CN115537577B - Preparation method of ultra-high purity copper - Google Patents
Preparation method of ultra-high purity copper Download PDFInfo
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- CN115537577B CN115537577B CN202211184827.3A CN202211184827A CN115537577B CN 115537577 B CN115537577 B CN 115537577B CN 202211184827 A CN202211184827 A CN 202211184827A CN 115537577 B CN115537577 B CN 115537577B
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 159
- 239000010949 copper Substances 0.000 title claims abstract description 159
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000002844 melting Methods 0.000 claims abstract description 146
- 230000008018 melting Effects 0.000 claims abstract description 146
- 239000000463 material Substances 0.000 claims abstract description 64
- 238000007670 refining Methods 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000005266 casting Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 23
- 238000003723 Smelting Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 9
- 230000000284 resting effect Effects 0.000 claims 4
- 238000010309 melting process Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000003466 welding Methods 0.000 description 12
- 229910000881 Cu alloy Inorganic materials 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000013077 target material Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009461 vacuum packaging 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
- C22B15/0028—Smelting or converting
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to a preparation method of ultra-high purity copper, which comprises the following steps: sequentially carrying out first vacuum melting, second vacuum melting and third vacuum melting after copper material filling, sequentially carrying out standing refining and pouring, vibrating a pouring die, and cooling and demoulding to obtain the ultra-high purity copper; the absolute vacuum degree of the second vacuum melting is less than the absolute vacuum degree of the first vacuum melting is less than the absolute vacuum degree of the third vacuum melting; the addition amount of the copper material in the second vacuum melting is larger than that in the third vacuum melting. According to the preparation method provided by the invention, through the design of the vacuum melting process, the high-efficiency removal of volatile impurities in copper in the melting stage is realized, the high-efficiency preparation of ultra-high purity copper is realized, and the purity of the obtained ultra-high purity copper is more than or equal to 99.9999%.
Description
Technical Field
The invention relates to the field of ultra-high purity copper preparation, in particular to a preparation method of ultra-high purity copper.
Background
At present, ultra-high-purity copper (purity is more than or equal to 99.9999%) is a raw material for manufacturing ultra-high-purity copper sputtering target materials for semiconductors, is mainly used for wiring of integrated circuit chips, and is an indispensable raw material in high-quality chip production.
As CN113894401a discloses a method for low-temperature diffusion welding of ultra-high purity copper target components, the method comprises the following steps: preprocessing the welding surface of the ultra-high purity copper target; turning threads on the welding surface of the copper alloy backboard; the pitch of the threads is 0.2-0.45mm, and the depth of the threads is 0.1-0.15mm; assembling the treated ultra-high-purity copper target and the copper alloy backboard, and then vacuum packaging and then putting the ultra-high-purity copper target and the copper alloy backboard into a sheath for degassing treatment; performing diffusion welding after the degassing treatment, and then cooling to obtain an ultra-high-purity copper target component; by turning threads on the welding surface of the back plate and further controlling the thread size, the ultra-high-purity copper target material and the copper alloy back plate are welded together at a lower temperature, and the grain size, the electric conductivity, the heat conductivity and the welding strength of the ultra-high-purity copper target material are ensured.
CN111001921a discloses a diffusion welding method for ultra-high purity copper target, said welding method comprising the following steps: (1) Preparing an ultra-high-purity copper target and a back plate with threads, adding copper powder to the threads on the back plate, and then assembling with the ultra-high-purity copper target; (2) Placing the assembled ultra-high purity copper target and backboard into a sheath, welding the sheath and vacuumizing; (3) Performing hot isostatic pressing treatment on the evacuated sheath, cooling and removing the sheath to finish welding; wherein the pitch of the threads is 0.35-0.45mm; the depth of the thread is 0.2-0.3mm. Through reasonable setting of the screw thread size and configuration of the whole process conditions, the target can still keep good electric conduction, heat conduction and welding strength in the ultra-high copper target welding process, so that the uniformity of the sputtering rate of the target can be ensured, and abnormal phenomena of Partical, peeling, arcing and the like of the target in the sputtering process can be avoided.
