxidation of the metal, thereby further improving the purity of the liquid metal and further alloying the melt.
Preferably, the alloy is added during the refining.
Preferably, the alloy comprises manganese and/or aluminium.
Preferably, the alloy has a purity of 5N or more, for example, 99.999wt%, 99.9991wt%, 99.9992wt% or 99.9993wt%, but not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the cooling water temperature for the casting in the step (3) is 35-40 ℃, for example, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃ or 40 ℃, but not limited to the listed values, and other non-listed values in the numerical range are equally applicable.
Preferably, the casting speed is 28-32mm/min, for example 28mm/min, 29mm/min, 30mm/min, 31mm/min or 32mm/min, but not limited to the values recited, other values not recited in the numerical range are equally applicable.
According to the invention, the temperature of the cooling water and the casting speed are controlled within a specific range, so that the grain size of the cast ingot can be further controlled, the tissue structure uniformity of the cast ingot is promoted, and the yield is higher.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) Firstly placing a circular copper gasket with the diameter of 180-220mm and the thickness of 40-60mm into a crucible, then placing a circular copper sheet with the diameter of 250-350mm and the thickness of 3-7mm, wherein the purity of the circular copper sheet and the circular copper gasket are more than or equal to 6N, and firstly vacuumizing until the final vacuum degree is (5-7) multiplied by 10 -3 Pa；
Then performing first stage heat treatment, including first heating to 145-155 deg.C, and then performing first heat preservation for 25-35min, wherein vacuum degree is (5-7) x 10 during the first heat preservation -2 Pa；
Then carrying out second-stage heat treatment, namely carrying out second heating to 780-800 ℃ at the speed of 6-8 ℃/min, carrying out third heating to 1180-1200 ℃ at the speed of 3-5 ℃/min, carrying out second heat preservation at the temperature of 1100-1150 ℃, carrying out fourth heating to 1180-1220 ℃, and carrying out third heat preservation for 25-35min;
then carrying out a third stage heat treatment, which comprises fifth heating to 1240-1260 ℃ at a speed of 3-4 ℃/min to obtain copper liquid;
(2) Displacing with inert gas for at least 2 times, and continuously introducing inert gas until vacuum degree is (0.8-1.2) x 10 2 Pa, refining the copper liquid obtained in the step (1) at 1300-1350 ℃ for 50-70min, and adding alloy material with purity more than or equal to 5N in the refining process to obtain a purifying liquid;
(3) Casting the purified liquid obtained in the step (2) under the conditions that the temperature of cooling water is 35-40 ℃ and the speed is 28-32mm/min, so as to obtain the ultra-high purity copper-containing cast ingot.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method provided by the invention can effectively solve the problems of deoxidation, degassing, impurity removal and the like in the smelting process, avoid shrinkage cavity, crack and oxidation of the ingot, effectively improve the purity of the ingot, and has the advantages that under the optimal condition, the purity of the ultra-high purity copper-containing ingot is more than or equal to 6N, and the yield is higher.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a preparation method of an ultra-high purity copper-containing cast ingot, which comprises the following steps:
(1) Firstly placing a round copper gasket with the diameter of 200mm and the thickness of 50mm into a crucible, then placing a round copper sheet with the diameter of 300mm and the thickness of 5mm into the crucible, processing R-shaped chamfers on the edges of the round copper gasket, and carrying out vacuumizing treatment until the final vacuum degree is 6 multiplied by 10 on the round copper sheet and the round copper gasket, wherein the purities of the round copper sheet and the round copper gasket are 6N -3 Pa；
Then the first stage heat treatment is carried out, which comprises the steps of first heating to 150 ℃ and then carrying out first heat preservation for 30min, wherein the vacuum degree in the first heat preservation process is 6 multiplied by 10 -2 Pa；
Then carrying out second-stage heat treatment, namely carrying out second heating to 800 ℃ at the speed of 7 ℃/min, then carrying out third heating to 1200 ℃ at the speed of 4 ℃/min, then carrying out second heat preservation at 1120 ℃ until the gas is completely released, namely the liquid level is in a non-boiling state, then carrying out fourth heating to 1200 ℃, and then carrying out third heat preservation for 30min;
then carrying out a third-stage heat treatment, namely carrying out fifth temperature rise to 1250 ℃ at a speed of 3 ℃/min to obtain copper liquid;
(2) Argon is substituted for 2 times, and then argon is continuously introduced until the vacuum degree is 1 multiplied by 10 2 Pa, and refining the copper liquid obtained in the step (1) for 60min at 1320 ℃ to obtain a purified liquid;
(3) Casting the purified liquid obtained in the step (2) under the condition that the cooling water temperature is 38 ℃ and the speed is 30mm/min, so as to obtain the ultra-high purity copper-containing cast ingot.
