CN113737011B - Preparation method of ultra-high purity copper-manganese alloy - Google Patents
Preparation method of ultra-high purity copper-manganese alloy Download PDFInfo
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- CN113737011B CN113737011B CN202111049759.5A CN202111049759A CN113737011B CN 113737011 B CN113737011 B CN 113737011B CN 202111049759 A CN202111049759 A CN 202111049759A CN 113737011 B CN113737011 B CN 113737011B
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- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 title claims abstract description 177
- 229910000914 Mn alloy Inorganic materials 0.000 title claims abstract description 173
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000010894 electron beam technology Methods 0.000 claims abstract description 110
- 238000002844 melting Methods 0.000 claims abstract description 75
- 230000008018 melting Effects 0.000 claims abstract description 75
- 238000003723 Smelting Methods 0.000 claims abstract description 69
- 239000011572 manganese Substances 0.000 claims abstract description 65
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000010949 copper Substances 0.000 claims abstract description 63
- 229910052802 copper Inorganic materials 0.000 claims abstract description 62
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 52
- 238000001513 hot isostatic pressing Methods 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000007670 refining Methods 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 30
- 238000005554 pickling Methods 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 241001062472 Stokellia anisodon Species 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 4
- 230000009977 dual effect Effects 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 31
- 229910052799 carbon Inorganic materials 0.000 abstract description 27
- 229910052751 metal Inorganic materials 0.000 abstract description 26
- 239000002184 metal Substances 0.000 abstract description 26
- 230000006698 induction Effects 0.000 abstract description 11
- 238000004544 sputter deposition Methods 0.000 abstract description 7
- 239000013077 target material Substances 0.000 abstract description 5
- 238000005406 washing Methods 0.000 abstract description 3
- 238000011112 process operation Methods 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 description 23
- 229910045601 alloy Inorganic materials 0.000 description 11
- 239000000956 alloy Substances 0.000 description 11
- 230000001276 controlling effect Effects 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 238000010309 melting process Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010308 vacuum induction melting process Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000011374 ultra-high-performance concrete Substances 0.000 description 1
- 238000003466 welding 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
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/16—Remelting metals
- C22B9/22—Remelting metals with heating by wave energy or particle radiation
- C22B9/228—Remelting metals with heating by wave energy or particle radiation by particle radiation, e.g. electron beams
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F3/15—Hot isostatic pressing
-
- 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
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/05—Alloys based on copper with manganese as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/103—Other heavy metals copper or alloys of copper
-
- 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
- Y02P10/25—Process efficiency
Abstract
The invention provides a preparation method of an ultra-high purity copper-manganese alloy, which adopts electron beam melting to prepare the ultra-high purity copper-manganese alloy and comprises the following steps: the ultra-high purity copper raw material and the manganese raw material are subjected to acid washing and mixing, then hot isostatic pressing is carried out to obtain an ultra-high purity copper-manganese alloy blank, and the blank is subjected to electron beam smelting and ingot drawing to obtain the ultra-high purity copper-manganese alloy. The preparation method adopts hot isostatic pressing to promote the uniform mixing of the raw materials and reduce the loss of metal in the electron beam smelting process; the double electron guns are used for smelting, so that the refining of the ultra-high purity copper-manganese alloy solution can be realized while the ultra-high purity copper-manganese alloy blank is smelted, and the process of dripping the molten blank into the water-cooled copper crucible plays a role in mixing, so that the ultra-high purity copper-manganese alloy is more uniform; compared with the traditional vacuum induction smelting, the inclusion of the ultra-high purity copper-manganese alloy carbon particles obtained by electron beam smelting is reduced, and the sputtering performance of the prepared target material in the sputtering process can be ensured to be stable; and has the advantages of simple process operation and wide applicability.
Description
Technical Field
The invention belongs to the field of manufacturing of ultra-high purity copper-manganese alloy targets, and particularly relates to a preparation method of an ultra-high purity copper-manganese alloy.
Background
With the rapid development of very large scale integrated circuits, the chip size for semiconductors has been reduced to the nanometer level, the RC delay and electromigration phenomenon of metal interconnect lines become main factors affecting the chip performance, and conventional aluminum and aluminum alloy interconnect lines have not been able to meet the requirements of the process of very large scale integrated circuits. Copper has higher electromigration resistance and higher electrical conductivity than aluminum, wherein copper having a purity of 6N or more is called ultra-high purity copper (Ultra High Purity Copper, UHPC) and has an impurity content of 1ppm or less and thus has a minimum grain boundary area and few internal lattice defects, so that ultra-high purity copper has excellent electromigration resistance, electrical conductivity, ductility, thermal conductivity, corrosion resistance and, in addition, has a lower recrystallization temperature. At present, ultra-high purity copper is widely applied to interconnection materials in ultra-large integrated circuits below 45nm technology nodes, and has important significance for reducing chip interconnection line resistance and improving operation speed.
However, under the process node of 14nm, the electromigration problem of ultra-high purity copper is serious, and an ultra-high purity copper-manganese alloy target material with the manganese content of 0.1-1 wt% is adopted as a seed layer in wiring at present, wherein Mn element can spontaneously face a substrate SiO 2 Forming a barrier layer by intermediate diffusion, thereby reducing Cu atoms in the copper wire to the substrate SiO 2 Diffusion is carried out, so that electromigration can be effectively reduced, and the service performance and service life of the semiconductor chip are ensured.
CN103667783a discloses a copper-manganese alloy and a preparation method thereof, wherein the copper-manganese alloy comprises the following components in percentage by weight: mn 11.2-12.4wt%, sc 0.2-0.3wt%, nb 0.1-0.2wt%, zr 0.05-0.10wt%, cs 0.05-0.10wt% and copper for the rest. The copper-manganese alloy is obtained through the steps of high-temperature secondary smelting, cooling and the like according to the composition of the components, and the prepared copper-manganese alloy has lower friction coefficient and higher heat conductivity coefficient.
