CN105274386A - High-performance complex multi-element phosphor bronze alloy material and preparation method thereof - Google Patents
High-performance complex multi-element phosphor bronze alloy material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-performance complex multi-element phosphor bronze alloy material and a preparation method thereof, and belongs to the field of processing of nonferrous metal. The alloy material comprises the following components in percentage by weight: 3.9-4.4% of Sn, 0.05-0.1% of Ni, 0.05-0.2% of Zn, 0.05-0.2% of Fe, 0.02-0.08% of P, and the balance of Cu. In addition, the alloy further comprises two or more elements of Co, B and Zr. The material is obtained through such processes as smelting and casting, rough rolling, primary intermediate annealing, acid washing, intermediate rolling, secondary intermediate annealing, acid washing, finish rolling and low-temperature annealing. The method can omit a high-temperature and long-time uniform annealing process, the alloy production efficiency is improved, and the alloy production cost is greatly reduced. The alloy can replace a classic tin-phosphor bronze QSn8-0.3 alloy, and is applied to the manufacturing of such elements as contact pieces and connectors for electronic electric appliances and vehicles.
Description
Technical field
The present invention relates to a kind of high-performance complicated pluralism phosphor bronze alloy material and preparation method thereof, belong to non-ferrous metals processing field.
Background technology
Along with the development of modernization science and technology, electronics, communication and automobile industry are in the high speed development stage, day by day increase the demand of the elastic element such as connector, junctor Copper-Nickel-Aluminium Alloy.Meanwhile, harsher requirement is proposed to the performance of Copper-Nickel-Aluminium Alloy, as alloy requires to have high strength, high conductivity, snappiness, high resistance to stress relaxation property, high-fatigue strength etc.On domestic market, high-strength high elasticity copper base alloy is mainly based on alloy series such as berylliumbronze and high tin-phosphor bronzes (QSn8-0.3, QSn10-0.3), wherein berylliumbronze is as the king of nonferrous materials elasticity, there is the incomparable performance advantage of other materials, but because beryllium has serious detrimental effect to the health of people and environment, and the complete processing of beraloy is complicated and actual production difficulty is large, causes it to be applied in special dimension.Conventional high Sn-P-Cu alloy, Theil indices is up to 8-10%, alloy strand after horizontal casting is produced easily produces tin segregation phenomena, the homogenizing thermal treatment of long period and thermal treatment is repeatedly needed to eliminate, production efficiency is lower, and the price of Sn costly, the higher corresponding material cost of Theil indices is higher.In addition, the electric conductivity of high Sn-P-Cu alloy only has 12%IACS, is difficult to the growth requirement meeting snappiness conductive-type copper-based alloy material, affects further industrialization production and the marketing of high Sn-P-Cu alloy.
Summary of the invention
Main purpose of the present invention is the deficiency making up existing copper alloy property, the basis of classical tin-phosphor bronze (QSn8-0.3) carries out reducing Sn content and adds the alloying elements such as Ni, Zn, Fe and by the elementary composition composite refining agent of Co, B and Zr tri-kinds simultaneously, alloy composition and tissue improve, and the performance of alloy is compared favourably with it.Lower and the fine microstructures of Sn content due to alloy of the present invention, Sn segregation degree improves, and can save the long homogenizing annealing process of high temperature, improve the production efficiency of alloy, greatly reduce the production cost of alloy.
In order to achieve the above object, the present invention is achieved in that
A kind of high-performance complicated pluralism phosphor bronze alloy material, its weight percent consists of: Sn3.9 ~ 4.4%, Ni0.05 ~ 0.1%, Zn0.05 ~ 0.2%, Fe0.05 ~ 0.2%, P0.02 ~ 0.08%, and all the other are Cu.
Further, this alloy is also containing the two or more elements be selected from Co, B and Zr, and weight content is respectively Co0.002 ~ 0.015%, B0.003 ~ 0.015%, Zr0.005 ~ 0.015%, and total content is 0.01%≤Co+B+Zr≤0.03%.
Add alloys producing:
Nickel: nickel element can play solution strengthening effect, the interpolation of nickel element can also increase the heat resisting temperature of alloy in addition.