Example 2
The embodiment provides a preparation method of an ultra-high purity copper-containing cast ingot, which comprises the following steps:
(1) Firstly placing a round copper gasket with the diameter of 200mm and the thickness of 50mm into a crucible, then placing a round copper sheet with the diameter of 300mm and the thickness of 5mm into the crucible, processing R-shaped chamfers on the edges of the round copper gasket, and carrying out vacuumizing treatment until the final vacuum degree is 5 multiplied by 10 on the round copper sheet and the round copper gasket, wherein the purities of the round copper sheet and the round copper gasket are 6N -3 Pa；
Then the first stage heat treatment is carried out, which comprises the steps of first heating to 155 ℃ and then carrying out the first heat preservation for 25min, wherein the vacuum degree in the first heat preservation process is 7 multiplied by 10 -2 Pa；
Then carrying out second-stage heat treatment, namely carrying out second heating to 790 ℃ at the speed of 6 ℃/min, then carrying out third heating to 1190 ℃ at the speed of 5 ℃/min, then carrying out second heat preservation at 1150 ℃ until the gas is completely released, namely the liquid level is in a non-boiling state, then carrying out fourth heating to 1220 ℃, and then carrying out third heat preservation for 35min;
then carrying out a third-stage heat treatment, namely carrying out fifth heating to 1260 ℃ at the speed of 4 ℃/min to obtain copper liquid;
(2) Replaced 2 times with argon, thenArgon is continuously introduced until the vacuum degree is 1 multiplied by 10 2 Pa, refining the copper liquid obtained in the step (1) at 1350 ℃ for 70min, and adding manganese with the purity of 5N in the refining process to obtain a purified liquid;
(3) Casting the purified liquid obtained in the step (2) under the condition that the temperature of cooling water is 40 ℃ and the speed is 28mm/min, so as to obtain the ultra-high purity copper-containing cast ingot.
Example 3
The embodiment provides a preparation method of an ultra-high purity copper-containing cast ingot, which comprises the following steps:
(1) Firstly placing a round copper gasket with the diameter of 200mm and the thickness of 50mm into a crucible, then placing a round copper sheet with the diameter of 300mm and the thickness of 5mm into the crucible, processing R-shaped chamfers on the edges of the round copper gasket, and carrying out vacuumizing treatment until the vacuum degree of the end point is 7 multiplied by 10, wherein the purities of the round copper sheet and the round copper gasket are 6N -3 Pa；
Then the first stage heat treatment is carried out, which comprises the steps of first heating to 145 ℃, then carrying out the first heat preservation for 35min, wherein the vacuum degree is 5 multiplied by 10 in the first heat preservation process -2 Pa；
Then carrying out second-stage heat treatment, namely carrying out second heating to 780 ℃ at the speed of 8 ℃/min, then carrying out third heating to 1180 ℃ at the speed of 3 ℃/min, then carrying out second heat preservation at 1100 ℃ until the gas is completely released, namely the liquid level is in a non-boiling state, then carrying out fourth heating to 1180 ℃, and then carrying out third heat preservation for 25min;
then carrying out a third-stage heat treatment, namely carrying out fifth heating to 1240 ℃ at a speed of 3 ℃/min to obtain copper liquid;
(2) Argon is substituted for 2 times, and then argon is continuously introduced until the vacuum degree is 1 multiplied by 10 2 Pa, and refining the copper liquid obtained in the step (1) for 50min at the temperature of 1300 ℃ to obtain a purified liquid;
(3) Casting the purified liquid obtained in the step (2) under the condition that the temperature of cooling water is 35 ℃ and the speed is 32mm/min, so as to obtain the ultra-high purity copper-containing cast ingot.
Example 4
This example provides a method of preparing an ultra-high purity copper-containing ingot that differs from example 1 only in that the second elevated temperature has an elevated temperature rate of 3 ℃/min.
Example 5
This example provides a method of preparing an ultra-high purity copper-containing ingot that differs from example 1 only in that the second elevated temperature has an elevated temperature rate of 10 ℃/min.
Example 6
This example provides a method of preparing an ultra-high purity copper-containing ingot that differs from example 1 only in that the third elevated temperature has an elevated temperature rate of 1 ℃/min.