CN108411151a discloses a vacuum induction melting method of copper-manganese intermediate alloy with high manganese content, which comprises the following steps: 1. placing copper and manganese into a crucible of a vacuum induction smelting furnace, vacuumizing for one time, and then preheating; 2. refining the preheated raw materials to obtain a copper-manganese alloy melt, and then filling argon as a protective gas for heating; 3. casting the heated copper-manganese alloy melt to form a copper-manganese intermediate alloy cast ingot; and fourthly, placing the copper-manganese intermediate alloy cast ingot on an alumina brick or alumina sand for air cooling to room temperature to obtain the copper-manganese intermediate alloy with high manganese content. According to the method, high-purity argon is filled into a vacuum induction smelting furnace in the preheating process of copper and manganese raw materials, so that gas adsorbed on the surfaces of raw materials copper and manganese is discharged and mixed with the argon, the oxygen partial pressure in the furnace is reduced, the phenomenon of oxidizing and slagging of manganese element in the smelting process is avoided, and the content of manganese element in the copper and manganese intermediate alloy is more than 30% and not more than 50%.
The conventional preparation process of the ultra-high purity copper-manganese alloy at present refers to a preparation method of the ultra-high purity copper, and vacuum induction smelting is mostly adopted to prepare the ultra-high purity copper-manganese alloy, but the preparation method has some problems. On one hand, mn element volatilizes, so that the alloy components are uneven; on the other hand, a high-purity graphite crucible is used in the vacuum induction melting process, and an alloy solution can wash the graphite crucible to cause carbon particles to be mixed in the alloy.
Therefore, it is necessary to find a preparation method of an ultra-high purity copper-manganese alloy which is simple to operate, can reduce volatilization of manganese element and does not introduce impurities.
Disclosure of Invention
The invention aims to provide a preparation method of an ultra-high purity copper-manganese alloy, which adopts electron beam melting to prepare the ultra-high purity copper-manganese alloy. Compared with the traditional vacuum induction smelting, the electron beam smelting can ensure that the inclusion of the obtained ultra-high purity copper-manganese alloy carbon particles is reduced, further ensure that the sputtering performance of the prepared target material is stable in the sputtering process, promote the uniform mixing of raw materials, reduce the metal loss in the electron beam smelting process, and have the advantages of simple technological operation and wide applicability.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the invention aims at providing a preparation method of an ultra-high purity copper-manganese alloy, which adopts electron beam melting to prepare the ultra-high purity copper-manganese alloy.
The electron beam melting (Electron Beam Melting, EBM) is a vacuum melting method for converting kinetic energy of high-speed electron beam current into heat energy under high vacuum as a heat source to perform metal melting, and the electron beam melting bombards the surface of a material by using the high-energy electron beam current, has the characteristics of high melting temperature, adjustable furnace power and heating speed and good product quality, and is not only used for melting and refining steel and rare metals, but also widely used for welding, ceramic material melting and the like.
The traditional preparation method of the ultra-high purity copper-manganese alloy is vacuum induction melting, mn element volatilizes in the vacuum induction melting process, so that the alloy components are uneven, and a high-purity graphite crucible is used to cause carbon particle impurities in the ultra-high purity copper-manganese alloy. The invention adopts electron beam melting to solve the problems of volatilization of Mn element and uneven alloy components, and avoids pollution of the crucible to the alloy because of using a water-cooled copper crucible during electron beam melting.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Mixing an ultra-high purity copper raw material and a manganese raw material, and performing static pressure to obtain an ultra-high purity copper-manganese alloy blank;
(2) And (3) smelting the ultra-high purity copper-manganese alloy blank in the step (1) by using an electron beam and leading ingots to obtain the ultra-high purity copper-manganese alloy.
As a preferable technical scheme of the invention, the ultra-high-purity copper raw material in the step (1) is an ultra-high-purity copper electrolytic sheet.
Preferably, the purity of the ultra-high purity copper raw material in the step (1) is greater than or equal to 99.9999wt%, and may be, for example, 99.9999wt%,99.99991wt%,99.99992wt%,99.99993wt%,99.99994wt%,99.99995wt%,99.99996wt%,99.99997wt%,99.99998wt%,99.99999wt%, etc., but is not limited to the recited values, and other non-recited values in the above-mentioned numerical ranges are equally applicable.
Preferably, the manganese raw material in the step (1) is a manganese electrolyte sheet.
Preferably, the purity of the manganese raw material in the step (1) is equal to or greater than 99.999wt%, and may be, for example, 99.999wt%,99.9992wt%,99.9994wt%,99.9995wt%,99.9996wt%,99.9998wt%,99.9999wt%,99.99992wt%, 99.995 wt%,99.99999wt%, etc., but is not limited to the recited values, and other non-recited values within the above-mentioned numerical ranges are equally applicable.
Preferably, the Mn content in the ultra-high purity copper-manganese alloy billet in step (1) is 0.1 to 1.0wt%, for example, 0.1wt%,0.2wt%,0.3wt%,0.4wt%,0.5wt%,0.6wt%,0.7wt%,0.8wt%,0.9wt%,1.0wt%, etc., but is not limited to the recited values, and other non-recited values within the above-mentioned range of values are equally applicable.
In the hot isostatic pressing process, only mixing and compression of raw materials occur, and the situation of raw material loss does not occur, namely, the ultra-high pure copper content in the ultra-high pure copper-manganese alloy blank is the proportion of the ultra-high pure copper raw material to the total raw material addition amount when the raw materials are added, and the Mn content in the ultra-high pure copper-manganese alloy blank is the proportion of the manganese raw material to the total raw material addition amount when the raw materials are added.
According to the preferred technical scheme, before the step (1) is carried out, the ultra-high purity copper raw material and the manganese raw material are subjected to acid washing, impurities on the surfaces of the raw materials can be removed through acid washing, and the purity of the ultra-high purity copper-manganese alloy prepared later is ensured.
Preferably, the pickling solution used for pickling is an aqueous solution of nitric acid.