However, certain difficulties still exist in the current preparation of ultra-high purity copper.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a preparation method of ultra-high purity copper, so as to solve the problem that the purity of the existing ultra-high purity copper is not ideal during preparation.
To achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of ultra-high purity copper, which comprises the following steps: sequentially carrying out first vacuum melting, second vacuum melting and third vacuum melting after copper material filling, sequentially carrying out standing refining and pouring, vibrating a pouring die, and cooling and demoulding to obtain the ultra-high purity copper;
the absolute vacuum degree of the second vacuum melting is less than the absolute vacuum degree of the first vacuum melting is less than the absolute vacuum degree of the third vacuum melting;
the addition amount of the copper material in the second vacuum melting is larger than that in the third vacuum melting.
According to the preparation method provided by the invention, through the design of the vacuum melting process, the high-efficiency removal of volatile impurities in copper in the melting stage is realized, the high-efficiency preparation of ultra-high purity copper is realized, and the purity of the obtained ultra-high purity copper is more than or equal to 99.9999%.
In the invention, the purity of the used copper material is 99.99-99.999% of simple-substance copper ingot.
In a preferred embodiment of the present invention, the absolute vacuum degree of the first vacuum melting is 70 to 150Pa, for example, 70Pa, 75Pa, 80Pa, 85Pa, 90Pa, 95Pa, 100Pa, 105Pa, 110Pa, 115Pa, 120Pa, 125Pa, 130Pa, 135Pa, 140Pa, 145Pa, or 150Pa, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the copper material is added in an amount of 10-20% of the total amount of the smelting copper in the first vacuum melting, for example, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5% or 20%, etc., but not limited to the recited values, and other non-recited values in the range are equally applicable.
As a preferable embodiment of the invention, the absolute vacuum degree of the second vacuum melting is 0.005-0.009Pa, and may be, for example, 0.005Pa, 0.0051Pa, 0.0052Pa, 0.0053Pa, 0.0054Pa, 0.0055Pa, 0.0056Pa, 0.0057Pa, 0.0058Pa, 0.0059Pa, 0.006Pa, 0.0061Pa, 0.0062Pa, 0.0063Pa, 0.0064Pa, 0.0065Pa, 0.0066Pa, 0.0067Pa, 0.0068Pa, 0.0069Pa, 0.007Pa, 0.0071Pa, 0.0072Pa, 0.0073Pa, 0.0074Pa, 0.0075Pa, 0.0076Pa, 0.0078Pa, 0.009Pa, 0.008, 0.0081, 0.0082Pa, 0.0083Pa, 0.86 Pa, 0.0086Pa, 0.0088Pa, or the like, but is not limited to the other suitable values, such as those which are not exemplified.
Preferably, the copper material in the second vacuum melting is added in an amount of 50-60% of the total amount of the melted copper, for example, 50%, 50.5%, 51%, 51.5%, 52%, 52.5%, 53%, 53.5%, 54%, 54.5%, 55%, 55.5%, 56%, 56.5%, 57%, 57.5%, 58%, 58.5%, 59%, 59.5% or 60%, etc., but not limited to the recited values, and other non-recited values in the range are equally applicable.
In a preferred embodiment of the present invention, the absolute vacuum degree of the third vacuum melting is 250 to 350Pa, for example, 250Pa, 255Pa, 260Pa, 265Pa, 270Pa, 275Pa, 280Pa, 285Pa, 290Pa, 295Pa, 300Pa, 305Pa, 310Pa, 315Pa, 320Pa, 325Pa, 330Pa, 335Pa, 340Pa, 345Pa, 350Pa, or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above range are equally applicable.
Preferably, the copper material is added in an amount of 21-30% of the total amount of the smelting copper in the third vacuum melting, for example, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5% or 30%, etc., but not limited to the recited values, and other non-recited values in the range are equally applicable.
In the invention, the total addition amount of copper materials in three vacuum melting stages is 100 percent.