Tin: because tin atom differs comparatively large with copper atom radius, add tin element, can cause larger lattice distortion in copper alloy, the effective motion hindering dislocation, carries heavy alloyed intensity and elastic performance.In addition, the interpolation of tin element can significantly improve the corrosion resistance nature of alloy.
Phosphorus: the phosphoric of trace not only can play phlogistication, can also form phosphate copper compound, carry heavy alloyed anti-softening temperature and stress relaxation resistance with copper.
Zinc: zinc element mainly improves alloy in the alloy to scolding tin stain permeability and heat-resisting adhesive performance.
Iron: ferro element can effectively adjust alloy grain and organize size, improves the homogeneity of tissue, improves the anticorrosion stress-resistant susceptibility of alloy.
Boron, cobalt and zr element: the interpolation of three kinds of elements all can mainly play crystal grain thinning size, reduce the effect of tin segregation degree.When three kinds of elements add in alloy jointly, owing to there is interation between nutrients between three kinds of elements, energy is crystal grain thinning and the segregation of reduction tin obviously, and its effect is better than interpolation two kinds of alloying elements.
Another object of the present invention is to provide the preparation working method of above-mentioned high-performance complicated pluralism tin bronze alloys material.
A preparation working method for high-performance complicated pluralism tin copper alloy material, comprises following technical process: a. carries out preparing burden according to mass percent, feed intake, melting and casting, b. milling face, c. roughing, d. trimming, an e. process annealing, f. pickling, rolls in g., h. bis-process annealing, i. pickling, j. finish rolling, k. low-temperature annealing, l. pickling, m. stretch-bending straightening, n. sub-cut is put in storage.
In step a, adopt line frequency induction furnace to carry out melting and casting under non-vacuum environment, described smelting temperature is 1260 ~ 1300 DEG C, and described casting temp controls at 1220 ~ 1250 DEG C.
Before melting, in line frequency induction furnace, add the tin-phosphor bronze QSn6.5-0.1 scrap stock of 70w% and the virgin material of 30w%, carry out non-vacuum melting.Wherein virgin material comprises electrolytic copper, electrolytic nickel, electrolytic cobalt, pure zinc, copper boron, copper iron and copper zirconium master alloy, temperature is risen to 1260 ~ 1300 DEG C, after copper fusing to be electrolysed, the charcoal adding calcination covers, after fully stirring, leave standstill 15 ~ 25min, carry out horizontal casting casting, casting technological parameter is: the speed of being pulled is 14 ~ 16mm/s, stops 2.5 ~ 3.5s, the anti-speed that pushes away is 10 ~ 12mm/s, and made-up belt temperature out is 350 ~ 450 DEG C.
In step b, horizontal continuous casting blank is carried out the process of milling face, about 1mm is measured in upper and lower milling face, mainly removes surface imperfection.
In step c, the ingot blank behind milling face is carried out cold rolling cogging, the total deformation of roughing cogging is 65 ~ 85%.
In step e, placed in bell-type annealing furnace by the cold-reduced sheet after trimming and carry out process annealing, one time the heat treated temperature of process annealing is 475 ~ 525 DEG C, and soaking time is 4 ~ 6h.
In step g, roll in being carried out by the sheet material after pickling, the total deformation of rolling in described is 50 ~ 70%.
In step h, by roll after Strip carry out secondary process annealing process, secondary process annealing treatment temp is 450 ~ 500 DEG C, and soaking time is 4 ~ 6h.
In step j, the band after pickling is carried out finish rolling, finish rolling total deformation is 30 ~ 50%.
In step k, placed by the band after finish rolling in bell-jar annealing and carry out low-temperature annealing, low-temperature anneal temperature is 200 ~ 250 DEG C, and annealing time is 4 ~ 6h.