Preferably, the concentration of the aqueous nitric acid solution is 28-32wt%, for example, 28wt%,28.5wt%,29wt%,29.5wt%,30wt%,30.5wt%,31wt%,31.5wt%,32wt%, but is not limited to the recited values, and other non-recited values within the above range are equally applicable.
As a preferable technical scheme of the invention, the static pressure mode in the step (1) is hot isostatic pressing.
According to the invention, the ultra-high-purity copper raw material and the manganese raw material are mixed by hot isostatic pressing, so that the mixing effect can be promoted, the mixing uniformity is increased, and in addition, the raw materials can be more tightly combined together by the hot isostatic pressing, so that the loss of metal in the subsequent electron beam melting process is reduced.
The temperature of the hot isostatic pressing is preferably 850-950 ℃, and may be 850 ℃,860 ℃,870 ℃,880 ℃,890 ℃,900 ℃,910 ℃,920 ℃,930 ℃,940 ℃,950 ℃, or the like, for example, but not limited to the values listed, and other values not listed in the above-mentioned numerical ranges are equally applicable.
The temperature of the hot isostatic pressing is controlled to 850-950 ℃, the melting point of copper is 1083.4 ℃, when the temperature of the hot isostatic pressing exceeds 950 ℃, the temperature is very close to the melting point of copper, and in addition, the temperature cannot be completely and accurately controlled in actual operation, some errors often exist, so that the state of the ultra-high purity copper is possibly changed, the strength is reduced, and the compactness of the ultra-high purity copper-manganese alloy blank is influenced; if the temperature of the hot isostatic pressing is lower than 850 ℃, the tightness of the ultra-high purity copper-manganese alloy blank is affected, and partial metal volatilizes in the subsequent electron beam melting process due to the insufficient tightness, so that the uniformity of the ultra-high purity copper-manganese alloy is affected.
The pressure of the hot isostatic pressing is preferably 180 to 200MPa, and may be 180MPa,182MPa,184MPa,186MPa,188MPa,190MPa,192MPa,194MPa,196MPa,198MPa,200MPa, etc., but is not limited to the values recited above, and other values not recited in the above-mentioned numerical ranges are equally applicable.
The pressure of the hot isostatic pressing is 180-200MPa, if the pressure is smaller than 180MPa, the tightness degree of the ultra-high purity copper-manganese alloy blank is insufficient, and further partial metal volatilizes in the electron beam melting process, so that the uniformity of the ultra-high purity copper-manganese alloy is poor; and the pressure of more than 200MPa is not realized by the prior instrument.
Preferably, the dwell time of the hot isostatic pressing is 5-6h, for example, 5h,5.1h,5.2h,5.3h,5.4h,5.5h,5.6h,5.7h,5.8h,5.9h,6h, etc., but not limited to the recited values, other non-recited values within the above-recited ranges are equally applicable.
The pressure maintaining time of the hot isostatic pressing is 5-6h, and if the pressure maintaining time is less than 5h, the tightness of the ultra-high purity copper-manganese alloy blank is poor, and finally the uniformity of the ultra-high purity copper-manganese alloy is poor; the dwell time does not need to exceed 6 hours, and the dwell time is 5-6 hours just can satisfy the demand of production, if the dwell time exceeds 6 hours, can increase the energy consumption, is unfavorable for industrial production.
Preferably, the ultra-high purity copper-manganese alloy billet in step (1) is cylindrical, has a diameter of 190-210mm and a height of 900-1100mm, for example, 190mm,192mm,194mm,196mm,198mm,200mm,202mm,204mm,206mm,208mm,210mm, etc., and has a height of 900mm,920mm,940mm,960mm, 900mm, 1000mm, 10200 mm,1040mm,1060mm,1080mm,1100mm, etc., but is not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
As a preferred embodiment of the present invention, the electron beam melting in step (2) is performed in an electron beam melting furnace.
Preferably, the ultra-high purity copper-manganese alloy blank in the step (1) is fixed right above a water-cooled copper crucible in an electron beam melting furnace before the electron beam melting in the step (2).
Preferably, after the ultra-high purity copper-manganese alloy blank in the step (1) is fixed, and before the electron beam melting in the step (2), the electron beam melting furnace is vacuumized.
As a preferable technical scheme of the invention, the electron beam melting in the step (2) uses a double electron gun for melting.
Preferably, a first electron gun of the double electron guns is used for melting the ultra-high purity copper-manganese alloy blank, and a second electron gun is used for refining the ultra-high purity copper-manganese alloy solution obtained by melting.
Preferably, the electron beam melting of the step (2) includes the following operations: and starting a first electron gun to smelt, and starting a second electron gun to refine when the ultra-high purity copper-manganese alloy blank starts to smelt and is dripped into the water-cooled copper crucible.
The invention utilizes the double electron guns to finish two processes of smelting and refining in the same equipment, and compared with the existing vacuum induction smelting process, the invention greatly simplifies the operation process, saves the operation time, and simultaneously can reduce the energy consumption in the whole process.
Preferably, the speed of the vertical downward ingot from the water-cooled copper crucible is 15-20mm/min, for example, 15mm/min,15.5mm/min,16mm/min,16.5mm/min,17mm/min,17.5mm/min,18mm/min,18.5mm/min,19mm/min,19.5mm/min,20mm/min, etc., but not limited to the listed values, and other non-listed values within the above range are equally applicable.
The invention controls the forming of the ultra-high purity copper-manganese alloy cast ingot by controlling the speed of the dummy ingot, the speed of the dummy ingot is preferably 15-20mm/min, if the speed of the dummy ingot is more than 20mm/min, namely the dummy ingot speed is too high, the ultra-high purity copper-manganese alloy solution is pulled out without complete solidification, and liquid leakage is caused; if the speed of the dummy ingot is less than 15mm/min, namely the dummy ingot speed is too slow, the ultra-high purity copper-manganese alloy solution can be cooled in the traction process, and the traction difficulty is increased.
