CN102994768A - Electro-slag re-melting slag and preparation method thereof - Google Patents
Electro-slag re-melting slag and preparation method thereof Download PDFInfo
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- CN102994768A CN102994768A CN2012102856099A CN201210285609A CN102994768A CN 102994768 A CN102994768 A CN 102994768A CN 2012102856099 A CN2012102856099 A CN 2012102856099A CN 201210285609 A CN201210285609 A CN 201210285609A CN 102994768 A CN102994768 A CN 102994768A
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- 239000002893 slag Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000002844 melting Methods 0.000 title claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 12
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 12
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000010436 fluorite Substances 0.000 claims abstract description 12
- 239000004571 lime Substances 0.000 claims abstract description 12
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 12
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 12
- 235000014380 magnesium carbonate Nutrition 0.000 claims abstract description 12
- 239000011575 calcium Substances 0.000 claims abstract description 11
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000003723 Smelting Methods 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 239000004927 clay Substances 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- 239000007858 starting material Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000013467 fragmentation Methods 0.000 claims description 3
- 238000006062 fragmentation reaction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000006698 induction Effects 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 229910001570 bauxite Inorganic materials 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000005266 casting Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910001315 Tool steel Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Landscapes
- Treatment Of Steel In Its Molten State (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides electro-slag re-melting slag, consisting of the following components in percentage by weight: 20%-25% of fluorite, 35%-40% of bauxite, 30%-35% of high-calcium lime, 3%-8% of fused magnesite and 5%-10% of silica. A preparation method of the electro-slag re-melting slag comprises the following process steps of checking, finely grinding, proportioning, balling, drying, electrically smelting, deslagging, cooling, crashing, checking, packaging and storing. The electro-slag re-melting slag provided by the invention can be used for reducing the introduction of hydrogen, oxygen and nitrogen, and has the advantages of ensuring the surface smoothness of cast ingots and low power consumption.
Description
Technical field
The invention belongs to the metallurgic auxiliary materials technical field, relate to a kind of electro slag remelting slag, the invention still further relates to the preparation method of this electro slag remelting slag.
Background technology
At present, at metallurgy industry, electro slag remelting slag commonly used is binary slag system and ternary slag system.The binary slag system is molten to be CaF
2-TiO
2Slag, it represents composition is CaF
270%+Al
2O
330%.This slag for comprehensive processing performance is better, adapts to different technology conditions, has certain desulfurization and goes to be mingled with ability, is applicable to remelting ball bearing stee, structural alloy steel, rapid tool steel, die steel and stainless refractory steel etc.But this slag exists some shortcomings, and not on low melting eutectics point, fusing point is higher such as slag ingredient; The specific conductivity of slag is high, and the remelting power consumption is high; CaF in the slag
2Content is high, easy contaminate environment in the melting; Steel inclusion is take fragility aluminate and corundum as main, affects the plasticity of steel and toughness etc.For fear of CaF
2-Al
2O
3The above-mentioned shortcoming of slag system has been developed CaF in recent years
2-CaO-Al
2O
3The ternary slag system, CaF
2-CaO-Al
2O
3-MgO quaternary slag system and CaF
2-CaO-Al
2O
3-MgO-SiO
2Five yuan of slag systems etc.The composition of these slag systems is chosen on the ternary eutectic line substantially, and the fusing point of slag is lower, and segregation phenomena was slighter when slag crust solidified, and slag ingredient is stable, the ingot casting any surface finish, and moulding is good.And these slag systems have lower specific conductivity, have improved electrical efficiency, because of CaF in the slag
2Reduce, the pollution that causes also alleviates to some extent, contains a small amount of MgO or SiO in the slag
2, prevented that molten steel is air-breathing, make the ingot casting any surface finish.The shortcoming of these slag systems is to contain CaO, is easy to suction, therefore must pay close attention to the drying that keeps slag charge, inhales hydrogen oxygenation to prevent molten steel.
Summary of the invention
Technical problem to be solved by this invention provides that a kind of remelting slag system is stable, ingot casting smooth surface, product ingredient stability homogeneous, electro slag remelting slag that current consumption is low, and another technical problem to be solved by this invention provides the preparation method of this electro slag remelting slag.
