CN114990440B - Powder metallurgy high-speed steel wire and preparation method thereof - Google Patents

Powder metallurgy high-speed steel wire and preparation method thereof Download PDF

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CN114990440B
CN114990440B CN202210618275.6A CN202210618275A CN114990440B CN 114990440 B CN114990440 B CN 114990440B CN 202210618275 A CN202210618275 A CN 202210618275A CN 114990440 B CN114990440 B CN 114990440B
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powder
cooling
temperature
keeping
alloy
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CN114990440A (en
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陈业高
彭凌剑
潘海成
邵国友
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Jiangsu Applied Element Technology Co ltd
Suqian College
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Jiangsu Applied Element Technology Co ltd
Suqian College
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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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/142—Thermal or thermo-mechanical treatment
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/145—Chemical treatment, e.g. passivation or decarburisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007—Atmosphere
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    • 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
    • B22F3/115—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by spraying molten metal, i.e. spray sintering, spray casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B22F3/24—After-treatment of workpieces or articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/12—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of wires
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
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    • B22F9/14—Making metallic powder or suspensions thereof using physical processes using electric discharge
    • 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
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • 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
    • C21D6/04—Hardening by cooling below 0 degrees Celsius
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/16—Remelting metals
    • C22B9/18—Electroslag remelting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0207—Using a mixture of prealloyed powders or a master alloy
    • C22C33/0228—Using a mixture of prealloyed powders or a master alloy comprising other non-metallic compounds or more than 5% of graphite
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    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • C22C33/06—Making ferrous alloys by melting using master alloys
    • 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
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
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    • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
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    • C22C38/30—Ferrous alloys, e.g. steel alloys containing chromium with cobalt
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/36—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.7% by weight of carbon
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    • 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
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/248—Thermal after-treatment
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    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention relates to the technical field of powder metallurgy, and discloses a powder metallurgy high-speed steel wire and a preparation method thereof, wherein the powder metallurgy high-speed steel wire comprises the following components in percentage by weight: c: 1.5-1.8%, mn: 0.28-0.38%, si: 0.6-0.75%, cr: 3.8-4.5%, V or Nb+V: 2.8-3.2%, W: 5.8-6.5%, mo: 4.8-5.5%, co: 7.8-8.5%, ti: 1.8-2.3%, re: 1-3%, S: <0.03%, P: <0.05%, o+n+h: <0.005%, the balance being Fe. The powder metallurgy high-speed steel prepared by the method has the advantages of fine structure, uniform carbide, less harmful impurity quantity, and obviously improved bending strength, toughness and wear resistance.

Description

Powder metallurgy high-speed steel wire and preparation method thereof
Technical Field
The invention relates to the technical field of powder metallurgy, in particular to a high-speed steel wire for powder metallurgy and a preparation method thereof.
Background
The high-speed steel has the characteristics of high hardness, high strength and good wear resistance, and is widely applied to the manufacturing of precision cutters and the manufacturing industry of dies. Compared with the traditional cast high-speed steel, the high-speed steel prepared by the powder metallurgy method remarkably improves the problem of carbide segregation in the microstructure, and greatly improves the mechanical property of the material and the stability during working. The current commercial powder metallurgy high-speed steel is mainly prepared by an air atomization alloy powder-hot isostatic pressing combination method, the obtained high-speed steel has obvious fine grain structure, carbides are uniformly distributed, the strength performance is above 3500MPa, the performance of part of brands can reach above 4000MPa, but the large-scale application of the high-speed steel is severely limited due to high production cost. Research reports that the densification of the material can be basically realized at 1160 ℃ by utilizing the mode of ball milling activation and cold pressing sintering of commercial M2 alloy powder doped with vanadium nitride powder, the relative density is up to 99.4%, the strength performance can be maintained at about 2500-3000 MPa, and the production cost is greatly reduced. Accordingly, the invention aims to disclose a method for preparing low-cost and high-performance powder metallurgy high-speed steel by a cold-press sintering method.
Disclosure of Invention
The invention aims to: aiming at the problem of low service life of high-speed steel materials, the invention provides the powder metallurgy high-speed steel wire and the preparation method thereof, and the prepared powder metallurgy high-speed steel has the advantages of fine structure, uniform carbide, less harmful impurity quantity and obviously improved bending strength, toughness and wear resistance.
The technical scheme is as follows: the invention provides a powder metallurgy high-speed steel wire, which comprises the following components in percentage by weight: c: 1.5-1.8%, mn: 0.28-0.38%, si: 0.6-0.75%, cr: 3.8-4.5%, V or Nb+V: 2.8-3.2%, W: 5.8-6.5%, mo: 4.8-5.5%, co: 7.8-8.5%, ti: 1.8-2.3%, re: 1-3%, S: <0.03%, P: <0.05%, o+n+h: <0.005%, the balance being Fe.
The invention also provides a preparation method of the powder metallurgy high-speed steel wire, which comprises the following steps: s1: smelting a master alloy: taking pure metal of raw material Fe, pure metal or intermediate alloy of W, mo, co, V, nb, cr and intermediate alloy of C-Fe, si-Fe, mn-Fe and Ti-C, re-M according to the proportion, and drying all raw materials; at a vacuum level of 10 -5 ~10 3 Smelting master alloy under the condition of Pa; firstly, melting pure metal in Fe, W, mo, co, V, nb, cr at 1380-1580 ℃, and preserving heat for 10-15 min; adding W, mo, co, V, nb, cr intermediate alloy and C-Fe, si-Fe and Mn-Fe intermediate alloy at 1280-1580 ℃, preserving heat for 10-15 min, stirring uniformly, and removing slag; adding a block material pressed by Ti-C powder at 1280-1580 ℃ again, and preserving heat for 15-35 min; then adding Re-M intermediate alloy at 1280-1480 ℃, preserving heat for 3-5 min, and carrying out electromagnetic stirring all the time in the heat preservation process; finally casting in a vacuum furnace and discharging to obtain master alloy; s2: electroslag purification: electroslag remelting is carried out on the master alloy prepared in the step S1, and the slag system of the electroslag is CaF 2 -CaO-Al 2 O 3 -TiO 2 The content is 65-70%, 10-15% and 5-10% respectively; s3: pulverizing: pulverizing the master alloy purified by the S2 electroslag to obtain alloy powder; s4: annealing and compacting: alloy powderSequentially carrying out reduction annealing and powder compacting to prepare a powder block blank; s5: sintering: sintering the powder block blank obtained in the step S4; s6: and (3) heat treatment: carrying out grading heat treatment on the sintered powder block blank obtained in the step S5; s7: deformation: forging and/or extruding, rolling and drawing the powder block blank obtained in the step S6 to obtain a wire with the diameter of 1-3 mm; s8: and (3) heat treatment: and (5) carrying out grading heat treatment on the silk material obtained in the step (S7) again.