The power of the first electron gun is preferably 80 to 120kW, for example, 80kW,85kW,90kW,95kW,100kW,105kW,110kW,115kW,120kW, etc., but not limited to the values listed, and other values not listed in the above-mentioned value range are equally applicable.
The power of the second electron gun is preferably 80-120kW, for example 80kW,85kW,90kW,95kW,100kW,105kW,110kW,115kW,120kW, etc., but not limited to the values listed, other values not listed in the above-mentioned value range are equally applicable.
According to the invention, the energy of the electron beam light spot emitted by the second electron gun is regulated by regulating the power of the second electron gun, so that the heating temperature of the ultra-high purity copper-manganese alloy solution in the water-cooled copper crucible can be regulated, the power of the second electron gun is 80-120kW, if the power of the second electron gun is higher than 120W, the temperature of the ultra-high purity copper-manganese alloy solution in the water-cooled copper crucible is overhigh, the ingot is required to be guided at a slower speed in the subsequent ingot guiding process, otherwise, the ultra-high purity copper-manganese alloy can be molded, the operation time is increased due to the too slow ingot guiding speed, the mass industrialized production is not facilitated, in addition, the volatilization and serious burning loss of metal materials in the ultra-high purity copper-manganese alloy solution are caused after the power of the second electron gun is higher than 120kW, and the metal loss in the ultra-high purity copper-manganese alloy is increased, and the yield is reduced; if the power of the second electron gun is lower than 80W, the temperature of the ultra-high purity copper-manganese alloy solution in the water-cooled copper crucible is too low, and the situation of premature cooling easily occurs in the subsequent ingot guiding process.
As the preferable technical scheme of the invention, the electron beam spot of the electron beam smelting in the step (2) is round, so that the ultra-high purity copper-manganese alloy blank and the ultra-high purity copper-manganese alloy solution are ensured to be heated uniformly and stably.
Preferably, the electron beam melting mode in the step (2) is vertical melting.
As a preferable technical scheme of the invention, the vacuum degree of the electron beam melting in the step (2) is 1 multiplied by 10 -4 -1×10 -3 Pa may be, for example, 1×10 -4 Pa，2×10 -4 Pa，3×10 -4 Pa，4×10 -4 Pa，5×10 -4 Pa，6×10 -4 Pa，7×10 - 4 Pa，8×10 -4 Pa，9×10 -4 Pa，1×10 -3 Pa, etc., but is not limited to the recited values, and other values not recited in the above-described numerical ranges are equally applicable.
The vacuum degree of the electron beam melting is controlled to be 1 multiplied by 10 -4 -1×10 -3 In the Pa range, if the vacuum degree is insufficient, elements such as sulfur, nitrogen and the like existing in the atmosphere pollute the melted ultra-high purity copper-manganese alloy solution, so that impurities exist in the obtained ultra-high purity copper-manganese alloy cast ingot, the stability of sputtering performance of a target material prepared subsequently is affected, in addition, the vacuum degree is related to the concentration degree of electron beam energy, and the insufficient vacuum degree can cause the insufficient concentration of electron beam energy, so that the melting of an ultra-high purity copper-manganese alloy blank and the refining of the ultra-high purity copper-manganese alloy solution are affected; the purity and uniformity of the ultra-high purity copper-manganese alloy cannot be affected due to the fact that the vacuum degree is too high, unnecessary energy consumption is caused, the production cost of the process is increased, and industrial application is not facilitated.
Preferably, the voltage of the electron beam melting in the step (2) is 25-45kV, for example, 25kV,27kV,30kV,32kV,34kV,36kV,38kV,40kV,43kV,45kV, etc., but the voltage is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical ranges are equally applicable.
Preferably, the current of the electron beam melting in the step (2) is 6-10A, for example, 6a,6.5a,7a,7.5a,8a,8.5a,9a,9.5a,10A, etc., but not limited to the listed values, and other non-listed values within the above-mentioned range are equally applicable.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Respectively pickling an ultra-high purity copper electrolytic sheet with the purity of more than or equal to 99.9999wt% and a manganese electrolytic sheet with the purity of more than or equal to 99.999wt% by adopting a nitric acid aqueous solution with the concentration of 28-32wt% as pickling solution, then mixing the two raw materials for hot isostatic pressing, controlling the temperature of the hot isostatic pressing to be 850-950 ℃, the pressure to be 180-200MPa, and the pressure maintaining time to be 5-6h to obtain an ultra-high purity copper-manganese alloy blank with the Mn content of 0.1-1.0wt%, wherein the ultra-high purity copper-manganese alloy blank is cylindrical with the diameter of 190-210mm and the height of 900-1100 mm;
(2) Fixing the ultra-high purity copper-manganese alloy blank in the step (1) above a water-cooled copper crucible in an electron beam melting furnace, and vacuumizing the electron beam melting furnace until the vacuum degree is 1 multiplied by 10 -4 -1×10 -3 Pa, carrying out electron beam smelting under the conditions of voltage 25-45kV and current 6-10A, controlling electron beam spots of the electron beam smelting to be round, and carrying out vertical smelting in the electron beam smelting mode, and then carrying out dummy ingot at the speed of 15-20mm/min to obtain the ultra-high purity copper-manganese alloy;
the electron beam smelting is carried out by using a double electron gun, wherein a first electron gun in the double electron gun is used for smelting the ultra-high purity copper-manganese alloy blank, a second electron gun is used for heating and smelting the obtained ultra-high purity copper-manganese alloy solution, when the electron beam smelting is carried out, the first electron gun is started and the power is gradually increased to 80-120kW for smelting, and when the ultra-high purity copper-manganese alloy blank starts to be molten and is dripped into a water-cooled copper crucible, the second electron gun is started and the power is adjusted to 80-120kW for refining.
