CN106756174A - A kind of densification process of high-quality chromiumcopper - Google Patents
A kind of densification process of high-quality chromiumcopper Download PDFInfo
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- CN106756174A CN106756174A CN201611178552.7A CN201611178552A CN106756174A CN 106756174 A CN106756174 A CN 106756174A CN 201611178552 A CN201611178552 A CN 201611178552A CN 106756174 A CN106756174 A CN 106756174A
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- 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
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- 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
- B22F3/17—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
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- 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
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- 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
- B22F3/17—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging
- B22F2003/175—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging by hot forging, below sintering temperature
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- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- 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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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Abstract
The invention provides a kind of high-quality chromiumcopper densification process, the technique is with chromium powder, copper powder and graphite powder as raw material, raw material is sequentially passed through into dispensing, Vacuum Mixture and vacuum debulk, obtain cylinder blank, the relative density of cylinder blank is 80%~90%, then cylinder blank is carried out into vacuum-sintering and obtains CuCr sintered samples, CuCr sintered samples are finally carried out into densification of swaging, obtain high-quality chromiumcopper.Technique of the invention is with chromium powder, copper powder and graphite powder as raw material, the process integration of densification of swaging is combined using vacuum Relative compaction, vacuum-sintering, make alloy structure entirely fine and close, and oxygen content is low, the utilization rate of material is higher simultaneously, solves the contradiction existed between alloy structure consistency and oxygen content；By adjusting dispensing, different Cr contents, difference Cr chromium crystallite dimension, the serial CuCr alloy materials of different-diameter specification can be produced.
Description
Technical field
The invention belongs to high-voltage appliance switch contact material field, it is related to copper-chromium contact material, and in particular to a kind of Gao Pin
The densification process of matter chromiumcopper.
Background technology
CuCr alloys are a kind of novel contact materials for being widely used in vacuum circuit breaker.Due to two kinds of constituent element density of Cu, Cr,
The physical properties such as fusing point are differed greatly so that the extremely difficult conventional casting of CuCr alloys is produced, and fine grain low oxygen content CuCr is touched
The preparation of head has great difficulty.Low gas and impurity content, it is ensured that vacuum circuit breaker will not be because of putting in interrupting process
Gas causes arc reignition and melting welding.Cr particle sizes are as tiny as possible, are evenly distributed.Ensureing will not be because of Cr in interrupting process
Skewness excessive cause arc energy aggregation causes the excessive ablation of contact surface and melting welding and causes and cut-off mistake at chromium-rich place
Lose.
The method that current powder metallurgy produces copper chromium system contact alloy, mainly there is following several：
Powder mixing method, infiltration method, vacuum melting method and consumable method, wherein powder mixing method are a kind of traditional widely used sides
Method, this method is to be sufficiently mixed a certain proportion of Cu powder and Cr powder, cold moudling, then through vacuum-sintering or high temperature insostatic pressing (HIP)
Into the advantage of powder mixing method is process is simple, and maturity is high, has the disadvantage there are extremely strict requirements to raw gas content, very
Hardly possible obtains the product of low-gas content, and it is also an important shortcoming that consistency is relatively low.
Every kind of preparation method has its advantage and disadvantage, it can be seen that current powder metallurgy produces copper chromium system contact alloy
The advantage of method substantially, the grain size of Cr contents and Cr is changed by dispensing, and the copper chromium that can prepare various different sizes is closed
Golden product, but it significantly has the disadvantage that consistency is low, it is difficult to obtain the product of low-gas content.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the present invention to provide a kind of densification of high-quality chromiumcopper
Chemical industry skill, to obtain the contact material of chrome copper alloy of high-performance, low-gas content and low field trash.
In order to solve the above-mentioned technical problem, the present invention is adopted the following technical scheme that and is achieved：
A kind of high-quality chromiumcopper densification process, the technique with chromium powder, copper powder and graphite powder as raw material, by raw material according to
It is secondary to obtain cylinder blank by dispensing, Vacuum Mixture and vacuum Relative compaction, the relative density of cylinder blank for 80%~
90%, cylinder blank is then carried out into vacuum-sintering and obtains CuCr sintered samples, finally CuCr sintered samples are swaged
Densification, obtains high-quality chromiumcopper.
The present invention also has following distinguishing feature：
The relative density of described cylinder blank is 85%~90%.