For solving the problems of the technologies described above, to be designed electro slag remelting slag be comprised of the raw material of following weight percent the technical solution used in the present invention:
Fluorite 20-25%, bauxitic clay 35-40%, high calcium lime 30-35%, electrosmelted magnesite clinker 3-8%, silica 5-10%;
In above-mentioned each raw material, C in the fluorite
aF
2Content 〉=95%, S
iO
2Content≤2%, P content≤0.05%, S content≤0.05%, granularity is 15-20mm; Al in the bauxitic clay
2O
3Content 〉=97%, granularity≤0.5mm; C in the high calcium lime
aO content 〉=90%, S
iO
2Content≤2.5%, P content≤0.05%, S content≤0.05%, granularity is 10-50mm; M in the electrosmelted magnesite clinker
gO content 〉=95%, S
iO
2Content≤2%, P content≤0.01%, S content≤0.01%, granularity is 3-5mm; S in the silica
iO
2Content 〉=95%, granularity are 1-5mm.
The preparation technology of electro slag remelting slag of the present invention is:
⑴. check: every kind of starting material are checked out satisfactory starting material by the requirement of moiety content separately;
⑵. fine grinding: will check satisfactory each starting material to make granularity by crusher, Raymond mill is fine powder more than 100 orders;
⑶. proportioning: above-mentioned each fine powder is mixed by composition and ratio;
⑷. ball processed: mixed raw material is made the ball that granularity is 10-30mm through the dry-pressing apparatus for making pearl ball;
⑸. oven dry: the ball that is 10-30mm to the above-mentioned granularity that makes toasts;
⑹. electric smelting: to putting into the Medium Frequency Induction Heating Furnace high temperature melting through the ball of overbaking, make it form homogeneous, stable Composite burden;
⑺. slag tap:
⑻. cooling: pour above-mentioned Composite burden in furnace charge basin naturally cooling;
⑼. fragmentation: cooled furnace charge is broken, sub-sieve, make the product that granularity is 2-8mm;
⑽. check: the said products is tested;
⑾. packing: the product that is up to the standards is packed;
⑿. warehouse-in: the product warehousing after packing is deposited.
The advantage of electro slag remelting slag product performance of the present invention:
⑴ this slag is through special processing, and moisture resistance is strong, is difficult for hydration occurs, thereby has reduced bringing into of hydrogen, oxygen;
⑵ this slag is pressed proportioning, fritting after the first homogenizing, and physics, Chemical Composition are stablized, and ventilation property is little, has reduced bringing into of nitrogen;
⑶ different according to steel grade, make suitable electrical conductivity materials, reduce power consumption, save steel-making cost.
Embodiment
Electro slag remelting slag of the present invention is comprised of the raw material of following weight percent:
Fluorite 20-25%, bauxitic clay 35-40%, high calcium lime 30-45%, electrosmelted magnesite clinker 3-8%, silica 5-10%.
In each raw material of the electro slag remelting slag that the present invention makes, moiety content and the granularity requirements of every kind of raw material are as shown in the table:
Embodiment 1
Electro slag remelting slag of the present invention is comprised of the raw material of following weight percent:
Fluorite 20%, bauxitic clay 40%, high calcium lime 30%, electrosmelted magnesite clinker 5%, silica 5%.
Its preparation method is:
⑴. check: every kind of starting material are checked out satisfactory starting material by the requirement of moiety content separately;
⑵. fine grinding: will check satisfactory each starting material to make granularity by crusher, Raymond mill is fine powder more than 100 orders;
⑶. proportioning: above-mentioned each fine powder is mixed by composition and ratio;
⑷. ball processed: mixed raw material is made the ball that granularity is 10-30mm through the dry-pressing apparatus for making pearl ball;
⑸. oven dry: the ball that is 10-30mm to the above-mentioned granularity that makes toasts;
⑹. electric smelting: to putting into the Medium Frequency Induction Heating Furnace high temperature melting through the ball of overbaking, make it form homogeneous, stable Composite burden;
⑺. slag tap;
⑻. cooling: pour above-mentioned Composite burden in furnace charge basin naturally cooling;
⑼. fragmentation: cooled furnace charge is broken, sub-sieve, make the product that granularity is 2-8mm;
⑽. check: the said products is tested;
⑾. packing: the product that is up to the standards is packed;
⑿. warehouse-in: the product warehousing after packing is deposited.
Embodiment 2
Electro slag remelting slag of the present invention is comprised of the raw material of following weight percent:
Fluorite 20%, bauxitic clay 35%, high calcium lime 30%, electrosmelted magnesite clinker 5%, silica 10%.
Its preparation method is with embodiment 1.