The numerical ranges recited herein include not only the above-listed point values, but also any point values between the above-listed numerical ranges that are not listed, and are limited in space and for the sake of brevity, the present invention is not intended to be exhaustive of the specific point values that the stated ranges include.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the preparation method of the ultra-high purity copper-manganese alloy, the ultra-high purity copper-manganese alloy blank is prepared through hot isostatic pressing, so that on one hand, the uniform mixing of raw materials can be promoted, and on the other hand, the loss of metal in the electron beam melting process can be reduced;
(2) According to the preparation method of the ultra-high purity copper-manganese alloy, the double electron guns are used for smelting, the first electron gun is used for smelting an ultra-high purity copper-manganese alloy blank, the second electron gun is used for refining an ultra-high purity copper-manganese alloy solution which is smelted in the water-cooled copper crucible, the process of dripping the ultra-high purity copper-manganese alloy blank into the water-cooled copper crucible after smelting plays a role in mixing, and the obtained ultra-high purity copper-manganese alloy is more uniform;
(3) Compared with the traditional vacuum induction smelting, the ultra-high purity copper-manganese alloy prepared by adopting the electron beam smelting method has the advantages that carbon particles of the ultra-high purity copper-manganese alloy obtained by the electron beam smelting are greatly reduced in inclusion, and the sputtering performance of the prepared target material in the sputtering process is ensured to be stable;
(4) The ultra-high purity copper-manganese alloy obtained by the preparation method meets the requirement below a 14nm process node, and the preparation method is simple in process operation and wide in applicability.
Drawings
Fig. 1 is a schematic view of an electron beam melting furnace.
Wherein 1-a first electron gun; 2-a second electron gun; 3-ultra-high purity copper-manganese alloy blank; 4-ultra-high purity copper-manganese alloy solution; 5-water-cooling the copper crucible; 6-a viewing window; 7-a first electron beam; 8-a second electron beam; 9-a traction system; 10-vacuum pump system.
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.
It should be noted that, in the embodiments of the present invention, the electron beam melting furnace shown in fig. 1 is used to prepare the ultra-high purity copper-manganese alloy, and the thick arrow in fig. 1 indicates the flow direction of the cooling water.
Example 1
The embodiment provides a preparation method of an ultra-high purity copper-manganese alloy, which comprises the following steps:
(1) Respectively pickling an ultra-high purity copper electrolytic sheet with the purity of 99.9999wt% and a manganese electrolytic sheet with the purity of 99.999wt% by taking a nitric acid aqueous solution with the purity of 30wt% as pickling solutions, then mixing the two raw materials, performing hot isostatic pressing, controlling the temperature of the hot isostatic pressing to be 900 ℃, controlling the pressure to be 200MPa, and controlling the dwell time to be 5.5h to obtain an ultra-high purity copper-manganese alloy blank with the Mn content of 0.5wt%, wherein the ultra-high purity copper-manganese alloy blank is cylindrical with the diameter of 200mm and the height of 1000 mm;
(2) Fixing the ultra-high purity copper-manganese alloy blank in the step (1) above a water-cooled copper crucible in an electron beam melting furnace, and vacuumizing the electron beam melting furnace until the vacuum degree is 5 multiplied by 10 -4 Pa, carrying out electron beam smelting under the conditions of voltage 35kV and current 8A, controlling electron beam spots of the electron beam smelting to be round, and carrying out vertical smelting in the electron beam smelting mode, and then carrying out dummy ingot at the speed of 18mm/min to obtain the ultra-high purity copper-manganese alloy;
the electron beam smelting is carried out by using a double electron gun, wherein a first electron gun in the double electron gun is used for smelting the ultra-high purity copper-manganese alloy blank, a second electron gun is used for heating and smelting the obtained ultra-high purity copper-manganese alloy solution, when the electron beam smelting is carried out, the first electron gun is started and the power is gradually increased to 100kW for smelting, and when the ultra-high purity copper-manganese alloy blank starts to be molten and is dripped into a water-cooled copper crucible, the second electron gun is started and the power is adjusted to 100kW for refining.
Example 2
The embodiment provides a preparation method of an ultra-high purity copper-manganese alloy, which comprises the following steps:
(1) An ultra-high purity copper electrolyte sheet with the purity of 99.9999995 weight percent and a manganese electrolyte sheet with the purity of 99.9995 weight percent are respectively pickled by adopting a nitric acid aqueous solution with the purity of 32 weight percent as pickling solution, then the two raw materials are mixed and subjected to hot isostatic pressing, the temperature of the hot isostatic pressing is controlled to be 850 ℃, the pressure is 180MPa, the dwell time is 6 hours, an ultra-high purity copper-manganese alloy blank with the Mn content of 0.1 weight percent is obtained, and the ultra-high purity copper-manganese alloy blank is cylindrical with the diameter of 190mm and the height of 900 mm;
(2) Fixing the ultra-high purity copper-manganese alloy blank in the step (1) above a water-cooled copper crucible in an electron beam melting furnace, and vacuumizing the electron beam melting furnace until the vacuum degree is 1 multiplied by 10 -4 Pa, carrying out electron beam smelting under the conditions of voltage 25kV and current 6A, controlling electron beam spots of the electron beam smelting to be round, and carrying out vertical smelting in the electron beam smelting mode, and then carrying out dummy ingot at the speed of 20mm/min to obtain the ultra-high purity copper-manganese alloy;
the electron beam smelting is carried out by using a double electron gun, wherein a first electron gun in the double electron gun is used for smelting the ultra-high purity copper-manganese alloy blank, a second electron gun is used for heating and smelting the obtained ultra-high purity copper-manganese alloy solution, when the electron beam smelting is carried out, the first electron gun is started and the power is gradually increased to 80kW for smelting, and when the ultra-high purity copper-manganese alloy blank starts to be molten and is dripped into a water-cooled copper crucible, the second electron gun is started and the power is adjusted to 80kW for refining.