The technique is specifically followed the steps below：
Step one, dispensing：
Chromium powder, copper powder and graphite powder are carried out into dispensing, preliminary mixed-powder is obtained；
In described preliminary mixed-powder, in terms of parts by weight, the ratio of chromium powder and copper powder is (1.5~50)：(50~
98.5), chromium powder and the parts by weight sum of copper powder are 100 parts；The addition of graphite powder is chromium powder and copper powder gross mass
0.1%~0.3%；
Step 2, Vacuum Mixture：、
Preliminary mixed-powder is fitted into batch mixing machine jar body, is then vacuumized, pour inert gas, in inert gas shielding
Lower use three-dimensional mixer rotates 3~4h of mixing to preliminary mixed-powder three-dimensional, obtains mixed-powder；
Step 3, vacuum Relative compaction：
Mixed-powder is put into vacuum in mould and is pressed into cylinder blank, the relative density of cylinder blank for 80%~
90%；
Step 4, vacuum-sintering：
Cylinder blank is put into crucible, vacuum-sintering is carried out, furnace pressure≤6.5 × 10 are first evacuated to-3Pa, so
Reheat afterwards and be warming up to 980 DEG C~1050 DEG C, be incubated 2~4h, cool to room temperature with the furnace and take out CuCr sintered samples；
Step 5, densification of swaging：
CuCr sintered samples are heated to 800~850 DEG C in batch-type furnace, 0.5~1h is incubated, being put into swager is carried out
Forge until reach diameter specifications size, last thermally treated, cutting, machine adds and obtains high-quality chromiumcopper.
Preferably, in step one, in described preliminary mixed-powder, in terms of parts by weight, the ratio of chromium powder and copper powder is (15
~50)：(50~85), chromium powder is 100 parts with the parts by weight sum of copper powder；The addition of graphite powder is chromium powder and the total matter of copper powder
The 0.2%~0.3% of amount.
Specifically, in step 2, the pressure≤10Pa in batch mixing machine jar body, then it is that argon gas or helium are arrived to pour inert gas
1 atmospheric pressure.
Specifically, in step 3, in order to realize that vacuum is suppressed, pressure≤6.5 × 10 in the corresponding mould of vacuum environment- 2Pa。
Preferably, in step 3, vacuum is pressed into cylinder blank during mixed-powder is put into mould, cylinder blank
Relative density is 85%~90%.
Specifically, in step 5, the single decrement in CuCr sintered samples cross section is less than 15%~20%, mould when swaging
Tool cycle is 1500~3000 times per minute, and the feed rate of CuCr sintered samples is 1000mm/min.
The present invention compared with prior art, has the following technical effect that：
Technique of the invention combines rotation with chromium powder, copper powder and graphite powder as raw material using vacuum Relative compaction, vacuum-sintering
The process integration of densification is forged, makes alloy structure entirely fine and close, and oxygen content is low, while the utilization rate of material is higher, solves conjunction
The contradiction existed between payment organization consistency and oxygen content；By adjusting dispensing, different Cr contents, difference Cr chromium can be produced brilliant
The serial CuCr alloy materials of particle size, different-diameter specification.
During vacuum Relative compaction, the relative density of cylinder blank is 80%~90%, and relative density can not mistake
Height can not be too low, too high, and gas is difficult to exclude in follow-up densification process of swaging, too low, can be to follow-up vacuum-sintering
Densification process is impacted with swaging, and causes the consistency of final products not high.
Brief description of the drawings
Fig. 1 is process flow diagram of the invention.
Fig. 2 is principle schematic of swaging.
Explanation is further explained in detail to particular content of the invention with reference to embodiments.
Specific embodiment
Swage i.e. swaging.Loose porous sintered state bar stock is processed into the densification gold with some strength of densification
The deformation process of category, it is that polylith hammers mould into shape while being rotated at a high speed around the longitudinal axis to swage, and the forging of high-speed high frequency rate is carried out to forging stock
Beat (as shown in Figure 2).Swage processing had concurrently in technique it is multidirectional forge the characteristics of being forged with pulse, forging is made by three-dimensional compressive stress
With the process for making blank be axially extended by radial compression.
Specific embodiment of the invention given below is, it is necessary to explanation is the invention is not limited in implementing in detail below
Example, all equivalents done on the basis of technical scheme each fall within protection scope of the present invention.
