CN107653416B - One kind having high tenacity, high iso advanced hot die steel ZW868 - Google Patents

One kind having high tenacity, high iso advanced hot die steel ZW868 Download PDF

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CN107653416B
CN107653416B CN201710716046.7A CN201710716046A CN107653416B CN 107653416 B CN107653416 B CN 107653416B CN 201710716046 A CN201710716046 A CN 201710716046A CN 107653416 B CN107653416 B CN 107653416B
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die steel
hot die
hot
carbide
high tenacity
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CN107653416A (en
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冯明明
刘道献
赵伟东
曹立军
姚宏康
张健
张长春
张海英
王建华
崔瑞婷
蒋大鹏
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Tangshan Zhiwei Yulong Roll Technology Co ltd
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TANGSHAN ZWELL TECHNOLOGY Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C21D1/32—Soft annealing, e.g. spheroidising
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/008—Heat treatment of ferrous alloys containing Si
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum

Abstract

The present invention relates to high tenacity, high iso hot die steel ZW868, it is 0.35-0.40%, Si≤0.25% that group, which becomes C, Mn is 0.30-0.50%, Cr is 5.00-5.30%, Mo 2.20-2.40%, V 0.50-0.65%, P≤0.010%, S≤0.001%, Ni≤0.20%, Cu≤0.10%, Nb is 0.005-0.020%, and surplus is Fe and inevitable impurity.The mould steel spheroidizing state microscopic structure is uniform, there is the crystal grain distribution of preferable spherodized structure and fine uniform；Impact fracture pattern has more quasi- understanding face and dimple band to make it have high tenacity, high tropism.It can be used for manufacturing hot-extrusion mold, plug, die hammer hammer mould, forging press mold into shape, and use for finish forge machine mold especially can be used as the high-end compression mod with aluminium, copper and its alloy.