Preferably, in the step S2, in the process of electroslag remelting, a means of cooling a discharge hole of a crystallizer in an enhanced manner and properly preserving heat on a side wall is adopted to control the temperature gradient of a molten pool, so that an acute angle part interval of an included angle between a solidification direction and the side wall of the molten pool is 0-30 degrees, and a purified master alloy melt is obtained.
Preferably, in the step S3, the master alloy after the purification of the S2 electroslag is transferred into a middle furnace with protective atmosphere protection and a protective layer plated on the inner wall of a hearth, and then the powder is directly prepared in the middle furnace, so as to obtain the alloy powder.
Further, in the step S3, the powder preparation method is gas atomization powder preparation, argon atomization is adopted, the purity of the argon is 99.9%, the atomization pressure is 10-30 MPa, and the D50 of the prepared alloy powder is 20-60 mu m; or the powder preparation method is water and gas combined atomization powder preparation, wherein the adopted gas is argon, the purity is 99.9%, the atomization pressure is 10-30 MPa, the water pressure is 8-50 MPa, and the D50 of the prepared alloy powder is 8-20 mu m; or the powder preparation method is ball milling powder preparation, and the D50 of the prepared alloy powder is 8-50 mu m; or the powder preparation method is rotary ionization powder preparation, and the D50 of the prepared alloy powder is 30-70 mu m.
Preferably, in S4, the process of the reduction annealing is as follows: the method comprises the steps of carrying out in a vacuum furnace, wherein the vacuum state or the inert gas protection state is formed in the furnace, spreading powder on a substrate, wherein the thickness of the powder is 5-10 mm, placing a plurality of layers of substrates in a superposition mode, keeping the distance between adjacent substrates at 30-100 mm, keeping the temperature at 400-680 ℃ for 60-300 min, cooling the powder to room temperature along with the furnace, and taking out the powder. In the process, the oxygen content of the atmosphere in the furnace is detected to be less than 10ppm.
Further, in the step S4, the process of the powder compact is a non-HIP compact: weighing the alloy powder subjected to reduction annealing, then placing the alloy powder into a compact die, and performing bidirectional die pressing on the powder to obtain a block blank; the pressure is 500-1200 MPa.
Further, in S5, the sintering mode is normal pressure protective atmosphere sintering: (1) The protective inert gas is injected into the sintering furnace, and oxygen is discharged, so that the oxygen content in the sintering furnace is less than 1ppm; (2) Heating to 650-850 ℃ at a speed of 6-10 ℃/min, and keeping the temperature for a period of time t=3-5 min/cm multiplied by d; (3) Heating to 1180-1260 ℃ at a speed of 8-10 ℃/min, and keeping the temperature for t=10-30 min/cm multiplied by d; (4) cooling to room temperature along with the furnace; where d is the maximum wall thickness of the sample in cm.
Preferably, in S6 and/or S8, the process of the graded heat treatment is as follows: (1) preheating: heating to 580-620 ℃ at a heating rate of 5-10 ℃/min, and keeping the temperature for a period of time t=3-5 min/cm multiplied by d; (2) secondary preheating: heating to 840-860 ℃ at a heating rate of 5-10 ℃/min, and keeping the temperature for a period of time t=2-4 min/cm×d; (3) quenching and heat preservation: heating to 1170-1260 ℃ at a heating rate of 5-10 ℃/min, and keeping the temperature for a period of time t=2-4 min/cm×d; (4) quenching and cooling: next, when d.gtoreq.10, first 10 3 ~10 5 Cooling to 300-500 ℃ at a cooling speed of DEG C/s, keeping the temperature for a period of time t=0.1-1.5 min/cm multiplied by d, and then cooling to 10℃/s 3 ~10 5 Cooling to 20-40 ℃ at a cooling speed of DEG C/s, and keeping the temperature for a period of time t=0.1-1.5 min/cm multiplied by d; when 10 is greater than or equal to d is greater than or equal to 5, the ratio of 10 3 ~10 5 Cooling to 200-400 ℃ at a cooling speed of DEG C/s, keeping the temperature for a period of time t=0.1-1.5 min/cm multiplied by d, and then cooling to 10℃/s 3 ~10 5 Cooling to 20-40 ℃ at a cooling speed of DEG C/s, and keeping the temperature for a period of time t=0.1-1.5 min/cm multiplied by d; when d is less than or equal to 5cm, the ratio is 10 3 ~10 5 Cooling to 20-40 ℃ at a cooling speed of DEG C/s, and keeping the temperature for a period of time t=0.1-1.5 min/cm multiplied by d; (5) cryogenic treatment: immediately after 10 5 ~10 7 Cooling to-50 to-150 ℃ at a cooling speed of the temperature per second, wherein the heat preservation time t=1-2 min/cm multiplied by d; (6) tempering: heating to 560-570 ℃ at a heating rate of 5-10 ℃/min, and keeping the temperature for a period of time t=1-3 h/cm multiplied by d; (7) cooling: then rapidly cooling to 200-300 ℃, keeping the temperature for a period of time t=0.3-1 h/cm multiplied by d, discharging, and air cooling to 20-40 DEG CThe method comprises the steps of carrying out a first treatment on the surface of the (8) repeating (6) and (7) 0-1 times; where d is the maximum wall thickness of the sample in cm. Because of the specificity of the powder high-speed steel, the heat treatment process is also different from that of common metals, and the main differences are that preheating, higher quenching temperature, high tempering temperature and more tempering times are needed; the powder high-speed steel bar after deformation has large internal stress and high hardness, so that annealing is needed first. The annealing temperature is 840-880 ℃, and