Embodiment 1：CuCr15 alloy preparation technologies
The present embodiment provides a kind of high-quality chromiumcopper densification process, as shown in figure 1, the technique is specifically according to following
Step is carried out：
Step one, dispensing：
Chromium powder (particle diameter≤60 μm, oxygen content≤2000ppm), electrolytic copper powder (particle diameter≤40 μm, oxygen content≤
1200ppm), graphite (C) powder (particle diameter≤40 μm).
Chromium powder, copper powder and graphite powder are carried out into dispensing, preliminary mixed-powder is obtained；
In described preliminary mixed-powder, in terms of parts by weight, the ratio of chromium powder and copper powder is 15：85, chromium powder and copper powder
Parts by weight sum is 100 parts, and the addition of graphite powder is chromium powder and the 0.2% of copper powder gross mass；
Step 2, Vacuum Mixture：、
Preliminary mixed-powder is fitted into batch mixing machine jar body, is then vacuumized, pour inert gas, in inert gas shielding
Lower use three-dimensional mixer rotates mixing 3h to preliminary mixed-powder three-dimensional, obtains mixed-powder；Pressure in batch mixing machine jar body
≤ 10Pa, then it is argon gas to 1 atmospheric pressure to pour inert gas.
Step 3, vacuum Relative compaction：
Vacuum is pressed into cylinder blank during mixed-powder is put into mould, and the relative density of cylinder blank is 85%；
In order to realize that vacuum is suppressed, pressure≤6.5 × 10 in the corresponding mould of vacuum environment-2Pa。
Step 4, vacuum-sintering：
Cylinder blank is put into crucible, vacuum-sintering is carried out, furnace pressure≤6.5 × 10 are first evacuated to-3Pa, so
Reheat afterwards and be warming up to 980 DEG C, be incubated 4h, cool to room temperature with the furnace and take out CuCr sintered samples；
Step 5, densification of swaging：
CuCr sintered samples are heated to 800 DEG C in batch-type furnace, 1h is incubated, being put into swager forge until reaching
Last thermally treated to diameter specifications size, cutting, machine adds and obtains high-quality chromiumcopper CuCr15 alloys；
The single decrement in CuCr sintered samples cross section is less than 15% when swaging, and mould cycle is per minute 1500
Secondary, the feed rate of CuCr sintered samples is 1000mm/min.
CuCr15 alloy materials are prepared by test, oxygen content in material<200ppm, nitrogen content<10ppm, carbon content<
60ppm, relative density 100% (complete fine and close), hardness HB>68, electrical conductivity>40Ms/m.
Embodiment 2：CuCr50 alloy preparation technologies
The present embodiment provides a kind of high-quality chromiumcopper densification process, as shown in figure 1, the technique is specifically according to following
Step is carried out：
Step one, dispensing：
Chromium powder (particle diameter≤60 μm, oxygen content≤2000ppm), electrolytic copper powder (particle diameter≤40 μm, oxygen content≤
1200ppm), graphite (C) powder (particle diameter≤40 μm).
Chromium powder, copper powder and graphite powder are carried out into dispensing, preliminary mixed-powder is obtained；
In described preliminary mixed-powder, in terms of parts by weight, the ratio of chromium powder and copper powder is 50：50, chromium powder and copper powder
Parts by weight sum is 100 parts, and the addition of graphite powder is chromium powder and the 0.3% of copper powder gross mass；
Step 2, Vacuum Mixture：、
Preliminary mixed-powder is fitted into batch mixing machine jar body, is then vacuumized, pour inert gas, in inert gas shielding
Lower use three-dimensional mixer rotates mixing 4h to preliminary mixed-powder three-dimensional, obtains mixed-powder；Pressure in batch mixing machine jar body
≤ 10Pa, then it is helium to 1 atmospheric pressure to pour inert gas.
Step 3, vacuum Relative compaction：
Vacuum is pressed into cylinder blank during mixed-powder is put into mould, and the relative density of cylinder blank is 90%；
In order to realize that vacuum is suppressed, pressure≤6.5 × 10 in the corresponding mould of vacuum environment-2Pa。
Step 4, vacuum-sintering：
Cylinder blank is put into crucible, vacuum-sintering is carried out, furnace pressure≤6.5 × 10 are first evacuated to-3Pa, so
Reheat afterwards and be warming up to 1050 DEG C, be incubated 2h, cool to room temperature with the furnace and take out CuCr sintered samples；
Step 5, densification of swaging：
CuCr sintered samples are heated to 850 DEG C in batch-type furnace, 0.5h is incubated, be put into swager forge until
Diameter specifications size is reached, last thermally treated, cutting, machine adds and obtains high-quality chromiumcopper CuCr50 alloys；
The single decrement in CuCr sintered samples cross section is less than 20% when swaging, and mould cycle is per minute 3000
Secondary, the feed rate of CuCr sintered samples is 1000mm/min.