Description

One kind having high tenacity, high iso advanced hot die steel ZW868
Technical field
The invention belongs to technical field of alloy steel, and in particular to one kind has high tenacity, high iso advanced Forming Die Has steel ZW868, which is suitable for the use of high-end compression mod.
Background technique
Hot die steel is the important component of mould steel, is mainly used for making red-hot solid-state under certain load Metal generates plastic deformation, or would be heated to the solid metallic or high-temp liquid metal of recrystallization temperature or more as die casting Compression moulding.It is compared with the purposes of other molds, its working environment is more severe, its alloying element content is higher.With Development of the modern manufacturing industry to large size, complexity, precision, high efficiency, high life direction, proposes more the performance of hot die steel High requirement.Hot die steel ZW868 proposed by the present invention, based on H13 steel, using reducing, Si, V content and raising Mo are first Micro Nb is added to steel grade while cellulose content and carries out alloying element design, and the preferable structure property of the product and mechanical property are more Requirement of the modern production to high terminal mould is adapted to well.
Summary of the invention
The present invention proposes a kind of with high tenacity, high iso advanced hot die steel ZW868.Wherein ZW868 is to be somebody's turn to do The trade mark title of hot die steel.The product annealed state microstructure is uniform, there is preferable spherodized structure and fine uniform Crystal grain distribution, tempered structure of quenching is uniform, the tiny precipitated phase of Mo, Cr carbide play in use dispersion-strengtherning work With, improve the performance of material, make material have high tenacity, high tropism.The product can be widely used for manufacture hot-extrusion mold, The hammer mould of plug, die hammer, forging press mold, use for finish forge machine mold especially can be used as with the high-end of aluminium, copper and its alloy Compression mod.
It is realized especially by following technological means:
A kind of high tenacity, high tropism hot die steel, hot die steel content meter by mass percentage are as follows: C is 0.35-0.40%, Si≤0.25%, Mn 0.30-0.50%, Cr 5.00-5.30%, Mo 2.20-2.40%, V are 0.50-0.65%, P≤0.010%, S≤0.001%, Ni≤0.20%, Cu≤0.10%, Nb 0.005-0.020%, it is remaining Amount is Fe and inevitable impurity.
The hot die steel spheroidizing state microstructure is uniform, and tiny spherical proeutectoid carbide is uniformly distributed in On ferrite matrix, (3.45~4.72) × 10 are dispersed in every square millimeter of ferrite base bulk area in section4A secondary carbon Compound, the size range of the proeutectoid carbide is in 400~1000nm.
The hot die steel keeps the temperature 30min, oil quenching to room temperature, 605 DEG C are tempered 2 times through 1025 ± 10 DEG C of austenitizings Afterwards, in the microstructure in centre: the carbide that main body is Mo and Cr disperse educt on matrix, shape are irregular spherical Perhaps elongated rod shape equivalent diameter or length range are in 80~300nm.
The hot die steel cleavage surface and dimple band subject to fracture apperance main body after impacting.
The types of bodies of the proeutectoid carbide of the spheroidizing is M23C6, M7C3 and M6C type, in M23C6 and M7C3 Bulk alloy element is Cr, and the bulk alloy element in M6C is Mo and Cr.
The hot die steel core part keeps the temperature 30min through 1025 ± 10 DEG C of austenitizings, and oil quenching is at least tempered 2 It is secondary, carry out non-notch impact, it is ensured that single non-notch side knock function >=380J, average intact when 45 ± 1HRC of final hardness Mouth side knock performance >=400J；The ratio between horizontal, longitudinal non-notch ballistic work (etc. tropisms) >=0.96.
The method of above-mentioned microstructure of the invention as follows obtains:
(1) electric furnace smelting carries out the ingredient of the pig iron and alloy material according to the constituent content of hot die steel, melts in electric furnace Change and smelt, oxidation is skimmed when temperature is 1630~1650 DEG C, and Antaciron, lime, fluorite are added after skimming, and tapping temperature is 1650~1660 DEG C, in tapping process plus aluminium carries out deoxidation.
(2) LF furnace refines, and connects argon gas after entering LF furnace, then feeding temperature-raising, and lime and fluorite adjustment clinker flowing is added Property, using SiC powder and aluminum shot diffusive deoxidation, the heating and thermal insulation time is 10~20min, sampling analysis after slag is white, when white slag is kept Between be 30~50min, trimming is carried out after sampling analysis based on the analysis results, LF furnace tapping temperature is 1680~1690 ℃。
(3) VD is refined, final vacuum < 67Pa, keeps 18~35min of the final vacuum, sampling point after vacuum breaker Analysis, soft blow enters argon gas to bull ladle after ingredient is qualified, and the time of soft blow argon gas is 18~39min, and bull ladle temperature is 1550~1568 ℃。
(4) casting electrode base, preheating ingot mould are 80~200 DEG C, are then filled with argon gas to ingot mould, when each wharve applying argon gas Between be 3~5min, then withdraw from tunger tube, cast after being covered ingot mould with lid, casting overall process is using carrying additionally asbestos The argon gas protective casting part of cloth is protected, and it is 15~26m that argon gas, which protects flow,3/ h, casting time are 4~8min, electrode billet Diameter is 560~610mm, is demoulded after 3~5h.
(5) it anneals, 710~760 DEG C of annealing temperature, 1~1.5min/mm of soaking time is furnace-cooled to 300~350 DEG C.
(6) electroslag remelting, the electrode billet obtained using step (4), removing surface polishing, using calcirm-fluoride and aluminium oxide two First slag system is smelted, and the molten speed value of the starting point of electroslag smelting steady-state process is 7~10kg/min, the molten speed value of terminal for 5.0~ 8.0kg/min obtains ESR ingot, then send forging process after the cold 80~100min of power failure furnace.
(7) it forges, the ESR ingot that step (6) obtains is heated to 1240~1260 DEG C, 15~25h of heat preservation is diffused Then matter is again heated to 1240~1260 DEG C, 15~25h of heat preservation is diffused then through upset pulling hammer cogging Matter, then carry out again tri- directions X, Y and Z it is upset after pulled out again to finished size.