the annealing time t=2-20 min/cm×d. The high-speed steel has more alloy element content and poor thermal conductivity, and the high-speed steel needs to be preheated before being heated, wherein the preheating temperature is 580-620 ℃ and 840-880 ℃ in sequence, and the preheating time t=2-5 min/cm multiplied by d. The quenching temperature is 1170-1260 ℃, and the quenching is performed by water cooling or oil cooling to room temperature. Finally, tempering is carried out for three times at 560-570 ℃, and each time, the heat preservation time t=1-3 h multiplied by d. The tempering of high-speed steel must be performed at four points: the tempering is needed to be performed in time after the quenching, or the austenite is stabilized, so that the retained austenite is not easy to eliminate (generally not more than 8 hours), (2) the tempering temperature is required to be uniform, preferably in a salt bath furnace or a well tempering furnace with a fan, the heating is required to be uniform, (3) the tempering is needed to be cooled to room temperature after each tempering so as to repeat each tempering, and (4) the tempering is needed to be cooled to room temperature so as to be cleaned, otherwise, the tempering is easy to deform and crack. The grains and the second phase of the powder high-speed steel prepared under the condition are refined uniformly, and fine and dispersed granular carbide is distributed on a tempered martensite base. The non-closed pores are circular or oval. The hardness reaches 67.5HRC, the red hardness reaches 63.2HRC, and the bending strength can reach 4146.3MPa. Preferably, in the step S6, the annealing treatment before deformation is performed as follows: heating the powder block blank to 850-870 ℃ in a vacuum furnace or a salt bath furnace at a heating rate of less than or equal to 2.5 ℃/min, preserving heat for 110-130 min, heating to 1100-1300 ℃ at a heating rate of less than or equal to 400 ℃/h, preserving heat for 15-30 min, then cooling to 850-870 ℃, preserving heat for 60-120 min, then cooling to 500-600 ℃ in the furnace at a cooling rate of 10-30 ℃/h, and then cooling to about 200 ℃ in an air or cooling with the furnace, and then discharging and cooling to room temperature.
The invention also provides a preparation method of the powder metallurgy high-speed steel wire, which comprises the following steps: s1: taking pure metal of raw material Fe according to a proportion, W, mo, co, V, nbPure metals or intermediate alloys of Cr and intermediate alloys of C-Fe, si-Fe, mn-Fe and Ti-C, re-M, and drying all the raw materials; at a vacuum level of 10 -5 ~10 3 Smelting master alloy by adopting a vacuum induction smelting technology under the condition of Pa; firstly, melting pure metal in Fe, W, mo, co, V, nb, cr at 1380-1580 ℃, and preserving heat for 10-15 min; adding W, mo, co, V, nb, cr intermediate alloy and C-Fe, si-Fe and Mn-Fe intermediate alloy at 1280-1580 ℃, preserving heat for 10-15 min, stirring uniformly, and removing slag; adding a block material pressed by Ti-C powder at 1280-1580 ℃ again, and preserving heat for 15-35 min; then adding Re-M intermediate alloy at 1280-1480 ℃, preserving heat for 3-5 min, and carrying out electromagnetic stirring all the time in the heat preservation process; finally casting in a vacuum furnace and discharging to obtain master alloy; s2: electroslag remelting is carried out on the master alloy prepared in the step S1; s3: dropwise casting the master alloy subjected to S2 electroslag remelting into a copper mold in a protective atmosphere to obtain a dropwise cast ingot; s4: crushing the cast ingot of the step S3, and ball milling to prepare powder; s5: sequentially carrying out reduction annealing and powder compaction on the S4 alloy powder to prepare a powder block blank; s6: sintering the powder block blank obtained in the step S5; s7: carrying out grading heat treatment on the sintered powder block blank obtained in the step S6; s8: forging and/or extruding, rolling and drawing the powder block blank obtained in the step S7 to obtain a wire with the diameter of 1-3 mm; s9: and (5) carrying out grading heat treatment on the silk material obtained in the step (S8) again.
Preferably, in S4, the process of ball milling is as follows: s4-1: crushing the drop casting ingot obtained in the step S3 to 0.1-1 mm; s4-2: mixing the powder into alcohol by using a planetary ball mill, wherein the weight ratio of the ball to the powder is 3-6: 1, grinding for 24-72 hours; s4-3: drying the ground mixed slurry at 75-80 ℃ for 5-10 hours, sieving, and transferring the mixed slurry into a drying chamber with low oxygen partial pressure for certain pre-oxidation; s4-4: and (3) sealing and storing the powder obtained in the step S3.
Preferably, tiC, VN, WC, mo is also added in the ball milling process 2 C、Cr 3 C 2 One or a combination of VC and NbC powder. Because of element burning during smelting, the components of the powder are slightly deviated after being made into powder, and carbide or nitrogen of corresponding alloy elements are addedThe composition of the raw powder can be precisely adjusted to the upper or lower limit to better determine the microstructure and ultimately the properties.
Further, in step S6, the sintering manner is HIP sintering: (1) Filling the powder block blank into a hollow shell, vacuumizing and sealing; (2) Heating to 600-700 ℃ at a speed of 8-12 ℃/min, and keeping the temperature for a period of time t=2-8 min/cm multiplied by d; (3) Heating to 1100-1250 ℃ at a speed of 5-15 ℃/min, and keeping the temperature for a period of time t=15-25 min/cm multiplied by d; (4) cooling to room temperature along with the furnace; where d is the maximum wall thickness of the sample in cm.