The CuCr50 contact materials prepared are by test.Oxygen content in contact material<300ppm, nitrogen content<10ppm,
Carbon content<60ppm, relative density 100% (complete fine and close), hardness HB>80, electrical conductivity>17Ms/m.
Embodiment 3：CuCr1.5 alloy preparation technologies
The present embodiment provides a kind of high-quality chromiumcopper densification process, as shown in figure 1, the technique is specifically according to following
Step is carried out：
Step one, dispensing：
Chromium powder (particle diameter≤60 μm, oxygen content≤2000ppm), electrolytic copper powder (particle diameter≤40 μm, oxygen content≤
1200ppm), graphite (C) powder (particle diameter≤40 μm).
Chromium powder, copper powder and graphite powder are carried out into dispensing, preliminary mixed-powder is obtained；
In described preliminary mixed-powder, in terms of parts by weight, the ratio of chromium powder and copper powder is 1.5：89.5, chromium powder and copper powder
Parts by weight sum be 100 parts, the addition of graphite powder is chromium powder and the 0.1% of copper powder gross mass；
Step 2, Vacuum Mixture：、
Preliminary mixed-powder is fitted into batch mixing machine jar body, is then vacuumized, pour inert gas, in inert gas shielding
Lower use three-dimensional mixer rotates mixing 3h to preliminary mixed-powder three-dimensional, obtains mixed-powder；Pressure in batch mixing machine jar body
≤ 10Pa, then it is argon gas to 1 atmospheric pressure to pour inert gas.
Step 3, vacuum Relative compaction：
Vacuum is pressed into cylinder blank during mixed-powder is put into mould, and the relative density of cylinder blank is 80%；
In order to realize that vacuum is suppressed, pressure≤6.5 × 10 in the corresponding mould of vacuum environment-2Pa。
Step 4, vacuum-sintering：
Cylinder blank is put into crucible, vacuum-sintering is carried out, furnace pressure≤6.5 × 10 are first evacuated to-3Pa, so
Reheat afterwards and be warming up to 1000 DEG C, be incubated 3h, cool to room temperature with the furnace and take out CuCr sintered samples；
Step 5, densification of swaging：
CuCr sintered samples are heated to 800 DEG C in batch-type furnace, 1h is incubated, being put into swager forge until reaching
Last thermally treated to diameter specifications size, cutting, machine adds and obtains high-quality chromiumcopper CuCr1.5 alloys；
The single decrement in CuCr sintered samples cross section is less than 18% when swaging, and mould cycle is per minute 2000
Secondary, the feed rate of CuCr sintered samples is 1000mm/min.
CuCr1.55 alloy materials are prepared by test, oxygen content in material<200ppm, nitrogen content<10ppm, carbon contains
Amount<60ppm, relative density 100% (complete fine and close), hardness HB>65, electrical conductivity>43Ms/m.
Claims (8)
1. a kind of high-quality chromiumcopper densification process, it is characterised in that the technique is former with chromium powder, copper powder and graphite powder
Material, dispensing, Vacuum Mixture and vacuum Relative compaction are sequentially passed through by raw material, obtain cylinder blank, cylinder blank it is relative
Density is 80%~90%, cylinder blank then is carried out into vacuum-sintering and obtains CuCr sintered samples, finally sinters CuCr
Sample carries out densification of swaging, and obtains high-quality chromiumcopper.
2. high-quality chromiumcopper densification process as claimed in claim 1, it is characterised in that described cylinder blank
Relative density is 85%~90%.