Example 3
The embodiment provides a preparation method of an ultra-high purity copper-manganese alloy, which comprises the following steps:
(1) Respectively pickling an ultra-high purity copper electrolytic piece with the purity of 99.99992wt% and a manganese electrolytic piece with the purity of 99.9995wt% by taking a nitric acid aqueous solution with the purity of 28wt% as pickling solutions, then mixing the two raw materials, performing hot isostatic pressing, controlling the temperature of the hot isostatic pressing to 950 ℃, controlling the pressure to 190MPa, and keeping the pressure for 5 hours to obtain an ultra-high purity copper-manganese alloy blank with the Mn content of 1.0wt%, wherein the ultra-high purity copper-manganese alloy blank is cylindrical with the diameter of 210mm and the height of 1100 mm;
(2) Fixing the ultra-high purity copper-manganese alloy blank in the step (1) above a water-cooled copper crucible in an electron beam melting furnace, and vacuumizing the electron beam melting furnace until the vacuum degree is 1 multiplied by 10 -3 Pa, carrying out electron beam smelting under the conditions of voltage 45kV and current 10A, controlling electron beam spots of the electron beam smelting to be round, and carrying out vertical smelting in the electron beam smelting mode, and then carrying out dummy ingot at the speed of 15mm/min to obtain the ultra-high purity copper-manganese alloy;
the electron beam smelting is carried out by using a double electron gun, wherein a first electron gun in the double electron gun is used for smelting the ultra-high purity copper-manganese alloy blank, a second electron gun is used for heating and smelting the obtained ultra-high purity copper-manganese alloy solution, when the electron beam smelting is carried out, the first electron gun is started and the power is gradually increased to 120kW for smelting, and when the ultra-high purity copper-manganese alloy blank starts to be molten and is dripped into a water-cooled copper crucible, the second electron gun is started and the power is adjusted to 120kW for refining.
Example 4
This example provides a method for preparing an ultra-high purity copper-manganese alloy, and the conditions are exactly the same as in example 1, except that the temperature of the hot isostatic pressing in step (1) is changed to 800 ℃.
Example 5
This example provides a method for preparing an ultra-high purity copper-manganese alloy, and the conditions are exactly the same as in example 1, except that the temperature of the hot isostatic pressing in step (1) is changed to 1000 ℃.
Example 6
This example provides a method for preparing an ultra-high purity copper-manganese alloy, and the conditions are exactly the same as in example 1, except that the pressure of the hot isostatic pressing in step (1) is replaced by 170MPa with 200 MPa.
Example 7
This example provides a method for preparing an ultra-high purity copper-manganese alloy, and the conditions are exactly the same as in example 1, except that the dwell time of the hot isostatic pressing in step (1) is replaced by 4h, which is 5.5 h.
Example 8
This example provides a method for preparing an ultra-high purity copper-manganese alloy, and the conditions are exactly the same as in example 1, except that the dwell time of the hot isostatic pressing in step (1) is replaced by 7h, which is 5.5 h.
Example 9
The embodiment provides a method for preparing an ultra-high purity copper-manganese alloy except that the electron beam melting in the step (2) is performed at a vacuum degree of 5×10 -4 Pa is replaced by 1×10 -5 Pa, other conditions were exactly the same as in example 1.
Example 10
The embodiment provides a method for preparing an ultra-high purity copper-manganese alloy except that the electron beam melting in the step (2) is performed at a vacuum degree of 5×10 -4 Pa is replaced by 3×10 -3 Pa, other conditions were exactly the same as in example 1.
Example 11
The present example provides a method for preparing an ultra-high purity copper-manganese alloy, and the conditions are exactly the same as in example 1 except that the power of the electron gun in the electron beam melting in step (2) is replaced by 70kW with 100 kW.
Example 12
The present example provides a method for preparing an ultra-high purity copper-manganese alloy, and the conditions are exactly the same as in example 1 except that 100kW of the power of the second electron gun in the electron beam melting in step (2) is replaced by 130 kW.
Comparative example 1
This comparative example provides a method for preparing an ultra-high purity copper-manganese alloy by vacuum induction melting, which is described in CN111534708B, according to the raw material formulation described in example 1.
The purity of the ultra-high-purity copper electrolyte sheet and the manganese electrolyte sheet used in the preparation process of the ultra-high-purity copper-manganese alloy cannot reach 100%, other metal impurities and carbon impurities inevitably exist, but the influence of a small amount of carbon on the subsequent application of the ultra-high-purity copper-manganese alloy is small, and in actual use, the number of carbon particles with the particle size of more than or equal to 1.3 mu m is required to be less than or equal to 5000 carbon particles per gram. The ultra-high purity copper-manganese alloy obtained in the above examples and comparative examples is characterized by the manganese content, the metal impurity content and the number of carbon particles with the particle diameter of not less than 1.3 μm, and the characterization method is as follows:
manganese content: detecting the manganese content in the ultra-high purity copper-manganese alloy by utilizing an inductively coupled plasma emission spectrometer (ICP-OES); during characterization, sampling from different positions of the ultra-high purity copper-manganese alloy, testing the manganese content of the ultra-high purity copper-manganese alloy, if the manganese content of each position is consistent, considering that the manganese element in the ultra-high purity copper-manganese alloy is uniformly distributed, and if the manganese content of each position is inconsistent, considering that the manganese element in the ultra-high purity copper-manganese alloy is unevenly distributed;
metal impurity content: detecting the content of metal impurities except manganese in the ultra-high purity copper-manganese alloy by utilizing a Glow Discharge Mass Spectrometry (GDMS);
the number of carbon particles with the particle diameter of more than or equal to 1.3 mu m: and detecting the number of carbon particles with the particle size of more than or equal to 1.3 mu m in each gram of ultra-high purity copper-manganese alloy by using an insoluble particle detector (LPC).
The loss of the manganese element can be obtained through calculation in the following manner:
manganese loss amount= (manganese content in ultra-high purity copper-manganese alloy blank-manganese content in ultra-high purity copper-manganese alloy)/(manganese content in 1-ultra-high purity copper-manganese alloy);
because the loss of manganese is very small and the influence on the ratio of the total components is very small, the difference between the manganese content in the ultra-high purity copper-manganese alloy blank and the manganese content in the ultra-high purity copper-manganese alloy is taken as the loss of manganese, namely, the loss of manganese=the manganese content in the ultra-high purity copper-manganese alloy blank-the manganese content in the ultra-high purity copper-manganese alloy.