The beneficial effects are that: (1) In the invention, during electroslag remelting, the slag system of the electroslag is CaF 2 -CaO-Al 2 O 3 -TiO 2 Nonmetallic inclusion falling off from the inner wall of a hearth and the surface of a casting mold in the smelting stage of the master alloy can be removed, the purity of the master alloy is improved, the problem of stress concentration caused by nonmetallic inclusion is reduced, and the toughness and fatigue resistance of the material are improved; and due to the addition of TiO to the slag system 2 According to the chemical kinetics balance principle, the Ti in the master alloy can be prevented from diffusing to the slag layer, the yield of the Ti in the master alloy is improved, grains are refined, and the performance is improved.
(2) In the invention, the master alloy after electroslag purification is directly transferred into an intermediate furnace and then atomized to prepare powder, and the method has the advantages that the purity of the master alloy after electroslag purification is higher, secondary pollution caused by remelting is avoided, and the purity of the obtained powder is higher, and compared with the common method, the content of nonmetallic inclusion and harmful gas is reduced by 90%.
(3) In the invention, re rare earth elements are added into the components, and the components are mainly used for removing impurity element oxygen. Because the chemical property of Re element is very active, almost all metal oxides can be reduced to generate Re-O oxides with stable property, not only can the components be purified and the harm of harmful element O be reduced, but also the Re-O oxides formed can be used as the core of heterogeneous nucleation, so that the heterogeneous nucleation rate is increased, the grains are refined, and the toughness is improved. In addition, the intermediate alloy of Re-M is added in the vacuum smelting and electroslag refining stages respectively, so as to improve the utilization rate of Re-M, prevent the burning loss from being too serious when the vacuum smelting stages are all added, and can not ensure that oxygen in the melt is sufficiently removed, so that the melt is purer finally.
(4) TiC, VN, WC, mo is added during the preparation process 2 C、Cr 3 C 2 Alloy powder such as VC, nbC and the like provides a large number of cores with heterogeneous nucleation for solidification and recrystallization, promotes heterogeneous nucleation, plays a role in refining grain and carbide size, and is beneficial to improving mechanical properties such as hardness, wear resistance, bending strength and the like of the material.
(5) In the invention, the master alloy after electroslag remelting is dripped into a copper mold in protective atmosphere to obtain the dripped cast ingot, and the method has the advantages that: the drop casting liquid drop size is small, the solidification speed is high, the segregation of alloy elements can be effectively inhibited, the alloy components are more uniform, and the method is very important for ensuring the performance of high-speed steel; drop casting into copper mould, which can make heat quickly dispersed, further quicken solidification speed and ensure uniformity of components; drop casting is carried out in protective atmosphere, so that oxygen in the air is prevented from polluting a solution, and the harm of oxygen is reduced; the cast ingot subjected to drop casting has a plurality of weld marks, so that the cast ingot is convenient to break in the next step.
(6) According to the invention, the material is subjected to graded quenching according to the wall thickness, and different isothermal temperatures are selected according to different wall thicknesses, so that the temperature of the material and the heat on the surface and the inside of the material can be uniformly and rapidly dissipated, stress cracking caused by uneven heat distribution can be eliminated, and the quenching purpose of the material (the austenite is converted into martensite or lower bainite) can be better realized. In addition, the deep cooling treatment after quenching can further promote the transformation from the retained austenite to the martensite, and improve the hardness and toughness of the material.
Drawings
FIG. 1 is a process diagram of a staged heat treatment (d. Gtoreq.10 or 10. Gtoreq.d. Gtoreq.5);
FIG. 2 is a process diagram of the classification heat treatment (d.ltoreq.5 cm).
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
The invention provides a powder metallurgy high-speed steel wire, which comprises the following components in percentage by weight: c: 1.5-1.8%, mn: 0.28-0.38%, si: 0.6-0.75%, cr: 3.8-4.5%, V or Nb+V: 2.8-3.2%, W: 5.8-6.5%, mo: 4.8-5.5%, co: 7.8-8.5%, ti: 1.8-2.3%, re: 1-3%, S: <0.03%, P: <0.05%, o+n+h: <0.005%, the balance being Fe.
The preparation method of the powder metallurgy high-speed steel wire material comprises the following steps:
example 1:
the embodiment provides a preparation method of a powder metallurgy high-speed steel wire, which comprises the following steps: s1: smelting a master alloy: taking pure metal of raw material Fe, pure metal or intermediate alloy of W, mo, co, V, nb, cr and intermediate alloy of C-Fe, si-Fe, mn-Fe and Ti-C, re-M according to the proportion, and drying all raw materials; at a vacuum level of 10 -5 ~10 3 Smelting master alloy under the condition of Pa; firstly, melting pure metal in Fe, W, mo, co, V, nb, cr at 1380-1580 ℃ and preserving heat for 12min; adding W, mo, co, V, nb, cr intermediate alloy and C-Fe, si-Fe and Mn-Fe intermediate alloy at 1280-1580 ℃, preserving heat for 12min, stirring uniformly, and removing slag; adding a block material pressed by Ti-C powder at 1280-1580 ℃ again, and preserving heat for 30min; then adding an intermediate alloy of Re-M at 1280-1480 ℃, preserving heat for 4min, and carrying out electromagnetic stirring all the time in the heat preservation process; finally casting in a vacuum furnace and discharging to obtain master alloy;
s2: electroslag purification: electroslag remelting is carried out on the master alloy prepared in the step S1, and the slag system of the electroslag is CaF 2 -CaO-Al 2 O 3 -TiO 2 The contents are respectively 70%, 12% and 8%, and the master alloy after electroslag purification is obtained;
and controlling the temperature gradient of the molten pool by a method (coil heating+sensor) of strengthening the cooling capacity of a discharge hole of a crystallizer (using cooling water or directly pulling one end of a blank into water) and insulating the side wall of the molten pool, so that the included angle between the solidification direction and the side wall of the molten pool is kept at 20-30 degrees, and obtaining the purified master alloy melt.
S3: pulverizing: pulverizing the master alloy purified by the S2 electroslag to obtain alloy powder;
the powder preparation method is gas atomization powder preparation, argon gas atomization is adopted, the purity of the argon gas is 99.9%, the atomization pressure is 10MPa, and the D50 of the prepared alloy powder is 20 mu m.