As a preferable embodiment of the present invention, the stationary refining includes a first stationary stage and a second stationary stage which are sequentially performed.
In a preferred embodiment of the present invention, the first standing temperature is 1080 to 1100 ℃, for example 1080 ℃, 1085 ℃, 1090 ℃, 1095 ℃, 1100 ℃, or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above range are equally applicable.
Preferably, the first standing time is 10-20min, for example, 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min or 20min, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
In the present invention, the vacuum degree at the start of the first standing is the absolute vacuum degree after the third vacuum melting.
In a preferred embodiment of the present invention, the second standing temperature may be 1200 to 1300 ℃, for example, 1200 ℃, 1210 ℃, 1220 ℃, 1230 ℃, 1240 ℃, 1250 ℃, 1260 ℃, 1270 ℃, 1280 ℃, 1290 ℃, 1300 ℃, or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above range are equally applicable.
PreferablyThe second standing vacuum degree is less than or equal to 6.7X10 -3 Pa may be, for example, 6.7X10 -3 Pa、6.6×10 -3 Pa、6.4×10 -3 Pa、6.2×10 -3 Pa、6.0×10 -3 Pa、5.8×10 -3 Pa、5.6×10 -3 Pa、5.4×10 -3 Pa、5.2×10 -3 Pa、5.0×10 -3 Pa、4.8×10 -3 Pa、4.6×10 -3 Pa、4.4×10 -3 Pa、4.4×10 -3 Pa、4.2×10 -3 Pa、4×10 -3 Pa、3×10 -3 Pa、2×10 -3 Pa or 1X 10 -3 Pa, etc., but are not limited to the recited values, and other non-recited values within this range are equally applicable.
Preferably, the second standing time is 10-30min, for example, 10min, 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min, 28min or 30min, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
In a preferred embodiment of the present invention, the temperature of the copper liquid at the time of casting is 1200 to 1300 ℃, for example, 1200 ℃, 1205 ℃, 1210 ℃, 1215 ℃, 1220 ℃, 1225 ℃, 1230 ℃, 1235 ℃, 1240 ℃, 1245 ℃, 1250 ℃, 1255 ℃, 1260 ℃, 1265 ℃, 1270 ℃, 1275 ℃, 1280 ℃, 1285 ℃, 1290 ℃, 1295 ℃, 1300 ℃, etc., but the present invention is not limited to the above-mentioned values, and other non-mentioned values within the above range are equally applicable.
As a preferable technical scheme of the invention, the vibration of the mould is that the frequency of the vibration of the mould increases along with the casting.
In the present invention, the vibration frequency ranges from 0 to 200Hz, for example, may be 0Hz, 5Hz, 10Hz, 15Hz, 20Hz, 25Hz, 30Hz, 35Hz, 40Hz, 45Hz, 50Hz, 55Hz, 60Hz, 65Hz, 70Hz, 75Hz, 80Hz, 85Hz, 90Hz, 95Hz, 100Hz, 105Hz, 110Hz, 115Hz, 120Hz, 125Hz, 130Hz, 135Hz, 140Hz, 145Hz, 150Hz, 155Hz, 160Hz, 165Hz, 170Hz, 175Hz, 180Hz, 185Hz, 190Hz, 195Hz or 200Hz, etc., but are not limited to the values recited, and other non-enumerated values within this range are equally applicable.
In the invention, the frequency of the vibration of the die increases gradually along with the increase of the casting time, the increasing rate is 10-15Hz for increasing the frequency of 1min per casting, the frequency can be increased per minute, and the frequency can also be increased in a direct accumulation way after casting for a certain period of time, for example, the casting rate is controlled, the complete time of all casting is confirmed to be 20min, the casting vibration is started to be 0Hz, the vibration is regulated to be 50Hz after 5min, the vibration is regulated to be 100Hz after 10min, the vibration is regulated to be 150Hz after 15min, and the vibration is regulated to be 200Hz after 20min.