(8) workpiece that step (7) obtains is placed in heating furnace and is warming up to 1010~1040 DEG C with furnace by ultra fine, Keep the temperature 5~10h after, cooled down using sky-water-sky-water gap type of cooling, specifically: come out of the stove be air-cooled to surface 840~ At 860 DEG C, be quickly put into 25~30 DEG C of water and cooled down, water cooling to after 860 DEG C~890 DEG C of central temperature, air-cooled 2~ Then 5min is reentered after being water-cooled to 700 DEG C~730 DEG C of central temperature, air-cooled 2~5min is entered back into and is cooled to center portion in water 540 DEG C~560 DEG C or so of temperature, then workpiece is cooled down into 0.5h~2h in air, so that workpiece surface highest returns temperature is 300~330 DEG C, be that 250 DEG C of -300 DEG C or so fed to boiler carry out spheroidizing to surface temperature.
(9) spheroidizing in the workpiece merging annealing furnace for obtaining step (8), is heated to 830~860 DEG C, and heat preservation 25~ 45h carries out spheroidizing, obtains the product of spheroidizing.
Then the specific processing step of performance detection is carried out:
(10) centre on blank along section cuts horizontal, longitudinal non-notch impact specimen, specimen size be 7mm × 10mm × 55mm, sample, to 1020~1040 DEG C, keep the temperature 30min oil quenching to room temperature with stove heating.
(11) it is tempered, by the impact specimen merging tempering furnace obtained after step (10) quenching, is heated to 600~630 DEG C, Soaking time 120min, is then air-cooled to room temperature.
(12) tempering step 2~3 times of step (11) are repeated, so that impact specimen hardness carries out after reaching 44~46HRC Ballistic work performance detection.
Effect of the invention is that:
1, the mold materials spheroidizing state microstructure is uniform, and tiny spherical proeutectoid carbide is uniformly distributed in iron On ferritic matrix, density is every 1mm2(3.45~4.72) × 10 are dispersed on area4A carbide, the ruler of proeutectoid carbide For very little range in 400~1000nm, the type of carbide mainly has M23C6, M7C3, M6C type, contained by different types of carbide Main alloy element is different, and the main alloy element in M23C6 and M7C3 is Cr, and the main alloy element in M6C is Mo and Cr； It grades by NADCA#207-2011 standard, rank reaches within AS6.It is abundant that the spherodized structure is conducive to austenitization Dissolution reduces undissolved carbide quantity and size.Tempered process disperse educt again achievees the purpose that improve impact flexibility.
2, the mold materials most of alloying elements in quenching process are dissolved into matrix, from matrix in drawing process Upper disperse educt, the predominantly carbide of Mo, Cr.Exactly these tiny precipitated phases play dispersion-strengtherning work in use With improving the performance of material.The single non-notch side knock function >=380J of the mold materials center portion, average non-notch laterally rush Hit performance >=400J；The ratio between horizontal, longitudinal non-notch ballistic work (etc. tropisms) >=0.96.
Detailed description of the invention
Fig. 1 is hot die steel spheroidizing organization chart of the present invention.
Fig. 2 is the microstructure schematic diagram of hot-work die tempered structure of the present invention.
Fig. 3 is a kind of embodiment position impact specimen microfractograph schematic diagram of hot-work die of the present invention.
Fig. 4 is a kind of other position impact specimen microfractograph schematic diagram of embodiment of hot-work die of the present invention.
Specific embodiment
Embodiment 1
A kind of high tenacity, high tropism ZW868 hot forming dies materials, the ingredient and its percentage composition of the mold materials are as follows:
Embodiment 2
A kind of high tenacity, high tropism ZW868 hot forming dies materials, the ingredient and its percentage composition of the mold materials are as follows:
Embodiment 3
A kind of high tenacity, high tropism ZW868 hot forming dies materials, the ingredient and its percentage composition of the mold materials are as follows:
Sampling carries out microstructure observation on high tenacity of the present invention, high tropism ZW868 die steel material and performance is surveyed Examination:
Spheroidizing tissue: sampling in cross section center portion, in 500 × times lower progress spheroidizing histological test, tiny ball Shape proeutectoid carbide is uniformly distributed on ferrite matrix, and density is every 1mm2(3.45~4.72) × 10 are dispersed on area4 A carbide, for the size range of proeutectoid carbide in 400~1000nm, the type of carbide mainly has M23C6, M7C3, M6C Type, main alloy element contained by different types of carbide is different, and the main alloy element in M23C6 and M7C3 is Cr, M6C In main alloy element be Mo and Cr；Attached drawing 1 is graded by NADCA#207-2011 standard, and rank reaches within AS6, Uniform spherodized structure, finally to quench, tempering heat treatment performs structural preparation；
Grain size: in 1/2 position sample of cross section, sample is through 1020 DEG C of austenitizings, heat preservation 30min, and grade quench is extremely 710 DEG C of heat preservation 30min, are then air-cooled to room temperature.Uniform small grains reach 8.0 grades of 6394 grain size of GB/T；
Quench tempered structure: sample keeps the temperature 30min, oil quenching, 605 DEG C are tempered 2 times through 1025 ± 10 DEG C of austenitizings.Quenching Most of alloying elements are dissolved into matrix in the process, in drawing process from matrix disperse educt, they be irregular ball Shape perhaps elongated rod shape equivalent diameter or length range in 80~300nm, the predominantly carbide of Mo, Cr.As shown in Figure 2.Just It is that these tiny precipitated phases play dispersion-strengthened action in use, improves the performance of material；
Impact flexibility experiment: taking lateral impact sample on blank, and specimen size is 7mm × 10mm × 55mm, sample warp 1025 ± 10 DEG C of austenitizings keep the temperature 30min, and oil quenching, 605 DEG C are tempered 2 times, it is ensured that when 45 ± 1HRC of final hardness, single nothing Notch side knock function >=380J, average non-notch side knock performance >=400J；The ratio between horizontal, longitudinal non-notch ballistic work (etc. Tropism) >=0.96.Specific inspection result is as shown in table 1；
Impact specimen Fracture scan: taking an impact specimen (impact value 400J), and using scanning electron microscopic observation, its fracture is micro- Pattern is seen, as shown in Figure 3, Figure 4.Formation of crack macro morphology is shown in attached drawing 3, and the flatness in fracture macro face reduces, and has tearing Obvious characteristic；Fracture origin high power pattern such as Fig. 4, the negligible amounts in grain boundary fracture face, size is smaller, and fracture face major part region is in Existing Quasi cleavage pattern, section big rise and fall have more tearing feature, and torn grain is that a large amount of shallow dimples are constituted, and dimple size is equal Even tiny, this is all the good feature of impact flexibility.
Mechanics properties testing the results are shown in Table 1:
1 ZW868 mechanical property result of table