S4: annealing and compacting: sequentially carrying out reduction annealing and powder compacting on the alloy powder to prepare a powder block blank;
the process of the reduction annealing is as follows:
the preparation method comprises the steps of carrying out in a vacuum furnace, laying powder on a substrate in a vacuum state or an inert gas protection state, placing multiple layers of substrates in a superposition manner, keeping the distance between adjacent substrates at 30mm, cooling to room temperature along with the furnace, and taking out. In the process, the oxygen content of the atmosphere in the furnace is detected to be less than 10ppm.
The powder compact process is non-HIP compact: weighing the alloy powder subjected to reduction annealing, then placing the alloy powder into a compact die, and performing bidirectional die pressing on the powder to obtain a block blank; the pressure is 1200MPa.
S5: sintering: sintering the powder block blank obtained in the step S4;
the sintering mode can be normal pressure protective atmosphere sintering: (1) The protective inert gas is injected into the sintering furnace, and oxygen is discharged, so that the oxygen content in the sintering furnace is less than 1ppm; (2) Heating to 650 ℃ at a speed of 10 ℃/min, and keeping the temperature for a period of time t=5 min/cm×d; (3) Heating to 1220 ℃ at a speed of 10 ℃/min, and keeping the temperature for a period of time t=20 min/cm×d; (4) cooling to room temperature along with the furnace; where d is the maximum wall thickness of the sample in cm.
S6: and (3) heat treatment: carrying out grading heat treatment on the sintered powder block blank obtained in the step S5;
the process of the above-mentioned classification heat treatment is as follows (see fig. 1 and 2):
(1) Preheating: heating to 580 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for a period of time t=3 min/cm×d;
(2) Secondary preheating: heating to 840 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for a period of time t=2 min/cm×d;
(3) Quenching and heat preservation: heating to 1170 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for a period of time t=2 min/cm×d;
(4) Quenching and cooling: in the immediate vicinity of the point of use,
when d is greater than or equal to 10, first 10 4 Cooling to 300 deg.C at a cooling rate of deg.C/s, maintaining for a period of time t=1 min/cm×d, and then cooling to 10 deg.C 4 The temperature reduction speed of the temperature/s is reduced to 20 ℃, and the heat preservation time t=1.5 min/cm multiplied by d (as shown in figure 1);
when 10 is greater than or equal to d is greater than or equal to 5, the ratio of 10 5 Cooling to 200deg.C at a cooling rate of 10deg.C/s, maintaining for a period of time t=1 min/cm×d, and cooling to 200deg.C at a cooling rate of 10deg.C/cm×d 4 The temperature reduction speed of the temperature/s is reduced to 40 ℃, and the heat preservation time t=1.5 min/cm×d (as shown in fig. 1);
when d is less than or equal to 5cm, the ratio is 10 5 The temperature reduction speed of the temperature/s is reduced to 40 ℃, and the heat preservation time t=1.5 min/cm×d (as shown in fig. 2);
(5) And (3) deep cooling treatment: immediately after 10 5 Cooling to-100 ℃ at a cooling speed of DEG C/s, and keeping the temperature for t=1 min/cm×d;
(6) Tempering: heating to 560 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for a period of time t=1 h/cm×d;
(7) And (3) cooling: then cooling to 200 ℃ along with the furnace, discharging and air cooling to 40 ℃;
(8) Repeating (6) and (7) at least once;
where d is the maximum wall thickness of the sample in cm.
S7: deformation: forging and/or extruding, rolling and drawing the powder block blank obtained in the step S6 to obtain a wire with the diameter of 2 mm;
the forging process is as follows:
preheating: firstly, heating the blank to 620 ℃ at a heating speed of 8 ℃/min, and keeping the temperature for t=3 min/cm×d; then heating to 860 ℃ at a heating rate of 8 ℃/min, and keeping the temperature for a period of time t=2 min/cm×d; wherein d is the maximum wall thickness of the sample in cm;
forging: forging the blank, wherein the reduction amount is 5% each time, and directly putting the blank into a furnace at 840 ℃ again for heating after each forging, wherein the heating time is t=3 min/cm×d until the blank is forged to the required size;
and (3) cooling: and (3) placing the forged blank into a furnace, cooling to 200 ℃ along with the furnace, and then discharging the blank from the furnace for air cooling to room temperature.
The extrusion mode is hot extrusion, and the process is as follows:
preheating: firstly, heating the blank to 620 ℃ at a heating speed of 7 ℃/min, and keeping the temperature for t=5 min/cm×d; then heating to 900 ℃ at a heating rate of 7 ℃/min, and keeping the temperature for t=4 min/cm×d; wherein d is the maximum wall thickness of the sample in cm;
hot extrusion: the extrusion mode is horizontal extrusion, the extrusion speed is 5mm/s, the single extrusion section is reduced by 8%, and the preheating temperature of an extrusion die is 750 ℃;
and (3) cooling: and (3) placing the extruded blank into a furnace, cooling to 260 ℃ along with the furnace, and then discharging the blank from the furnace for air cooling to room temperature.
S8: and (3) heat treatment: and (5) carrying out grading heat treatment on the silk material obtained in the step (S7) again. The step of the heat treatment is shown in fig. 1 and 2, which are the same as those in S6, and will not be described here again.
Example 2:
this example is similar to example 1, except that in the present embodiment, in step S3, the master alloy obtained by purifying S2 electroslag was pulverized by water and gas combined atomization, the gas was argon gas, the purity was 99.9%, the atomization pressure was 10MPa, the water pressure was 20MPa, and the D50 of the obtained alloy powder was 10 μm.
Otherwise, this embodiment is identical to embodiment 1, and a detailed description thereof will be omitted.
Example 3:
this example is substantially the same as example 1, except that in the present embodiment, in step S3, the master alloy after S2 electroslag refining is milled by ball milling, and the D50 of the produced alloy powder is 50 μm.
Otherwise, this embodiment is identical to embodiment 1, and a detailed description thereof will be omitted.