The test results of the manganese content, the manganese loss amount, the metal impurity content and the number of carbon particles with the particle diameter of not less than 1.3 μm in the ultra-high purity copper-manganese alloy obtained in the above examples and comparative examples are shown in Table 1.
TABLE 1
From table 1, the following points can be found:
(1) As can be seen from examples 1-3, the preparation method of the ultra-high purity copper-manganese alloy combines hot isostatic pressing and electron beam melting, the prepared ultra-high purity copper-manganese alloy cast ingot has little manganese element loss, low metal impurity content which is less than or equal to 0.3ppm, greatly reduced carbon particle inclusion, and the number of carbon particles with the particle diameter of more than or equal to 1.3 mu m which is less than or equal to 4500/g;
(2) Comparing example 1 with examples 4 and 5, since the hot isostatic pressing temperature in step (1) in example 4 is 800 ℃ which is lower than the preferred 850-950 ℃ of the invention, the ultra-high purity copper-manganese alloy blank is not tight enough, the manganese loss amount is increased from 0.001wt% to 0.179wt%, the elements in the ultra-high purity copper-manganese alloy are unevenly distributed, the metal impurity content is increased from 0.20ppm to 0.81ppm, and the number of carbon particles with the particle diameter of more than or equal to 1.3 μm is increased from 3500 to 4800 carbon particles per gram; since the temperature of the hot isostatic pressing in the step (1) in the example 5 is 1000 ℃ which exceeds the preferred 850-950 ℃ of the invention, and the temperature is too high, which is very close to the melting point 1083.4 ℃ of copper, the strength of the ultra-high purity copper becomes small, so that the ultra-high purity copper-manganese alloy blank is not compact enough, the manganese loss amount is increased from 0.001 to 0.240 weight percent, the distribution of each element in the ultra-high purity copper-manganese alloy is uneven, the metal impurity content is increased from 0.20 to 0.56ppm, and the number of carbon particles with the particle diameter of more than or equal to 1.3 mu m is increased from 3500 to 4650/g;
(3) Comparing example 1 with example 6, since the pressure of the hot isostatic pressing in the step (1) in example 6 is 170MPa, which is lower than the preferred 180-200MPa in the present invention, the tightness of the ultra-high purity copper-manganese alloy billet is insufficient, and the manganese loss amount in the electron beam melting process is increased from 0.001wt% to 0.199wt%, the uniformity of the ultra-high purity copper-manganese alloy is deteriorated, the metal impurity content is increased from 0.20ppm to 0.82ppm, and the number of carbon particles with the particle diameter of not less than 1.3 μm is increased from 3500 to 4680/g;
(4) Comparing example 1 with examples 7 and 8, since the dwell time of the hot isostatic pressing in step (1) of example 7 is 4 hours, which is lower than the preferred 5-6 hours of the present invention, the tightness of the ultra-high purity copper-manganese alloy billet is deteriorated, the manganese loss is increased from 0.001wt% to 0.140wt%, the metal impurity content is increased from 0.20ppm to 0.88ppm, and the number of carbon particles with a particle diameter of 1.3 μm or more is increased from 3500 to 4710/g; because the pressure maintaining time of the hot isostatic pressing in the step (1) in the implementation 8 is 7 hours, although the pressure maintaining time exceeds the preferable 5-6 hours of the invention, the tightness degree of the ultra-high purity copper-manganese alloy blank is not affected, the manganese loss is still 0.001wt%, the metal impurity content is unchanged, the number of carbon particles with the particle diameter of more than or equal to 1.3 mu m is slightly increased, therefore, the property of the ultra-high purity copper-manganese alloy prepared by increasing the pressure maintaining time of the hot isostatic pressing is not obviously improved, and the energy consumption is increased;
(5) Comparing example 1 with examples 9 and 10, the vacuum degree of electron beam melting in step (2) in example 9 was 1×10 -5 Pa, more than 1X 10 preferred in the present invention -4 -1×10 -3 The Pa range, namely the vacuum degree is too high, the influence on the ultra-high purity copper-manganese alloy is small, the manganese loss is still 0.001wt%, the metal impurity content is unchanged, and the number of carbon particles with the particle diameter of more than or equal to 1.3 mu m is slightly increased; since the electron beam melting of step (2) in the embodiment 10 is performed at a vacuum level of 3X 10 -3 Pa, more than 1X 10 preferred in the present invention -4 -1×10 -3 The Pa range, namely the vacuum degree is insufficient, so that impurities in the ultra-high purity copper-manganese alloy are increased, the manganese loss is increased from 0.001wt% to 0.068wt%, the metal impurity content is increased from 0.20ppm to 0.89ppm, and the number of carbon particles with the particle diameter of more than or equal to 1.3 mu m is increased from 3500 pieces/g to 4930 pieces/g; therefore, the ultra-high purity copper-manganese alloy cannot be more uniform due to the overlarge vacuum degree, and only the energy consumption is increased;
(6) Comparing example 1 with examples 11 and 12, since the power of the second electron gun in the electron beam melting of step (2) in example 11 is 70kW, which is lower than the preferred range of 80-120kW of the present invention, the manganese loss amount is increased from 0.001wt% to 0.185wt%, the metal impurity content is increased from 0.20ppm to 0.68ppm, and the number of carbon particles having a particle diameter of 1.3 μm or more is increased from 3500 to 4580/g; since the power of the second electron gun in the electron beam melting of the step (2) in the implementation 12 is 130kW, which exceeds the preferred range of 80-120kW in the invention, the manganese loss amount is increased from 0.001wt% to 0.288wt%, the metal impurity content is increased from 0.20ppm to 0.89ppm, and the number of carbon particles with the particle diameter of more than or equal to 1.3 μm is increased from 3500 to 4930 particles/g;
(7) Comparing example 1 with comparative example 1, the ultra-high purity copper-manganese alloy prepared by vacuum induction melting as described in CN111534708B is better in uniformity, less in manganese loss and less in metal impurity content, but the high-temperature ultra-high purity copper-manganese alloy solution flushing the high-purity graphite crucible in the preparation process can cause a large amount of carbon particles in the ultra-high purity copper-manganese alloy, the number of the carbon particles with the particle size of more than or equal to 1.3 mu m is 43922/g, and the requirement of less than or equal to 5000/g in the actual use process is far exceeded.