Advantage of the present invention: the present invention reduces Sn content on the basis of traditional tin-phosphor bronze (QSn8-0.3), and add Fe, Ni and Zn element, make the performance of alloy suitable with it, simultaneously a kind of by least two kinds of compound modifiers formed in Co, B and Zr tri-kinds of elements by adding in fusion-casting process, mainly structure refinement is played to invention alloy, reduce the effect of the segregation degree of Sn element, the long-time homogenizing annealing treatment process of high temperature is removed after saving, reduce production cost, improve the production efficiency of alloy.The chemical composition of the high-performance complicated pluralism phosphor bronze alloy material developed by the present invention is respectively: Theil indices 3.9 ~ 4.4%, nickel content 0.05 ~ 0.1%, iron level 0.05 ~ 0.20%, Zn content 0.05 ~ 0.2%, phosphorus content 0.02 ~ 0.08%, all the other are copper.In addition, also at least containing at least two kinds in cobalt, boron and zr element in copper alloy, wherein cobalt contents is 0.002 ~ 0.015%, and Boron contents is 0.003 ~ 0.015%, and zirconium content is 0.005 ~ 0.015%, and total content is 0.01%≤cobalt+boron+zirconium≤0.03%.In addition, the present invention further developed a kind of preparation working method being applicable to above-mentioned copper alloy, tensile strength through the high-performance complicated pluralism phosphor bronze alloy material of processing and heat treatment is 800 ~ 850MPa, electric conductivity is 20 ~ 25%, elongation 5 ~ 7%, Young's modulus is 110 ~ 120GPa, stress relaxation resistance is (125 DEG C, be 1000h) 75% ~ 80%, can substitute classical tin-phosphor bronze QSn8-0.3 alloy completely, application makes the components such as electronics, automobile connector and junctor.
Below by embodiment, the present invention will be further described, but and do not mean that limiting the scope of the invention.
Embodiment
High-performance complicated pluralism phosphor bronze alloy material of the present invention, it is containing, for example the chemical composition of lower weight percentage: Sn3.9 ~ 4.4%, Ni0.05 ~ 0.1%, Zn0.05 ~ 0.2%, P0.02 ~ 0.08%, Fe0.05 ~ 0.20%, and all the other are Cu.In addition, also at least containing at least two kinds in Co, B and Zr element in copper alloy, wherein Co0.002 ~ 0.015%, B0.003 ~ 0.015%, Zr0.005 ~ 0.015%, total content is 0.01% ~ 0.03%.
The preparation of above-mentioned high-performance complicated pluralism phosphor bronze alloy material and working method, comprise following technical process: a. carries out preparing burden according to mass percent, feed intake, melting and casting, b. milling face, c. roughing, d. trimming, e. first time process annealing, f. pickling, rolls in g., the process annealing of h. second time, i. pickling, j. finish rolling, k. low-temperature annealing, l. pickling, m. stretch-bending straightening, n. sub-cut is put in storage.Wherein, concrete feeding sequence is: the virgin material of the tin-phosphor bronze QSn6.5-0.1 scrap stock and 30w% that add 70w% in line frequency induction furnace carries out non-vacuum melting, wherein virgin material comprises electrolytic copper, electrolytic nickel, electrolytic cobalt, pure zinc, copper boron, copper iron and copper zirconium master alloy, temperature is risen to 1260 ~ 1300 DEG C, after copper fusing to be electrolysed, the charcoal adding calcination covers, after abundant stirring, leave standstill 15 ~ 25min, carry out horizontal casting casting, casting technological parameter is: the speed of being pulled is 14 ~ 16mm/s, stop 2.5 ~ 3.5s, the anti-speed that pushes away is 10 ~ 12mm/s, made-up belt temperature out is 350 ~ 450 DEG C.Milling face processes, and about 1mm is measured in upper and lower milling face, mainly removes surface imperfection.Cold rolling cogging, deflection is 65 ~ 85%.First time process annealing, annealing temperature is 475 ~ 525 DEG C, and annealing time is 4 ~ 6h.In to roll deflection be 50 ~ 70%.Second time process annealing process, annealing temperature is 450 ~ 500 DEG C, and annealing time is 4 ~ 6h.Finish rolling deflection is 30 ~ 50%.Low-temperature annealing, annealing temperature is 200 ~ 250 DEG C, and annealing time is 4 ~ 6h.
Embodiment 1
Alloy of the present invention adopts following raw material melting: tin-phosphor bronze QSn6.5-0.1 scrap stock, electrolytic copper, electrolytic nickel, electrolytic cobalt, pure zinc, copper boron and copper iron master alloy.The composition of alloy is in the embodiment 1 of table 1.