Example 7
This example provides a method of preparing an ultra-high purity copper-containing ingot that differs from example 1 only in that the third elevated temperature has an elevated temperature rate of 8 ℃/min.
Comparative example 1
This comparative example provides a method for preparing an ultra-high purity copper-containing ingot, which differs from example 1 only in that the first-stage heat treatment is not performed, and the second-stage heat treatment is directly performed after the vacuum treatment, i.e., in step (1):
vacuumizing to a final vacuum degree of (5-7) x 10 -3 Pa, directly performing second-stage heat treatment: directly carrying out second temperature rise to 780-800 ℃ at the speed of 6-8 ℃/min, then carrying out third temperature rise to 1180-1200 ℃ at the speed of 3-5 ℃/min, then carrying out second heat preservation at 1100-1150 ℃, then carrying out fourth temperature rise to 1180-1220 ℃, and then carrying out third heat preservation for 25-35min; and then carrying out a third stage heat treatment, namely carrying out fifth temperature rise to 1240-1260 ℃ at a speed of 3-4 ℃/min to obtain copper liquid.
Comparative example 2
This comparative example provides a process for the preparation of ultra-high purity copper-containing ingots, which differs from example 1 only in that the second stage heat treatment is not performed, and the first stage heat treatment is directly followed by the third stage heat treatment, i.e. in step (1):
and (3) after the first heat preservation is carried out for 25-35min, directly carrying out the third-stage heat treatment, namely, carrying out fifth temperature rise to 1240-1260 ℃ at the speed of 3-4 ℃/min, and obtaining the copper liquid.
Comparative example 3
This comparative example provides a process for the preparation of ultra-high purity copper-containing ingots which differs from example 1 only in that no third stage heat treatment is performed, i.e. in step (1): and carrying out third heat preservation for 25-35min to obtain copper liquid.
The purity of the ultra-high purity copper-containing ingots prepared in examples 1 to 7 and comparative examples 1 to 3 was measured by glow mass spectrometry (GDMS), and the results are shown in Table 1.
TABLE 1
From the data in Table 1, the following points can be seen:
(1) As can be seen from the data of examples 1-3, the preparation method provided by the invention can ensure that the purity of the obtained ultra-high purity copper-containing cast ingot is more than or equal to 99.99996wt% under the optimal condition.
(2) As can be seen from the data of comparative examples 1, 4-5 and 6-7, the difference between examples 4-5 and example 1 is that the second heating rate is not within the preferred range of the present invention, the difference between examples 6-7 and example 1 is that the third heating rate is not within the preferred range of the present invention, and the purity of examples 4-7 is significantly lower than that of example 1, so that the present invention can control the raw material off-gassing rate by controlling the heating rate, further facilitating the raw material off-gassing, and further improving the purity of the ingot.
(3) As can be seen from the data of comparative examples 1 and 1 to 3, comparative examples 1 to 3 differ from example 1 only in that the first stage heat treatment, the second stage heat treatment and the third stage heat treatment are not performed, respectively, and the purity in example 1 is significantly higher than that in comparative examples 1 to 3, and it can be seen that the present invention can significantly improve the purity of an ingot by performing the combined operation of the first stage heat treatment, the second stage heat treatment and the third stage heat treatment in this order.
In conclusion, the preparation method provided by the invention can effectively solve the problems of deoxidation, degassing, impurity removal and the like in the smelting process, avoid shrinkage cavity, crack and oxidation of the ingot, effectively improve the purity of the ingot, and under the preferred condition, the purity of the ultra-high purity copper-containing ingot is more than or equal to 6N, and the yield is higher.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (10)
1. The preparation method of the ultra-high purity copper-containing cast ingot is characterized by comprising the following steps of:
(1) Taking a round copper sheet as a raw material, and sequentially carrying out vacuumizing treatment, first-stage heat treatment, second-stage heat treatment and third-stage heat treatment to obtain copper liquid;
(2) Refining the copper liquid obtained in the step (1) to obtain a purified liquid;
(3) Casting the purifying liquid obtained in the step (2) to obtain the ultra-high purity copper-containing cast ingot.