Example 4:
the embodiment provides a preparation method of a powder metallurgy high-speed steel wire, which comprises the following steps: s1: smelting a master alloy: pressing the buttonProportioning pure metal of raw material Fe, pure metal or intermediate alloy of W, mo, co, V, nb, cr and intermediate alloy of C-Fe, si-Fe, mn-Fe and Ti-C, re-M, and drying all raw materials; at a vacuum level of 10 -5 ~10 3 Smelting master alloy under the condition of Pa; firstly, melting pure metal in Fe, W, mo, co, V, nb, cr at 1380-1580 ℃ and preserving heat for 12min; adding W, mo, co, V, nb, cr intermediate alloy and C-Fe, si-Fe and Mn-Fe intermediate alloy at 1280-1580 ℃, preserving heat for 12min, stirring uniformly, and removing slag; adding a block material pressed by Ti-C powder at 1280-1580 ℃ again, and preserving heat for 30min; then adding an intermediate alloy of Re-M at 1280-1480 ℃, preserving heat for 4min, and carrying out electromagnetic stirring all the time in the heat preservation process; finally casting in a vacuum furnace and discharging to obtain master alloy;
s2: electroslag remelting is carried out on the master alloy prepared in the step S1;
and controlling the temperature gradient of the molten pool by a method (coil heating+sensor) of strengthening the cooling capacity of a discharge hole of a crystallizer (using cooling water or directly pulling one end of a blank into water) and insulating the side wall of the molten pool, so that the included angle between the solidification direction and the side wall of the molten pool is kept at 20-30 degrees, and obtaining the purified master alloy melt.
S3: dropwise casting the master alloy subjected to S2 electroslag remelting into a copper mold in a protective atmosphere to obtain a dropwise cast ingot;
s4: crushing the cast ingot of the step S3, and ball milling to prepare powder;
the ball milling process comprises the following steps:
s4-1: crushing the drop casting ingot obtained in the step S3 to 0.1-1 mm;
s4-2: mixing the powder into alcohol by a planetary ball mill, wherein the weight ratio of the ball to the powder is 5:1, grinding for 50 hours;
s4-3: drying the ground mixed slurry at 78 ℃ for 8 hours, sieving, and transferring the mixed slurry into a drying chamber with low oxygen partial pressure for certain pre-oxidation;
s4-4: and (3) sealing and storing the alloy powder obtained in the step S4-3.
In the ball milling process, by detecting the average composition of the powder, if the alloy element isIs not satisfied, and corresponding addition of TiC, VN, WC, mo 2 C、Cr 3 C 2 One or the combination of VC and NbC powder, so that the finally prepared alloy powder meets the component requirement.
S5: sequentially carrying out reduction annealing and powder compaction on the S4 alloy powder to prepare a powder block blank;
the process of the reduction annealing is as follows:
the preparation method comprises the steps of carrying out in a vacuum furnace, laying powder on a substrate in a vacuum state or an inert gas protection state, placing multiple layers of substrates in a superposition manner, keeping the distance between adjacent substrates at 30mm, cooling to room temperature along with the furnace, and taking out. In the process, the oxygen content of the atmosphere in the furnace is detected to be less than 10ppm.
The powder compact process is non-HIP compact: weighing the alloy powder subjected to reduction annealing, then placing the alloy powder into a compact die, and performing bidirectional die pressing on the powder to obtain a block blank; the pressure is 1200MPa.
S6: sintering the powder block blank obtained in the step S5;
the sintering mode can be normal pressure protective atmosphere sintering: (1) The protective inert gas is injected into the sintering furnace, and oxygen is discharged, so that the oxygen content in the sintering furnace is less than 1ppm; (2) Heating to 650 ℃ at a speed of 10 ℃/min, and keeping the temperature for t=5 min/cm×d; (3) Heating to 1220 ℃ at a speed of 10 ℃/min, and keeping the temperature for a period of time t=20 min/cm×d; (4) cooling to room temperature along with the furnace; where d is the maximum wall thickness of the sample in cm.
S7: carrying out grading heat treatment on the sintered powder block blank obtained in the step S6;
the process of the above-mentioned classification heat treatment is as follows (see fig. 1 and 2):
(1) Preheating: heating to 580 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for a period of time t=3 min/cm×d;
(2) Secondary preheating: heating to 840 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for a period of time t=2 min/cm×d;
(3) Quenching and heat preservation: heating to 1170 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for a period of time t=2 min/cm×d;
(4) Quenching and cooling: in the immediate vicinity of the point of use,
when d is greater than or equal to 10, first 10 4 Cooling to 300 deg.C at a cooling rate of deg.C/s, maintaining for a period of time t=1 min/cm×d, and then cooling to 10 deg.C 4 The temperature reduction speed of the temperature/s is reduced to 20 ℃, and the heat preservation time t=1.5 min/cm multiplied by d (as shown in figure 1);
when 10 is greater than or equal to d is greater than or equal to 5, the ratio of 10 5 Cooling to 200deg.C at a cooling rate of 10deg.C/s, maintaining for a period of time t=1 min/cm×d, and cooling to 200deg.C at a cooling rate of 10deg.C/cm×d 4 The temperature reduction speed of the temperature/s is reduced to 40 ℃, and the heat preservation time t=1.5 min/cm×d (as shown in fig. 1);
when d is less than or equal to 5cm, the ratio is 10 5 The temperature reduction speed of the temperature/s is reduced to 40 ℃, and the heat preservation time t=1.5 min/cm×d (as shown in fig. 2);
(5) And (3) deep cooling treatment: immediately after 10 5 Cooling to-100 ℃ at a cooling speed of DEG C/s, and keeping the temperature for t=1 min/cm×d;
(6) Tempering: heating to 560 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for a period of time t=1 h/cm×d;
(7) And (3) cooling: then cooling to 200 ℃ along with the furnace, discharging and air cooling to 40 ℃;
(8) Repeating (6) and (7) at least once;
where d is the maximum wall thickness of the sample in cm.