According to the invention, the ultra-high purity of the obtained copper-aluminum alloy is realized by adopting the special die vibration control, so that the purity of the ultra-high purity copper-aluminum alloy can be further improved.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
sequentially carrying out first vacuum melting, second vacuum melting and third vacuum melting after copper material filling, sequentially carrying out standing refining and pouring, vibrating a pouring die, and cooling and demoulding to obtain the ultra-high purity copper;
the absolute vacuum degree of the second vacuum melting is less than the absolute vacuum degree of the first vacuum melting is less than the absolute vacuum degree of the third vacuum melting; the absolute vacuum degree of the first vacuum melting is 70-150Pa; the absolute vacuum degree of the second vacuum melting is 0.005-0.009Pa; the absolute vacuum degree of the third vacuum melting is 250-350Pa;
the addition amount of the copper material in the second vacuum melting is more than the addition amount of the copper material in the third vacuum melting is more than the addition amount of the copper material in the first vacuum melting; the addition amount of the copper material in the first vacuum melting is 10-20% of the total amount of smelting copper; the addition amount of the copper material in the second vacuum melting is 50-60% of the total amount of smelting copper; the addition amount of copper materials in the third vacuum melting is 21-30% of the total amount of smelting copper;
the stationary refining comprises a first stationary and a second stationary which are sequentially carried out, wherein the temperature of the first stationary is 1080-1100 ℃, the time of the first stationary is 10-20min, the temperature of the second stationary is 1200-1300 ℃, and the vacuum degree of the second stationary is less than or equal to 6.7X10 -3 Pa, wherein the second standing time is 10-30min;
the temperature of the copper liquid during casting is 1200-1300 ℃; the mold vibration is the frequency of the mold vibration increasing as the casting proceeds.
According to the invention, the protective gas can be filled again before casting, the protective gas is used as a conduction medium to promote solidification of the cast ingot, shrinkage cavities are reduced, and the yield of the cast ingot is improved.
In the present invention, the shielding gas may be nitrogen and/or an inert gas, and the inert gas may be helium, neon, argon, or the like.
In the invention, the mode of the cold area after pouring is adopted by a cooling mode which is conventional in the field, such as air cooling, furnace cooling and the like.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method provided by the invention, the preparation of the ultra-high purity copper is realized by adopting a staged vacuum melting stage and adopting a multi-gradient vacuum melting process with obvious difference, and the volatile impurities in the copper liquid are removed, so that the purity of the obtained copper product is more than or equal to 99.9999%.
Detailed Description
For a better illustration of the present invention, which is convenient for understanding the technical solution of the present invention, exemplary but non-limiting examples of the present invention are as follows:
example 1
The embodiment provides a preparation method of ultra-high purity copper, which comprises the following steps: sequentially carrying out first vacuum melting, second vacuum melting and third vacuum melting after copper material filling, sequentially carrying out standing refining and pouring, vibrating a pouring die, and cooling and demoulding to obtain the ultra-high purity copper;
the absolute vacuum degree of the second vacuum melting is less than the absolute vacuum degree of the first vacuum melting is less than the absolute vacuum degree of the third vacuum melting; the absolute vacuum degree of the first vacuum melting is 90Pa; the absolute vacuum degree of the second vacuum melting is 0.007Pa; the absolute vacuum degree of the third vacuum melting is 280Pa;
the addition amount of the copper material in the second vacuum melting is more than the addition amount of the copper material in the third vacuum melting is more than the addition amount of the copper material in the first vacuum melting; the addition amount of the copper material in the first vacuum melting is 20% of the total amount of smelting copper; the addition amount of copper materials in the second vacuum melting is 52% of the total amount of smelting copper; the addition amount of copper materials in the third vacuum melting is 28% of the total amount of smelting copper;
the stationary refining comprises a first stationary and a second stationary which are sequentially carried out, wherein the temperature of the first stationary is 1090 ℃, the time of the first stationary is 15min, the temperature of the second stationary is 1280 ℃, and the vacuum degree of the second stationary is 3.7X10% -3 Pa, wherein the second standing time is 14min;
the temperature of the copper liquid during casting is 1280 ℃; the die vibration is that the frequency of the die vibration increases along with the casting, the casting vibration starts to be 0Hz, the adjustment vibration starts to be 50Hz after 5min, the adjustment vibration starts to be 100Hz after 10min, the adjustment vibration starts to be 150Hz after 15min, and the adjustment vibration starts to be 200Hz after 20min.