1. melting: add the tin-phosphor bronze QSn6.5-0.1 scrap stock of 70% and the virgin material of 30% in line frequency induction furnace, wherein virgin material comprises electrolytic copper, electrolytic nickel, electrolytic cobalt, pure zinc, copper boron and copper iron master alloy, temperature is risen to 1260 DEG C, after copper fusing to be electrolysed, the charcoal adding calcination covers, after abundant stirring, leave standstill 15min, when holding temperature is 1220 DEG C, carry out horizontal casting casting, casting technological parameter is: the speed of being pulled is 14mm/s, stops 2.5s, the anti-speed that pushes away is 12mm/s, and made-up belt temperature out is 450 DEG C.
2. roughing: carry out cold rolling cogging to the alloy behind milling face, amount of finish is 65%.
3. first time process annealing thermal treatment: carry out process annealing process to slab after roughing, annealing temperature is 475 DEG C, and annealing time is 6h.
4. roll in: roll in carrying out the Strip after a process annealing process, pickling, amount of finish is 70%.
5. second time process annealing thermal treatment: centering roll after strip carry out process annealing process, annealing temperature is 500 DEG C, and annealing time is 4h.
6. finish rolling: carry out finish rolling to the band after secondary process annealing process, pickling, amount of finish is 30%.
7. low-temperature annealing process: carry out low-temperature annealing process to band after finish rolling, annealing temperature is 200 DEG C, and annealing time is 6h.
Through above melting and casting, roughing, a process annealing process, pickling, in roll, secondary process annealing process, pickling, finish rolling, after the processing treatment such as low-temperature annealing, its performance is in the embodiment 1 in table 2.
Embodiment 2
Alloy of the present invention adopts following raw material melting: tin-phosphor bronze QSn6.5-0.1 scrap stock, electrolytic copper, electrolytic nickel, electrolytic cobalt, pure zinc, copper iron and copper zirconium master alloy.The composition of alloy is in the embodiment 2 of table 1.
1. melting: add the tin-phosphor bronze QSn6.5-0.1 scrap stock of 70% and the virgin material of 30% in line frequency induction furnace, wherein virgin material comprises electrolytic copper, electrolytic cobalt, electrolytic nickel, pure zinc, copper iron and copper zirconium master alloy, temperature is risen to 1280 DEG C, after copper fusing to be electrolysed, the charcoal adding calcination covers, after abundant stirring, leave standstill 25min, when holding temperature is 1250 DEG C, carry out horizontal casting casting, casting technological parameter is: the speed of being pulled is 16mm/s, stops 3.5s, the anti-speed that pushes away is 10mm/s, and made-up belt temperature out is 350 DEG C.
2. roughing: carry out cold rolling cogging to the alloy behind milling face, amount of finish is 85%.
3. first time process annealing thermal treatment: carry out process annealing process to slab after roughing, annealing temperature is 500 DEG C, and annealing time is 4h.
4. roll in: roll in carrying out the Strip after a process annealing process, pickling, amount of finish is 50%.
5. second time process annealing thermal treatment: centering roll after strip carry out process annealing process, annealing temperature is 450 DEG C, and annealing time is 6h.
6. finish rolling: carry out finish rolling to the band after secondary process annealing process, pickling, amount of finish is 50%.
7. low-temperature annealing process: carry out low-temperature annealing process to band after finish rolling, annealing temperature is 250 DEG C, and annealing time is 4h.
Through above melting and casting, roughing, a process annealing process, pickling, in roll, secondary process annealing process, pickling, finish rolling, after the processing treatment such as low-temperature annealing, its performance is in the embodiment 2 in table 2.
Embodiment 3
Alloy of the present invention adopts following raw material melting: tin-phosphor bronze QSn6.5-0.1 scrap stock, electrolytic copper, electrolytic nickel, pure zinc, copper boron, copper iron and copper zirconium master alloy.The composition of alloy is in the embodiment 3 of table 1.
1. melting: add the tin-phosphor bronze QSn6.5-0.1 scrap stock of 70% and the virgin material of 30% in line frequency induction furnace, wherein virgin material comprises electrolytic copper, electrolytic nickel, pure zinc, copper boron, copper iron and copper zirconium master alloy, temperature is risen to 1300 DEG C, after copper fusing to be electrolysed, the charcoal adding calcination covers, after abundant stirring, leave standstill 20min, when holding temperature is 1230 DEG C, carry out horizontal casting casting, casting technological parameter is: the speed of being pulled is 15mm/s, stops 3s, the anti-speed that pushes away is 11mm/s, and made-up belt temperature out is 400 DEG C.