S8: forging, extruding, rolling and drawing the powder block blank obtained in the step S7 to obtain a wire with the diameter of 2 mm;
the forging process is as follows:
preheating: firstly, heating the blank to 620 ℃ at a heating speed of 8 ℃/min, and keeping the temperature for t=3 min/cm×d; then heating to 860 ℃ at a heating rate of 8 ℃/min, and keeping the temperature for a period of time t=2 min/cm×d; wherein d is the maximum wall thickness of the sample in cm;
forging: forging the blank, wherein the reduction amount is 5% each time, and directly putting the blank into a furnace at 840 ℃ again for heating after each forging, wherein the heating time is t=3 min/cm×d until the blank is forged to the required size;
and (3) cooling: and (3) placing the forged blank into a furnace, cooling to 200 ℃ along with the furnace, and then discharging the blank from the furnace for air cooling to room temperature.
The extrusion mode is hot extrusion, and the process is as follows:
preheating: firstly, heating the blank to 620 ℃ at a heating speed of 7 ℃/min, and keeping the temperature for t=5 min/cm×d; then heating to 900 ℃ at a heating rate of 7 ℃/min, and keeping the temperature for t=4 min/cm×d; wherein d is the maximum wall thickness of the sample in cm;
hot extrusion: the extrusion mode is horizontal extrusion, the extrusion speed is 5mm/s, the single extrusion section is reduced by 8%, and the preheating temperature of an extrusion die is 750 ℃;
and (3) cooling: and (3) placing the extruded blank into a furnace, cooling to 260 ℃ along with the furnace, and then discharging the blank from the furnace for air cooling to room temperature.
S9: and (5) carrying out grading heat treatment on the silk material obtained in the step (S8) again. The step of the heat treatment is shown in fig. 1 and 2, which are the same as those in S6, and will not be described here again.
Example 5:
this example is substantially the same as example 4, except that in this embodiment,
s5: sequentially carrying out reduction annealing and powder compaction on the S4 alloy powder to prepare a powder block blank; the process of the powder compact is HIP compact: and weighing the alloy powder subjected to reduction annealing, then placing the alloy powder into a compacting die, performing HIP compacting, and performing die pressing on the powder to obtain a block blank with the pressure of 120-500 MPa.
S6: sintering the powder block blank obtained in the step S5;
the sintering mode is HIP sintering: (1) Filling the powder block blank into a hollow shell, vacuumizing and sealing; (2) Heating to 650 ℃ at a speed of 10 ℃/min, and keeping the temperature for t=5 min/cm×d; (3) Heating to 1180 ℃ at a speed of 10 ℃/min, and keeping the temperature for a period of time t=20 min/cm×d; (4) cooling to room temperature along with the furnace; where d is the maximum wall thickness of the sample in cm.
Otherwise, this embodiment is identical to embodiment 4, and a detailed description thereof will be omitted.
Example 6:
this example is substantially the same as example 4, except that in this embodiment,
s8: forging, rolling and drawing the powder block blank obtained in the step S7 to obtain a wire with the diameter of 2 mm;
the forging process is as follows:
preheating: firstly, heating the blank to 620 ℃ at a heating speed of 8 ℃/min, and keeping the temperature for t=3 min/cm×d; then heating to 860 ℃ at a heating rate of 8 ℃/min, and keeping the temperature for a period of time t=2 min/cm×d; wherein d is the maximum wall thickness of the sample in cm;
forging: forging the blank, wherein the reduction amount is 5% each time, and directly putting the blank into a furnace at 840 ℃ again for heating after each forging, wherein the heating time is t=3 min/cm×d until the blank is forged to the required size;
and (3) cooling: and (3) placing the forged blank into a furnace, cooling to 200 ℃ along with the furnace, and then discharging the blank from the furnace for air cooling to room temperature.
Otherwise, this embodiment is identical to embodiment 4, and a detailed description thereof will be omitted.
Comparative example 1:
using the paper "Peng Hanlin, research on the heat treatment laws of powder metallurgy high speed steel S390/S790 for fine blanking dies, the formulation and method disclosed in university of science and technology, china 2020.
The properties of the wires prepared in examples 1 to 6 and those prepared in comparative example 1 are shown in the following table 1 by the formulations of examples a to c, respectively.
TABLE 1
The foregoing embodiments are merely illustrative of the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, not to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.

Claims (9)

1. The powder metallurgy high-speed steel wire is characterized by comprising the following components in percentage by weight: c: 1.5-1.8%, mn: 0.28-0.38%, si: 0.6-0.75%, cr: 3.8-4.5%, V or Nb+V: 2.8-3.2%, W: 5.8-6.5%, mo: 4.8-5.5%, co: 7.8-8.5%, ti: 1.8-2.3%, RE: 1-3%, S: <0.03%, P: <0.05%, o+n+h: <0.005%, the balance being Fe; the preparation method comprises the following steps:
s1: smelting a master alloy: taking pure metal of raw material Fe, pure metal or intermediate alloy of W, mo, co, V, nb, cr and intermediate alloy of C-Fe, si-Fe, mn-Fe and Ti-C, RE-M according to the proportion, and drying all raw materials; at a vacuum level of 10 -5 ~10 3 Smelting master alloy under the condition of Pa; firstly, melting pure metal in Fe, W, mo, co, V, nb, cr at 1380-1580 ℃, and preserving heat for 10-15 min; adding W, mo, co, V, nb, cr intermediate alloy and C-Fe, si-Fe and Mn-Fe intermediate alloy at 1280-1580 ℃, preserving heat for 10-15 min, stirring uniformly, and removing slag; adding a block material pressed by Ti-C powder at 1280-1580 ℃ again, and preserving heat for 15-35 min; then adding RE-M intermediate alloy at 1280-1480 ℃, preserving heat for 3-5 min, and carrying out electromagnetic stirring all the time in the heat preservation process; finally casting in a vacuum furnace and discharging to obtain master alloy;
s2: electroslag purification: electroslag remelting is carried out on the master alloy prepared in the step S1, and the slag system of the electroslag is CaF 2 -CaO-Al 2 O 3 -TiO 2 The content is 65-70%, 10-15% and 5-10% respectively;