The purity of the copper product obtained is shown in Table 1.
Example 2
The embodiment provides a preparation method of ultra-high purity copper, which comprises the following steps: sequentially carrying out first vacuum melting, second vacuum melting and third vacuum melting after copper material filling, sequentially carrying out standing refining and pouring, vibrating a pouring die, and cooling and demoulding to obtain the ultra-high purity copper;
the absolute vacuum degree of the second vacuum melting is less than the absolute vacuum degree of the first vacuum melting is less than the absolute vacuum degree of the third vacuum melting; the absolute vacuum degree of the first vacuum melting is 70Pa; the absolute vacuum degree of the second vacuum melting is 0.005Pa; the absolute vacuum degree of the third vacuum melting is 350Pa;
the addition amount of the copper material in the second vacuum melting is more than the addition amount of the copper material in the third vacuum melting is more than the addition amount of the copper material in the first vacuum melting; the addition amount of the copper material in the first vacuum melting is 20% of the total amount of smelting copper; the addition amount of the copper material in the second vacuum melting is 50% of the total amount of smelting copper; the addition amount of copper materials in the third vacuum melting is 30% of the total amount of smelting copper;
the stationary refining comprises a first stationary and a second stationary which are sequentially carried out, wherein the temperature of the first stationary is 1080 ℃, the time of the first stationary is 10min, the temperature of the second stationary is 1200 ℃, and the vacuum degree of the second stationary is 2.7X10 -3 Pa, the second standing time is 30min;
the temperature of the copper liquid during casting is 1200 ℃; the vibration of the die is that the frequency of the vibration of the die increases along with the casting, the vibration of the die starts to be 0Hz, and the frequency of the vibration of the die increases by 10Hz every 1min of casting.
The purity of the copper product obtained is shown in Table 1.
Example 3
The embodiment provides a preparation method of ultra-high purity copper, which comprises the following steps: sequentially carrying out first vacuum melting, second vacuum melting and third vacuum melting after copper material filling, sequentially carrying out standing refining and pouring, vibrating a pouring die, and cooling and demoulding to obtain the ultra-high purity copper;
the absolute vacuum degree of the second vacuum melting is less than the absolute vacuum degree of the first vacuum melting is less than the absolute vacuum degree of the third vacuum melting; the absolute vacuum degree of the first vacuum melting is 150Pa; the absolute vacuum degree of the second vacuum melting is 0.009Pa; the absolute vacuum degree of the third vacuum melting is 250Pa;
the addition amount of the copper material in the second vacuum melting is more than the addition amount of the copper material in the third vacuum melting is more than the addition amount of the copper material in the first vacuum melting; the addition amount of the copper material in the first vacuum melting is 10% of the total amount of smelting copper; the addition amount of the copper material in the second vacuum melting is 60% of the total amount of smelting copper; the addition amount of copper materials in the third vacuum melting is 30% of the total amount of smelting copper;
the stationary refining comprises a first stationary and a second stationary which are sequentially carried out, wherein the temperature of the first stationary is 1100 ℃, the time of the first stationary is 20min, the temperature of the second stationary is 1300 ℃, and the vacuum degree of the second stationary is 6.7X10 -3 Pa, wherein the second standing time is 10min;
the temperature of the copper liquid during casting is 1280 ℃; the die vibration is that the frequency of the die vibration increases along with the casting, the casting vibration starts to be 0Hz, the adjustment vibration starts to be 50Hz after 5min, the adjustment vibration starts to be 100Hz after 10min, the adjustment vibration starts to be 150Hz after 15min, and the adjustment vibration starts to be 200Hz after 20min.
The purity of the copper product obtained is shown in Table 1.