Embodiment 3
Electro slag remelting slag of the present invention is comprised of the raw material of following weight percent:
Fluorite 25%, bauxitic clay 35%, high calcium lime 30%, electrosmelted magnesite clinker 5%, silica 5%.
Its preparation method is with embodiment 1.
Embodiment 4
Electro slag remelting slag of the present invention is comprised of the raw material of following weight percent:
Fluorite 20%, bauxitic clay 35%, high calcium lime 35%, electrosmelted magnesite clinker 5%, silica 5%.
Its preparation method is with embodiment 1.
Embodiment 5
Electro slag remelting slag of the present invention is comprised of the raw material of following weight percent:
Fluorite 22%, bauxitic clay 36%, high calcium lime 32%, electrosmelted magnesite clinker 3%, silica 7%.
Its preparation method is with embodiment 1.
Electro slag remelting slag of the present invention is with lime, bauxitic clay, fluorite, electrosmelted magnesite clinker, wollastonite raw material, adopt homogenization installation that the raw material of different varieties fully is mixed and made into pelletizing, and in electromagnetic induction furnace, melt, make physical reaction fully occurs between the raw material, the product composition of producing is more stable, homogeneous, and suitable specific conductivity, fusing point, viscosity, surface tension etc. are arranged.Commercial test results shows: 1. it is electric energy conversion resistance heat, and metal electrode relies on the resistance heat of slag to melt, and satisfies the needs of smelting temperature; When 2. molten metal formation metal drop passes slag bath in the reflow process, slag and molten drop contact area increase, utilize the chemical property of slag can effectively remove harmful element sulphur, phosphorus etc. in the steel, remove obnoxious flavour hydrogen, oxygen, nitrogen etc., absorb, dissolve the non-metallic inclusion at molten metal and slag interface, make metal obtain purifying, purifying; 3. it forms one deck slag crust between ingot casting and crystallizer, this layer slag crust played insulation, heat insulation, lubrication, metal is not directly contacted with crystallizer, prevented electric shunting, hot-fluid is mainly conducted to end water tank direction, crystallization tends to y direction, and is conducive to the relative movement of ingot casting and crystallizer wall.In addition, the melting slag bath above metal pool makes molten metal avoid directly contacting with atmosphere, has played preventing burning and storing hot insulation effect.In esr process, metal melts under the coating of slag all the time, solidifies.Steel purity through esr is high, sulfur-bearing is low, non-metallic inclusion is few, surface of steel ingot is smooth, clean even compact, metallographic structure and chemical composition are even.
Claims (2)
1. electro slag remelting slag is characterized in that being comprised of the raw material of following weight percent:
Fluorite 20-25%, bauxitic clay 35-40%, high calcium lime 30-35%, electrosmelted magnesite clinker 3-8%, silica 5-10%;
In above-mentioned each raw material, C in the fluorite
aF
2Content 〉=95%, S
iO
2Content≤2%, P content≤0.05%, S content≤0.05%, granularity is 15-20mm; Al in the bauxitic clay
2O
3Content 〉=97%, granularity≤0.5mm; C in the high calcium lime
aO content 〉=90%, S
iO
2Content≤2.5%, P content≤0.05%, S content≤0.05%, granularity is 10-50mm; M in the electrosmelted magnesite clinker
gO content 〉=95%, S
iO
2Content≤2%, P content≤0.01%, S content≤0.01%, granularity is 3-5mm; S in the silica
iO
2Content 〉=95%, granularity are 1-5mm.
2. method of making the described electro slag remelting slag of claim 1 is characterized in that adopting following preparation method:
⑴. check: every kind of starting material are checked out satisfactory starting material by the requirement of moiety content separately;
⑵. fine grinding: will check satisfactory each starting material to make granularity by crusher, Raymond mill is fine powder more than 100 orders;
⑶. proportioning: above-mentioned each fine powder is mixed by composition and ratio;
⑷. ball processed: mixed raw material is made the ball that granularity is 10-30mm through the dry-pressing apparatus for making pearl ball;
⑸. oven dry: the ball that is 10-30mm to the above-mentioned granularity that makes toasts;
⑹. electric smelting: to putting into the Medium Frequency Induction Heating Furnace high temperature melting through the ball of overbaking, make it form homogeneous, stable Composite burden;
⑺. slag tap:
⑻. cooling: pour above-mentioned Composite burden in furnace charge basin naturally cooling;
⑼. fragmentation: cooled furnace charge is broken, sub-sieve, make the product that granularity is 2-8mm;
⑽. check: the said products is tested;
⑾. packing: the product that is up to the standards is packed;
⑿. warehouse-in: the product warehousing after packing is deposited.