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 (19)
1. The preparation method of the ultra-high purity copper-manganese alloy is characterized in that the ultra-high purity copper-manganese alloy is prepared by adopting electron beam melting;
the preparation method comprises the following steps:
(1) Mixing an ultra-high purity copper raw material and a manganese raw material, and performing static pressure to obtain an ultra-high purity copper-manganese alloy blank;
(2) The ultra-high purity copper-manganese alloy blank in the step (1) is subjected to electron beam smelting and ingot guiding to obtain the ultra-high purity copper-manganese alloy;
the ultra-high-purity copper raw material in the step (1) is an ultra-high-purity copper electrolytic sheet;
the purity of the ultra-high purity copper raw material in the step (1) is more than or equal to 99.999999wt%;
the manganese raw material in the step (1) is a manganese electrolyte sheet;
the purity of the manganese raw material in the step (1) is more than or equal to 99.999 weight percent;
the Mn content in the ultra-high purity copper-manganese alloy blank in the step (1) is 0.1-1.0wt%;
the static pressure mode in the step (1) is hot isostatic pressing;
the temperature of the hot isostatic pressing is 850-950 ℃;
the pressure of the hot isostatic pressing is 180-200MPa;
the pressure maintaining time of the hot isostatic pressing is 5-6h;
the ultra-high purity copper-manganese alloy blank in the step (1) is cylindrical, the diameter is 190-210mm, and the height is 900-1100mm.
2. The method of claim 1, wherein the ultra-high purity copper feedstock and manganese feedstock are acid washed prior to the mixing of step (1).
3. The method according to claim 2, wherein the pickling solution used for pickling is an aqueous nitric acid solution.
4. The method according to claim 3, wherein the aqueous nitric acid solution has a concentration of 28 to 32wt%.
5. The method of claim 1, wherein the electron beam melting of step (2) is performed in an electron beam melting furnace.
6. The method of claim 5, wherein the ultra-high purity copper-manganese alloy billet of step (1) is fixed directly above a water-cooled copper crucible in an electron beam melting furnace prior to the electron beam melting of step (2).
7. The method of manufacturing according to claim 6, wherein the electron beam melting furnace is evacuated after the ultra-high purity copper-manganese alloy billet is fixed in step (1) and before the electron beam melting in step (2).
8. The method of claim 6, wherein the electron beam melting of step (2) is performed using a twin electron gun.
9. The method of claim 8, wherein a first electron gun of said dual electron gun is used to melt said ultra-high purity copper-manganese alloy billet and a second electron gun is used to refine the ultra-high purity copper-manganese alloy solution obtained by melting.
10. The method of claim 9, wherein the electron beam melting of step (2) comprises the steps of: and starting a first electron gun to smelt, and starting a second electron gun to refine when the ultra-high purity copper-manganese alloy blank starts to smelt and is dripped into the water-cooled copper crucible.
11. The method of claim 10, wherein the rate of vertical downward ingot pulling from the water cooled copper crucible is 15-20mm/min.
12. The method of claim 10, wherein the first electron gun has a power of 80kW to 120kW.
13. The method of claim 10, wherein the second electron gun has a power of 80kW to 120kW.
14. The method of claim 1, wherein the electron beam spot of the electron beam melting in step (2) is circular.
15. The method of claim 1, wherein the electron beam melting in step (2) is performed by vertical melting.
16. The method according to claim 1, wherein the electron beam melting in the step (2) is performed under a vacuum of 1X 10 -4 -1×10 -3 Pa。
17. The method of claim 1, wherein the electron beam melting in step (2) is performed at a voltage of 25-45kV.
18. The method of claim 1, wherein the electron beam melting current in step (2) is from 6 to 10A.
19. The preparation method according to claim 1, characterized in that the preparation method comprises the steps of:
(1) Respectively pickling an ultra-high purity copper electrolytic sheet with the purity of more than or equal to 99.9999wt% and a manganese electrolytic sheet with the purity of more than or equal to 99.999wt% by adopting a nitric acid aqueous solution with the concentration of 28-32wt% as pickling solution, then mixing the two raw materials for hot isostatic pressing, controlling the temperature of the hot isostatic pressing to be 850-950 ℃, the pressure to be 180-200MPa, and the pressure maintaining time to be 5-6h to obtain an ultra-high purity copper-manganese alloy blank with the Mn content of 0.1-1.0wt%, wherein the ultra-high purity copper-manganese alloy blank is cylindrical with the diameter of 190-210mm and the height of 900-1100 mm;
(2) Fixing the ultra-high purity copper-manganese alloy blank in the step (1) above a water-cooled copper crucible in an electron beam melting furnace, and vacuumizing the electron beam melting furnace until the vacuum degree is 1 multiplied by 10 -4 -1×10 -3 Pa, carrying out electron beam smelting under the conditions of voltage 25-45kV and current 6-10A, controlling electron beam spots of the electron beam smelting to be round, and carrying out vertical smelting in the electron beam smelting mode, and then carrying out dummy ingot at the speed of 15-20mm/min to obtain the ultra-high purity copper-manganese alloy;
the electron beam smelting is carried out by using a double electron gun, wherein a first electron gun in the double electron gun is used for smelting the ultra-high purity copper-manganese alloy blank, a second electron gun is used for heating and smelting the obtained ultra-high purity copper-manganese alloy solution, when the electron beam smelting is carried out, the first electron gun is started and the power is gradually increased to 80-120kW for smelting, and when the ultra-high purity copper-manganese alloy blank starts to be molten and is dripped into a water-cooled copper crucible, the second electron gun is started and the power is adjusted to 80-120kW for refining.
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