Example 4
The embodiment provides a preparation method of ultra-high purity copper, which comprises the following steps: sequentially carrying out first vacuum melting, second vacuum melting and third vacuum melting after copper material filling, sequentially carrying out standing refining and pouring, vibrating a pouring die, and cooling and demoulding to obtain the ultra-high purity copper;
the absolute vacuum degree of the second vacuum melting is less than the absolute vacuum degree of the first vacuum melting is less than the absolute vacuum degree of the third vacuum melting; the absolute vacuum degree of the first vacuum melting is 120Pa; the absolute vacuum degree of the second vacuum melting is 0.008Pa; the absolute vacuum degree of the third vacuum melting is 310Pa;
the addition amount of the copper material in the second vacuum melting is more than the addition amount of the copper material in the third vacuum melting is more than the addition amount of the copper material in the first vacuum melting; the addition amount of the copper material in the first vacuum melting is 19% of the total amount of smelting copper; the addition amount of the copper material in the second vacuum melting is 60% of the total amount of smelting copper; the addition amount of copper materials in the third vacuum melting is 21% of the total amount of smelting copper;
the stationary refining comprises a first stationary and a second stationary which are sequentially carried out, wherein the temperature of the first stationary is 1085 ℃, the time of the first stationary is 17min, the temperature of the second stationary is 1250 ℃, and the vacuum degree of the second stationary is 6.7X10 -3 Pa, the second standing time is 25min;
the temperature of the copper liquid during casting is 1250 ℃; the vibration of the mould is that the frequency of the vibration of the mould increases along with the casting, the vibration of the casting is started to be 0Hz, and the vibration of the mould increases by 11Hz every 1 min.
The purity of the copper product obtained is shown in Table 1.
Example 5
The difference from example 1 is only that only the second vacuum melting, i.e. the total melting of the copper batch is carried out at a vacuum of 0.0079 Pa.
The purity of the copper product obtained is shown in Table 1.
Example 6
The only difference from example 1 is that the vacuum levels of the first vacuum melting and the second vacuum melting are exchanged.
The purity of the copper product obtained is shown in Table 1.
Example 7
The only difference from example 1 is that the vacuum levels of the first vacuum melting and the third vacuum melting are exchanged. That is, the degree of vacuum of the first vacuum melting at this time is 280Pa, and the degree of vacuum of the third vacuum melting is 90Pa.
The purity of the copper product obtained is shown in Table 1.
Example 8
The only difference from example 1 is that the vacuum levels of the second vacuum melting and the third vacuum melting are exchanged. That is, the second vacuum melting vacuum degree was 280Pa, and the third vacuum melting vacuum degree was 0.007Pa.
The purity of the copper product obtained is shown in Table 1.
Example 9
The difference from example 1 is only that the addition amounts of the copper materials for the second vacuum melting and the third vacuum melting were exchanged. Namely, the addition amount of the copper material melted in the second vacuum at this time was 28%, and the addition amount of the copper material melted in the third vacuum was 52%.
The purity of the copper product obtained is shown in Table 1.
Example 10
The difference from example 1 is only that the addition amounts of the copper materials for the first vacuum melting and the second vacuum melting were exchanged. Namely, the addition amount of the copper material melted in the first vacuum is 52% and the addition amount of the copper material melted in the second vacuum is 20%.
The purity of the copper product obtained is shown in Table 1.
TABLE 1
| Purity/% | |
| Example 1 | 99.99996 |
| Example 2 | 99.99998 |
| Example 3 | 99.99992 |
| Example 4 | 99.99991 |
| Example 5 | 99.99931 |
| Example 6 | 99.99923 |
| Example 7 | 99.99934 |
| Example 8 | 99.99911 |
| Example 9 | 99.99932 |
| Example 10 | 99.99923 |
In the present invention, the amount of the melted copper material and the casting speed were maintained the same in the above examples, and the casting time was controlled to be completed within 20 minutes, and the purity of the copper material used in examples 1 to 2 was 99.999% and the purity of the copper material used in examples 3 and 4 was 99.99%.