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|---|---|---|---|
| CN201210285609.9A CN102994768B (en) | 2012-08-13 | 2012-08-13 | Electro-slag re-melting slag and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210285609.9A CN102994768B (en) | 2012-08-13 | 2012-08-13 | Electro-slag re-melting slag and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN102994768A true CN102994768A (en) | 2013-03-27 |
| CN102994768B CN102994768B (en) | 2014-04-02 |
Family
ID=47923873
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|---|---|---|---|
| CN201210285609.9A Expired - Fee Related CN102994768B (en) | 2012-08-13 | 2012-08-13 | Electro-slag re-melting slag and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103233131A (en) * | 2013-05-08 | 2013-08-07 | 武汉钢铁(集团)公司 | Electroslag remelting slag for smelting plastic mould steel and preparation method thereof |
| CN105714125A (en) * | 2016-03-09 | 2016-06-29 | 西峡龙成冶金材料有限公司 | Electroslag remelting slag and production technology thereof |
| CN105936978A (en) * | 2016-06-24 | 2016-09-14 | 东北大学 | Slag system for preparing high-nitrogen austenitic stainless steel through pressurizing electroslag remelting gas phase nitriding |
| CN105950883A (en) * | 2016-06-24 | 2016-09-21 | 东北大学 | Slag system for preparing high-nitrogen martensitic stainless steel by adopting pressurized electroslag remelting gas-phase nitriding |
| CN108034834A (en) * | 2017-11-14 | 2018-05-15 | 邢台钢铁有限责任公司 | Production method of pre-melted slag for small-batch electroslag remelting |
| CN109604565A (en) * | 2018-12-24 | 2019-04-12 | 湖南三泰新材料股份有限公司 | A kind of device and preparation method of electroslag melting stainless steel composite base |
| CN111187918A (en) * | 2020-01-22 | 2020-05-22 | 上海电气上重铸锻有限公司 | A method for controlling non-metallic inclusions in 9Ni steel ingots over 30 tons |
| CN111378848A (en) * | 2020-04-07 | 2020-07-07 | 中国航发北京航空材料研究院 | Pre-melted slag for electroslag remelting for improving purity of GH4169 alloy return and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103233131A (en) * | 2013-05-08 | 2013-08-07 | 武汉钢铁(集团)公司 | Electroslag remelting slag for smelting plastic mould steel and preparation method thereof |
| CN105714125A (en) * | 2016-03-09 | 2016-06-29 | 西峡龙成冶金材料有限公司 | Electroslag remelting slag and production technology thereof |
| CN105936978A (en) * | 2016-06-24 | 2016-09-14 | 东北大学 | Slag system for preparing high-nitrogen austenitic stainless steel through pressurizing electroslag remelting gas phase nitriding |
| CN105950883A (en) * | 2016-06-24 | 2016-09-21 | 东北大学 | Slag system for preparing high-nitrogen martensitic stainless steel by adopting pressurized electroslag remelting gas-phase nitriding |
| CN105936978B (en) * | 2016-06-24 | 2017-12-29 | 东北大学 | A kind of electroslag remelting gas nitriding that pressurizes prepares the slag system of high-nitrogen austenitic stainless steel |
| CN108034834A (en) * | 2017-11-14 | 2018-05-15 | 邢台钢铁有限责任公司 | Production method of pre-melted slag for small-batch electroslag remelting |
| CN108034834B (en) * | 2017-11-14 | 2019-10-18 | 邢台钢铁有限责任公司 | Production method of pre-melted slag for small-batch electroslag remelting |
| CN109604565A (en) * | 2018-12-24 | 2019-04-12 | 湖南三泰新材料股份有限公司 | A kind of device and preparation method of electroslag melting stainless steel composite base |
| CN111187918A (en) * | 2020-01-22 | 2020-05-22 | 上海电气上重铸锻有限公司 | A method for controlling non-metallic inclusions in 9Ni steel ingots over 30 tons |
| CN111378848A (en) * | 2020-04-07 | 2020-07-07 | 中国航发北京航空材料研究院 | Pre-melted slag for electroslag remelting for improving purity of GH4169 alloy return and preparation method thereof |
| CN111378848B (en) * | 2020-04-07 | 2022-03-15 | 中国航发北京航空材料研究院 | Pre-melted slag for electroslag remelting for improving purity of GH4169 alloy return and preparation method thereof |
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