2. roughing: carry out cold rolling cogging to the alloy behind milling face, amount of finish is 75%.
3. first time process annealing thermal treatment: carry out process annealing process to slab after roughing, annealing temperature is 480 DEG C, and annealing time is 5h.
4. roll in: roll in carrying out the Strip after a process annealing process, pickling, amount of finish is 60%.
5. second time process annealing thermal treatment: centering roll after strip carry out process annealing process, annealing temperature is 475 DEG C, and annealing time is 5h.
6. finish rolling: carry out finish rolling to the band after secondary process annealing process, pickling, amount of finish is 40%.
7. low-temperature annealing process: carry out low-temperature annealing process to band after finish rolling, annealing temperature is 225 DEG C, and annealing time is 5h.
Through above melting and casting, roughing, a process annealing process, pickling, in roll, secondary process annealing process, pickling, finish rolling, after the processing treatment such as low-temperature annealing, its performance is in the embodiment 3 in table 2.
Embodiment 4
Alloy of the present invention adopts following raw material melting: tin-phosphor bronze QSn6.5-0.1 scrap stock, electrolytic copper, electrolytic nickel, electrolytic cobalt, pure zinc, copper boron, copper iron and copper zirconium master alloy.The composition of alloy is in the embodiment 4 of table 1.
1. melting: add the tin-phosphor bronze QSn6.5-0.1 scrap stock of 70% and the virgin material of 30% in line frequency induction furnace, wherein virgin material comprises electrolytic copper, electrolytic nickel, electrolytic cobalt, pure zinc, copper boron, copper iron and copper zirconium master alloy, temperature is risen to 1270 DEG C, after copper fusing to be electrolysed, the charcoal adding calcination covers, after abundant stirring, leave standstill 22min, when holding temperature is 1240 DEG C, carry out horizontal casting casting, casting technological parameter is: the speed of being pulled is 14mm/s, stops 3s, the anti-speed that pushes away is 10mm/s, and made-up belt temperature out is 425 DEG C.
2. roughing: carry out cold rolling cogging to the alloy behind milling face, amount of finish is 70%.
3. first time process annealing thermal treatment: carry out process annealing process to slab after roughing, annealing temperature is 500 DEG C, and annealing time is 5h.
4. roll in: roll in carrying out the Strip after a process annealing process, pickling, amount of finish is 50%.
5. second time process annealing thermal treatment: centering roll after strip carry out process annealing process, annealing temperature is 475 DEG C, and annealing time is 4h.
6. finish rolling: carry out finish rolling to the band after secondary process annealing process, pickling, amount of finish is 50%.
7. low-temperature annealing process: carry out low-temperature annealing process to band after finish rolling, annealing temperature is 200 DEG C, and annealing time is 5h.
Through above melting and casting, roughing, a process annealing process, pickling, in roll, secondary process annealing process, pickling, finish rolling, after the processing treatment such as low-temperature annealing, its performance is in the embodiment 4 in table 2.
The alloying constituent table (wt%) of table 1 embodiment 1-4
The alloy property table of table 2 embodiment 1-4
The present invention by melting and casting, roughing, a process annealing, pickling, in roll, secondary process annealing, pickling, finish rolling, obtains a kind of high-performance complicated pluralism phosphor bronze alloy material after the processing treatment such as low-temperature annealing process.Lower and the fine microstructures of Sn content due to alloy of the present invention, Sn segregation degree improves, and can save the long homogenizing annealing process of high temperature, improve the production efficiency of alloy, greatly reduce the production cost of alloy.
The tensile strength of blaster fuse frame material of the present invention is 800 ~ 850MPa, specific conductivity is 20 ~ 25%IACS, unit elongation is 5 ~ 7%, Young's modulus is 110 ~ 120GPa, stress relaxation resistance is (at 125 DEG C, be 1000h) 75% ~ 80%, classical tin-phosphor bronze QSn8-0.3 alloy can be substituted, be applied to components such as making electronic apparatus, automobile contact element and junctor.