Claims (3)

1. a kind of high tenacity, high tropism hot die steel, which is characterized in that hot die steel content by mass percentage It is calculated as: C 0.35-0.40%, Si≤0.25%, Mn 0.30-0.50%, Cr 5.00-5.30%, Mo 2.20- 2.40%, V 0.50-0.65%, P≤0.010%, S≤0.001%, Ni≤0.20%, Cu≤0.10%, Nb 0.005- 0.020%, surplus is Fe and inevitable impurity；
The hot die steel spheroidizing state microstructure is uniform, and tiny spherical proeutectoid carbide is uniformly distributed in iron element On body matrix, (3.45~4.72) × 10 are dispersed in every square millimeter of ferrite base bulk area in section4A proeutectoid carbide, The size range of the proeutectoid carbide is in 400~1000nm；
The hot die steel keeps the temperature 30min through 1025 ± 10 DEG C of austenitizings, oil quenching to room temperature, and 605 DEG C after tempering 2 times, in Quenching for center portion position is tempered in state microstructure: the carbide that main body is Mo and Cr disperse educt, shape on matrix are irregular Spherical perhaps elongated rod shape equivalent diameter or length range are in 80~300nm；
The hot die steel cleavage surface and dimple band subject to fracture apperance main body after impacting.
2. high tenacity according to claim 1, high tropism hot die steel, which is characterized in that the spheroidizing state The types of bodies of proeutectoid carbide is M23C6, M7C3 and M6C type in microstructure, the bulk alloy in M23C6 and M7C3 Element is Cr, and the bulk alloy element in M6C is Mo and Cr.
3. high tenacity according to claim 1 or 2, high tropism hot die steel, which is characterized in that the hot-work die Steel core part keeps the temperature 30min through 1025 ± 10 DEG C of austenitizings, and oil quenching is at least tempered 2 times, carries out non-notch impact, it is ensured that When 45 ± 1HRC of final hardness, single non-notch side knock function >=380J, average non-notch side knock performance >=400J； The ratio between horizontal, longitudinal non-notch ballistic work >=0.96.
CN201710716046.7A 2017-08-10 2017-08-10 One kind having high tenacity, high iso advanced hot die steel ZW868 Active CN107653416B (en)

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CN109957702A (en) * 2019-02-26 2019-07-02 唐山志威科技有限公司 The preparation method of high rigidity, high tenacity development machine cutter ring steel ZW552
CN109957720B (en) * 2019-02-26 2020-09-22 唐山志威科技有限公司 High-hardness and high-toughness ZW552 steel for heading machine cutter ring
CN111593257B (en) * 2019-09-07 2021-10-01 江苏宏晟模具钢材料科技有限公司 High-toughness and high-thermal-stability hot-work die steel and preparation method thereof
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