2. The method of claim 1, wherein the diameter of the round copper sheet in step (1) is 250-350mm;
preferably, the thickness of the round copper sheet is 3-7mm;
preferably, a circular copper gasket is arranged between the circular copper sheet and the bottom of the crucible;
preferably, the diameter of the circular copper gasket is 180-220mm;
preferably, the thickness of the circular copper gasket is 40-60mm;
preferably, the edge of the round copper gasket is provided with an R-shaped chamfer;
preferably, the purity of the round copper sheet and the round copper gasket are both more than or equal to 6N.
3. The method according to claim 1 or 2, wherein the final vacuum degree of the vacuum-evacuation treatment in step (1) is (5-7). Times.10 -3 Pa。
4. A method according to any one of claims 1 to 3, wherein the first stage heat treatment of step (1) comprises a first heat up and a first heat up carried out sequentially;
preferably, the end temperature of the first temperature rise is 145-155 ℃;
preferably, the first heat preservation time is 25-35min;
preferably, the vacuum degree in the first heat preservation process is (5-7) multiplied by 10 -2 Pa。
5. The method according to any one of claims 1 to 4, wherein the second-stage heat treatment of step (1) comprises sequentially performing a second temperature increase, a third temperature increase, a second heat preservation, a fourth temperature increase, and a third heat preservation;
preferably, the end temperature of the second heating is 780-800 ℃;
preferably, the temperature rising rate of the second temperature rising is 6-8 ℃/min;
preferably, the end temperature of the third temperature rise is 1180-1200 ℃;
preferably, the temperature rising rate of the third temperature rising is 3-5 ℃/min;
preferably, the temperature of the second insulation is 1100-1150 ℃;
preferably, the end temperature of the fourth heating is 1180-1220 ℃;
preferably, the time of the third heat preservation is 25-35min.
6. The method of any one of claims 1-5, wherein the third stage heat treatment of step (1) comprises a fifth elevated temperature;
preferably, the final temperature of the fifth temperature rise is 1240-1260 ℃;
preferably, the temperature rising rate of the fifth temperature rising is 3-4 ℃/min.
7. The method according to any one of claims 1 to 6, wherein the inert gas substitution is performed before the refining in step (2);
preferably, the inert gas comprises argon;
preferably, the number of inert gas substitutions is at least 2;
preferably, the inert gas is continuously introduced after the inert gas is replaced until the vacuum degree is (0.8-1.2) multiplied by 10 2 Pa。
8. The method of any one of claims 1-7, wherein the refining in step (2) is at a temperature of 1300-1350 ℃;
preferably, the refining time is 50-70min;
preferably, the alloy is added during the refining process;
preferably, the alloy comprises manganese and/or aluminium;
preferably, the purity of the alloy material is more than or equal to 5N.
9. The method of any one of claims 1-8, wherein the cooling water temperature for casting in step (3) is 35-40 ℃;
preferably, the casting speed is 28-32mm/min.
10. The preparation method according to any one of claims 1 to 9, characterized in that the preparation method comprises the steps of:
(1) Putting a round copper gasket with the diameter of 180-220mm and the thickness of 40-60mm into a crucible, and then putting the copper gasket with the diameter of 250-350mm and the thicknessThe purity of the round copper sheet and the round copper gasket is more than or equal to 6N, and the round copper sheet and the round copper gasket are vacuumized until the final vacuum degree is (5-7) multiplied by 10 -3 Pa；
Then performing first stage heat treatment, including first heating to 145-155 deg.C, and then performing first heat preservation for 25-35min, wherein vacuum degree is (5-7) x 10 during the first heat preservation -2 Pa；
Then carrying out second-stage heat treatment, namely carrying out second heating to 780-800 ℃ at the speed of 6-8 ℃/min, carrying out third heating to 1180-1200 ℃ at the speed of 3-5 ℃/min, carrying out second heat preservation at the temperature of 1100-1150 ℃, carrying out fourth heating to 1180-1220 ℃, and carrying out third heat preservation for 25-35min;
then carrying out a third stage heat treatment, which comprises fifth heating to 1240-1260 ℃ at a speed of 3-4 ℃/min to obtain copper liquid;
(2) Displacing with inert gas for at least 2 times, and continuously introducing inert gas until vacuum degree is (0.8-1.2) x 10 2 Pa, refining the copper liquid obtained in the step (1) at 1300-1350 ℃ for 50-70min, and adding alloy material with purity more than or equal to 5N in the refining process to obtain a purifying liquid;
(3) Casting the purified liquid obtained in the step (2) under the conditions that the temperature of cooling water is 35-40 ℃ and the speed is 28-32mm/min, so as to obtain the ultra-high purity copper-containing cast ingot.
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