3. high-quality chromiumcopper densification process as claimed in claim 1, it is characterised in that the technique is specifically according to following
Step is carried out：
Step one, dispensing：
Chromium powder, copper powder and graphite powder are carried out into dispensing, preliminary mixed-powder is obtained；
In described preliminary mixed-powder, in terms of parts by weight, the ratio of chromium powder and copper powder is (1.5~50)：(50~98.5), chromium
Powder is 100 parts with the parts by weight sum of copper powder；The addition of graphite powder be chromium powder and copper powder gross mass 0.1%~
0.3%；
Step 2, Vacuum Mixture：、
Preliminary mixed-powder is fitted into batch mixing machine jar body, is then vacuumized, pour inert gas, adopted under inert gas shielding
3~4h of mixing is rotated to preliminary mixed-powder three-dimensional with three-dimensional mixer, mixed-powder is obtained；
Step 3, vacuum Relative compaction：
Mixed-powder is put into vacuum in mould and is pressed into cylinder blank, the relative density of cylinder blank for 80%~
90%；
Step 4, vacuum-sintering：
Cylinder blank is put into crucible, vacuum-sintering is carried out, furnace pressure≤6.5 × 10 are first evacuated to-3Pa, Ran Houzai
980 DEG C~1050 DEG C are heated to, 2~4h is incubated, room temperature are cooled to the furnace and is taken out CuCr sintered samples；
Step 5, densification of swaging：
CuCr sintered samples are heated to 800~850 DEG C in batch-type furnace, 0.5~1h is incubated, are put into swager and are forged
Last thermally treated until reach diameter specifications size, cutting, machine adds and obtains high-quality chromiumcopper.
4. high-quality chromiumcopper densification process as claimed in claim 3, it is characterised in that in step one, it is described just
In step mixed-powder, in terms of parts by weight, the ratio of chromium powder and copper powder is (15~50)：The weight of (50~85), chromium powder and copper powder
Number sum is 100 parts；The addition of graphite powder is the 0.2%~0.3% of chromium powder and copper powder gross mass.
5. high-quality chromiumcopper densification process as claimed in claim 3, it is characterised in that in step 2, batch mixer tank
Internal pressure≤10Pa, then it is argon gas or helium to 1 atmospheric pressure to pour inert gas.
6. high-quality chromiumcopper densification process as claimed in claim 3, it is characterised in that in step 3, in order to realize
Vacuum is suppressed, pressure≤6.5 × 10 in the corresponding mould of vacuum environment-2Pa。
7. high-quality chromiumcopper densification process as claimed in claim 3, it is characterised in that in step 3, by mixed powder
Vacuum is pressed into cylinder blank during end is put into mould, and the relative density of cylinder blank is 85%~90%.
8. high-quality chromiumcopper densification process as claimed in claim 3, it is characterised in that in step 5, when swaging
The single decrement in CuCr sintered samples cross section is less than 15%~20%, and mould cycle is per minute 1500~3000
Secondary, the feed rate of CuCr sintered samples is 1000mm/min.
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| CN108165814A (en) * | 2017-12-08 | 2018-06-15 | 江西省科学院应用物理研究所 | A kind of carbon microalloy Cu-Cr based materials and preparation method thereof |
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| CN113118235A (en) * | 2021-04-20 | 2021-07-16 | 江苏天工工具有限公司 | Forming method of powder metallurgy high-speed steel |
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| CN114589308A (en) * | 2022-03-29 | 2022-06-07 | 深圳市千禾盛科技有限公司 | Copper-containing metal complex and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108165814A (en) * | 2017-12-08 | 2018-06-15 | 江西省科学院应用物理研究所 | A kind of carbon microalloy Cu-Cr based materials and preparation method thereof |
| CN112589101A (en) * | 2020-10-21 | 2021-04-02 | 陕西斯瑞新材料股份有限公司 | Preparation method of copper-chromium shielding case for vacuum arc-extinguishing chamber |
| CN112589101B (en) * | 2020-10-21 | 2022-09-09 | 陕西斯瑞新材料股份有限公司 | Preparation method of copper-chromium shielding case for vacuum arc-extinguishing chamber |
| CN113118235A (en) * | 2021-04-20 | 2021-07-16 | 江苏天工工具有限公司 | Forming method of powder metallurgy high-speed steel |
| CN113369479A (en) * | 2021-06-09 | 2021-09-10 | 北京有研粉末新材料研究院有限公司 | High-density powder metallurgy pure copper material part and preparation method thereof |
| CN114515831A (en) * | 2022-03-16 | 2022-05-20 | 桂林金格电工电子材料科技有限公司 | Method for preparing copper-chromium contact consumable electrode by using copper-chromium rim charge |
| CN114515831B (en) * | 2022-03-16 | 2024-04-26 | 桂林金格电工电子材料科技有限公司 | Method for preparing copper-chromium contact consumable electrode by utilizing copper-chromium rim charge |
| CN114589308A (en) * | 2022-03-29 | 2022-06-07 | 深圳市千禾盛科技有限公司 | Copper-containing metal complex and preparation method thereof |
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