s3: pulverizing: pulverizing the master alloy purified by the S2 electroslag to obtain alloy powder;
s4: annealing and compacting: sequentially carrying out reduction annealing and powder compacting on the alloy powder to prepare a powder block blank;
s5: sintering: sintering the powder block blank obtained in the step S4;
s6: and (3) heat treatment: carrying out grading heat treatment on the sintered powder block blank obtained in the step S5;
s7: deformation: forging and/or extruding, rolling and drawing the powder block blank obtained in the step S6 to obtain a wire with the diameter of 1-3 mm;
s8: and (3) heat treatment: carrying out grading heat treatment on the silk material obtained in the step S7 again;
in S6 and/or S8, the process of the graded heat treatment is as follows:
(1) Preheating: heating to 580-620 ℃ at a heating rate of 5-10 ℃/min, and keeping the temperature for a period of time t=3-5 min/cm multiplied by d;
(2) Secondary preheating: heating to 840-860 ℃ at a heating rate of 5-10 ℃/min, and keeping the temperature for a period of time t=2-4 min/cm×d;
(3) Quenching and heat preservation: heating to 1170-1260 ℃ at a heating rate of 5-10 ℃/min, and keeping the temperature for a period of time t=2-4 min/cm×d;
(4) Quenching and cooling: in the immediate vicinity of the point of use,
when d is greater than or equal to 10, first 10 3 ~10 5 Cooling to 300-500 ℃ at a cooling speed of DEG C/s, keeping the temperature for a period of time t=0.1-1.5 min/cm multiplied by d, and then cooling to 10℃/s 3 ~10 5 Cooling to 20-40 ℃ at a cooling speed of DEG C/s, and keeping the temperature for a period of time t=0.1-1.5 min/cm multiplied by d;
when 10 is greater than or equal to d is greater than or equal to 5, the ratio of 10 3 ~10 5 Cooling to 200-400 ℃ at a cooling speed of DEG C/s, keeping the temperature for a period of time t=0.1-1.5 min/cm multiplied by d, and then cooling to 10℃/s 3 ~10 5 Cooling to 20-40 ℃ at a cooling speed of DEG C/s, and keeping the temperature for a period of time t=0.1-1.5 min/cm multiplied by d;
when d is less than or equal to 5cm, the ratio is 10 3 ~10 5 Cooling to 20-40 ℃ at a cooling speed of DEG C/s, and keeping the temperature for a period of time t=0.1-1.5 min/cm multiplied by d;
(5) And (3) deep cooling treatment: immediately after 10 5 ~10 7 Cooling to-50 to-150 ℃ at a cooling speed of the temperature per second, wherein the heat preservation time t=1-2 min/cm multiplied by d;
(6) Tempering: heating to 560-570 ℃ at a heating rate of 5-10 ℃/min, and keeping the temperature for a period of time t=1-3 h/cm multiplied by d;
(7) And (3) cooling: rapidly cooling to 200-300 ℃, keeping the temperature for t=0.3-1 h/cm multiplied by d, discharging, and air cooling to 20-40 ℃;
(8) Repeating (6) and (7) 0-1 times;
where d is the maximum wall thickness of the sample in cm.
2. The powder metallurgy high-speed steel wire according to claim 1, wherein in the step S2, in the process of electroslag remelting, a means of reinforcing cooling at a discharge hole of a crystallizer and properly preserving heat at a side wall is adopted to control the temperature gradient of a molten pool, so that an acute angle part interval of an included angle between a solidification direction and the side wall of the molten pool is 0-30 degrees, and a purified master alloy melt is obtained.
3. The powder metallurgy high-speed steel according to claim 1, wherein in S3, the master alloy after S2 electroslag purification is transferred to an intermediate furnace with protective atmosphere protection and a protective layer plated on the inner wall of the hearth, and then the powder is directly prepared in the intermediate furnace, thereby obtaining the alloy powder.
4. The high-speed steel wire rod for powder metallurgy according to claim 1, wherein in the step S3, the powder is prepared by gas atomization, argon atomization is adopted, the purity of the argon is 99.9%, the atomization pressure is 10-30 mpa, and the D50 of the prepared alloy powder is 20-60 μm.
5. The powder metallurgy high-speed steel wire according to claim 1, wherein in the step S3, the powder is prepared by combining water and gas, the adopted gas is argon, the purity is 99.9%, the atomization pressure is 10-30 mpa, the water pressure is 8-50 mpa, and the D50 of the prepared alloy powder is 8-20 μm.
6. The powder metallurgy high-speed steel according to claim 1, wherein in S3, the powder preparation method is ball milling, and the prepared alloy powder has a D50 of 8-50 μm.
7. The powder metallurgy high-speed wire rod according to claim 1, wherein in S3, the powder preparation method is rotary ionization powder preparation, and the prepared alloy powder has a D50 of 30-70 μm.
8. The powder metallurgy high speed wire rod according to any one of claims 1 to 7, wherein in S4 the process of reduction annealing is as follows: the method comprises the steps of carrying out in a vacuum furnace, wherein the vacuum state or the inert gas protection state is formed in the furnace, flatly laying powder on a substrate, wherein the thickness is 5-10 mm, placing a plurality of layers of substrates in a superposition mode, spacing between adjacent substrates is 30-100 mm, the temperature is 400-680 ℃, the heat preservation time is 60-300 min, taking out after cooling to room temperature along with the furnace, and detecting the oxygen content of the atmosphere in the furnace to enable the oxygen content to be less than 10ppm.
9. The powder metallurgy high-speed wire rod according to any one of claims 1 to 7, wherein in S5 the sintering is performed by normal pressure protective atmosphere sintering: (1) The protective inert gas is injected into the sintering furnace, and oxygen is discharged, so that the oxygen content in the sintering furnace is less than 1ppm; (2) Heating to 650-850 ℃ at a speed of 6-10 ℃/min, and keeping the temperature for a period of time t=3-5 min/cm multiplied by d; (3) Heating to 1180-1260 ℃ at a speed of 8-10 ℃/min, and keeping the temperature for t=10-30 min/cm multiplied by d; (4) cooling to room temperature along with the furnace;
where d is the maximum wall thickness of the sample in cm.
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