Claims (10)
1. a high-performance complicated pluralism phosphor bronze alloy material, is characterized in that: its weight percent consists of: Sn3.9 ~ 4.4%, Ni0.05 ~ 0.1%, Zn0.05 ~ 0.2%, Fe0.05 ~ 0.2%, P0.02 ~ 0.08%, all the other are Cu.
2. high-performance complicated pluralism phosphor bronze alloy material according to claim 1, it is characterized in that: this alloy is also containing the two or more elements in Co, B and Zr, weight content is Co0.002 ~ 0.015%, B0.003 ~ 0.015%, Zr0.005 ~ 0.015%, total content is 0.01% ~ 0.03%.
3. the preparation working method of the high-performance complicated pluralism phosphor bronze alloy material described in claim 1 or 2, comprises the following steps: a. carries out preparing burden according to mass percent, feed intake, melting and casting, b. milling face, c. roughing, d. trimming, an e. process annealing, f. pickling, rolls in g., h. bis-process annealing, i. pickling, j. finish rolling, k. low-temperature annealing, l. pickling, m. stretch-bending straightening, n. sub-cut is put in storage.
4. the preparation working method of high-performance complicated pluralism phosphor bronze alloy material according to claim 3, it is characterized in that: in line frequency induction furnace, add the tin-phosphor bronze QSn6.5-0.1 scrap stock of 70% and the virgin material of 30%, carry out non-vacuum melting, wherein virgin material comprises electrolytic copper, electrolytic nickel, electrolytic cobalt, pure zinc, copper boron, copper iron and/or copper zirconium master alloy, heat up, after copper fusing to be electrolysed, the charcoal adding calcination covers, after abundant stirring, leave standstill 15 ~ 25min, carry out horizontal casting casting, smelting temperature is 1260 ~ 1300 DEG C, casting temp is 1220 ~ 1250 DEG C, casting technological parameter is: the speed of being pulled is 14 ~ 16mm/s, stop 2.5 ~ 3.5s, the anti-speed that pushes away is 10 ~ 12mm/s, made-up belt temperature out is 350 ~ 450 DEG C.
5. the preparation working method of high-performance complicated pluralism phosphor bronze alloy material according to claim 3, is characterized in that: the total deformation of described roughing is 65 ~ 85%.
6. the preparation working method of high-performance complicated pluralism phosphor bronze alloy material according to claim 3, is characterized in that: a described heat treated temperature of process annealing is 475 ~ 525 DEG C, and soaking time is 4 ~ 6h.
7. the preparation working method of high-performance complicated pluralism phosphor bronze alloy material according to claim 3, is characterized in that: the total deformation of rolling in described is 50 ~ 70%.
8. the preparation working method of high-performance complicated pluralism phosphor bronze alloy material according to claim 3, is characterized in that: described secondary process annealing treatment temp is 450 ~ 500 DEG C, and soaking time is 4 ~ 6h.
9. the preparation working method of high-performance complicated pluralism phosphor bronze alloy material according to claim 3, is characterized in that: described finish rolling total deformation is 30 ~ 50%.
10. the preparation working method of high-performance complicated pluralism phosphor bronze alloy material according to claim 3, it is characterized in that: described low-temperature anneal temperature is 200 ~ 250 DEG C, annealing time is 4 ~ 6h.
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| CN109434378A (en) * | 2018-10-31 | 2019-03-08 | 温州铜丰铜业有限公司 | A kind of copper strips production technology |
| CN111020280A (en) * | 2019-12-19 | 2020-04-17 | 福州大学 | Cu-Al-Hf-Ti-Zr copper alloy material and preparation method thereof |
| CN112853148A (en) * | 2020-12-31 | 2021-05-28 | 浙江惟精新材料股份有限公司 | High-strength high-elasticity bending-resistant copper alloy and preparation method and application thereof |
| CN112853148B (en) * | 2020-12-31 | 2021-09-17 | 浙江惟精新材料股份有限公司 | High-strength high-elasticity bending-resistant copper alloy and preparation method and application thereof |
| CN114525390A (en) * | 2022-02-21 | 2022-05-24 | 江西省科学院应用物理研究所 | Production method of copper-tin alloy strip |
| CN116875842A (en) * | 2023-07-19 | 2023-10-13 | 中国科学院金属研究所 | Rare earth copper-tin-phosphorus alloy material and preparation method thereof |
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