According to the embodiment, the specific stage vacuum melting process is adopted in the invention, so that the efficient preparation of the ultra-high purity copper is realized.
It is stated that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e., it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (16)
1. The preparation method of the ultra-high purity copper is characterized by comprising the following steps:
sequentially carrying out first vacuum melting, second vacuum melting and third vacuum melting after copper material filling, sequentially carrying out standing refining and pouring, vibrating a pouring die, and cooling and demoulding to obtain ultra-high purity copper;
the absolute vacuum degree of the second vacuum melting is less than the absolute vacuum degree of the first vacuum melting is less than the absolute vacuum degree of the third vacuum melting;
the addition amount of the copper material in the second vacuum melting is more than the addition amount of the copper material in the third vacuum melting is more than the addition amount of the copper material in the first vacuum melting;
the purity of the obtained copper product is more than or equal to 99.9999 percent.
2. The method of claim 1, wherein the absolute vacuum of the first vacuum melting is 70 to 150Pa.
3. The method of claim 1, wherein the copper charge is added to the first vacuum melt in an amount of 10-20% of the total amount of molten copper.
4. The method according to claim 1, wherein the absolute vacuum degree of the second vacuum melting is 0.005 to 0.009Pa.
5. The method of claim 1, wherein the copper charge is added to the second vacuum melt in an amount of 50-60% of the total amount of molten copper.
6. The method of claim 1, wherein the third vacuum melting has an absolute vacuum of 250 to 350Pa.
7. The method of claim 1, wherein the copper charge in the third vacuum melting is added in an amount of 21-30% of the total amount of melted copper.
8. The method of claim 1, wherein the stationary refining comprises a first stationary and a second stationary performed sequentially.
9. The method of claim 8, wherein the first resting temperature is 1080-1100 ℃.
10. The method of claim 8, wherein the first resting time is from 10 to 20 minutes.
11. The method of claim 8, wherein the second resting temperature is 1200-1300 ℃.
12. The method according to claim 8, wherein the second stationary state has a vacuum degree of 6.7X10 or less -3 Pa。
13. The method of claim 8, wherein the second resting time is 10 to 30 minutes.
14. The method according to claim 1, wherein the temperature of the copper liquid at the time of casting is 1200-1300 ℃.
15. The method of claim 1, wherein the mold vibration is an increasing frequency of mold vibration as casting proceeds.
16. The method of any one of claims 1-15, wherein the method of preparation comprises:
sequentially carrying out first vacuum melting, second vacuum melting and third vacuum melting after copper material filling, sequentially carrying out standing refining and pouring, vibrating a pouring die, and cooling and demoulding to obtain the ultra-high purity copper;
the absolute vacuum degree of the second vacuum melting is less than the absolute vacuum degree of the first vacuum melting is less than the absolute vacuum degree of the third vacuum melting; the absolute vacuum degree of the first vacuum melting is 70-150Pa; the absolute vacuum degree of the second vacuum melting is 0.005-0.009Pa; the absolute vacuum degree of the third vacuum melting is 250-350Pa;
the addition amount of the copper material in the second vacuum melting is more than the addition amount of the copper material in the third vacuum melting is more than the addition amount of the copper material in the first vacuum melting; the addition amount of the copper material in the first vacuum melting is 10-20% of the total amount of smelting copper; the addition amount of the copper material in the second vacuum melting is 50-60% of the total amount of smelting copper; the addition amount of copper materials in the third vacuum melting is 21-30% of the total amount of smelting copper;
the stationary refining comprises a first stationary and a second stationary which are sequentially carried out, wherein the temperature of the first stationary is 1080-1100 ℃, the time of the first stationary is 10-20min, the temperature of the second stationary is 1200-1300 ℃, and the vacuum degree of the second stationary is less than or equal to 6.7X10 -3 Pa, wherein the second standing time is 10-30min;
the temperature of the copper liquid during casting is 1200-1300 ℃; the mold vibration is the frequency of the mold vibration increasing as the casting proceeds.
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