CN112941406B - Stainless steel for knife and scissors - Google Patents

Stainless steel for knife and scissors Download PDF

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CN112941406B
CN112941406B CN202110104277.9A CN202110104277A CN112941406B CN 112941406 B CN112941406 B CN 112941406B CN 202110104277 A CN202110104277 A CN 202110104277A CN 112941406 B CN112941406 B CN 112941406B
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stainless steel
scissors
temperature
powder
heating
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CN112941406A (en
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梁晨
车洪艳
秦巍
黄赞军
张立冬
王铁军
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Advanced Technology and Materials Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12Both compacting and sintering
    • B22F3/14Both compacting and sintering simultaneously
    • B22F3/15Hot isostatic pressing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/06Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08Making 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
    • B22F9/082Making 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
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26Methods of annealing
    • C21D1/32Soft annealing, e.g. spheroidising
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0205Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226Hot rolling
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236Cold rolling
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/02Making ferrous alloys by powder metallurgy
    • C22C33/0257Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0285Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/001Ferrous alloys, e.g. steel alloys containing N
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/24Ferrous alloys, e.g. steel alloys containing chromium with vanadium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
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  • Physics & Mathematics (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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  • Powder Metallurgy (AREA)

Abstract

The invention belongs to the technical field of stainless steel materials, and particularly relates to stainless steel for knives and scissors. The stainless steel comprises the following components in percentage by weight: c:1.2 to 1.5%, si:0.3 to 0.6%, mn:0.3 to 0.6%, cr:12 to 16%, mo: 1.2-1.6%, V:2 to 4%, nb:0.4 to 0.7%, N:0.04 to 0.1%, S: less than or equal to 0.01 percent, P: less than or equal to 0.01 percent, O: less than or equal to 0.01 percent, and the balance of Fe and other inevitable impurities. Aiming at the defects of large structure, shrinkage cavity, looseness, component segregation and the like of stainless steel for preparing the scissors by the traditional method, the powder metallurgy method is adopted, the hot isostatic pressing technology is utilized, and the process parameters are reasonably controlled, so that the powder steel which has the same components as the powder, high density, good uniformity, high purity and excellent mechanical property and process property is obtained.

Description

Stainless steel for knife and scissors
Technical Field
The invention belongs to the technical field of stainless steel materials, and particularly relates to stainless steel for knives and scissors.
Background
With the continuous promotion of the industrialization process and the upgrade of civil consumption, the apparent consumption of stainless steel in China is increased by 12.73 percent in 2004-2016, which is 7.83 percent higher than that of crude steel in the same-period steel industry. From the statistical data of the national special steel association, the apparent consumption of stainless steel in China keeps increasing since 2004, and reaches 1883.53 ten thousand tons from 2004 to 2016, and the annual composite growth rate is as high as 12.73%. Meanwhile, the apparent consumption of crude steel in China is increased from 2.87 hundred million tons in 2004 to 7.10 hundred million tons in 2016, the annual composite growth rate is 7.83 percent, with the slowing of the increase of the macroscopic economy in China and the slowing of the consumption speed of downstream steel, the consumption of crude steel in China is 2014 or has been seen. The apparent consumption of stainless steel is accelerated more rapidly than that of common steel, and the consumption of stainless steel is expected to keep steadily increasing under the large trend of continuous popularization in the fields of future industrial use and civil use.
Although the stainless steel industry in China is developed rapidly at present, the development process of the stainless steel industry also has the problems that high-end stainless steel products such as low-end products are flooded, high corrosion resistance and high temperature resistance are still dependent on import to a great extent, and the like. Meanwhile, china enters the stage of upgrading of the manufacturing industry and the consumer market, people put more requirements on stainless steel for the cutter scissors, and the cutter scissors are attractive, practical, corrosion-resistant, sharp and tough, so that the market demand for high-end cutters is increased. Therefore, it is necessary to develop domestic high-end stainless steel products having proprietary intellectual property rights.
The traditional method for preparing stainless steel for the knife and the scissors mostly adopts methods of smelting, casting and the like, and the traditional preparation method has the defects of thick tissues, shrinkage, looseness, component segregation and the like, so that the strength, toughness, wear resistance and the like of the material are reduced, and the requirements of high-end cutters on the sharpness, durability and the like of the material are difficult to meet.
Disclosure of Invention
The invention aims to provide stainless steel for knives and scissors, which solves the problems of low strength, poor toughness and wear resistance and short service life of the existing stainless steel for knives and scissors.
In order to achieve the above purpose, the invention provides the following technical scheme:
the stainless steel for the knife scissors comprises the following components in percentage by weight: c:1.2 to 1.5%, si:0.3 to 0.6%, mn:0.3 to 0.6%, cr:12 to 16%, mo: 1.2-1.6%, V:2 to 4%, nb:0.4 to 0.7%, N:0.04 to 0.1%, S: less than or equal to 0.01%, P: less than or equal to 0.01 percent, O: less than or equal to 0.01 percent, and the balance of Fe and other inevitable impurities.
Preferably, the stainless steel has a room temperature tensile strength R m 850-1100 MPa, room temperature plastic elongation strength R p0.2 700-800 MPa, elongation A after room temperature break of 9-12%, impact absorption energy KV at room temperature 2 8 to 14J.
Preferably, the stainless steel for the knife and scissors is prepared by a method comprising the following steps of:
(1) Taking raw materials according to the designed components, smelting under the vacuum condition, alloying under the protection of nitrogen-containing inert gas in a smelting chamber, and preparing metal powder by utilizing high-pressure argon atomization;
(2) Removing impurities from the alloy powder, sieving, and taking undersize;
(3) Carrying out hot isostatic pressing treatment on the alloy powder treated in the step (2), and cooling to obtain a billet;
(4) Heating and rolling the billet obtained in the step (3) to obtain a plate;
(5) And (5) annealing and pickling the plate obtained in the step (4).
Preferably, in step (1), the nitrogen-containing inert gas is nitrogen or a mixture of nitrogen and argon.
Preferably, in the step (1), the temperature of the smelting is 1550-1650 ℃.
Preferably, in the step (1), the oxygen content of the alloy powder is 0.004 to 0.02%.
Preferably, the alloy powder is spherical and has a particle size of 0.006 to 0.35mm.
Preferably, in the step (3), the hot isostatic pressing pressure is 100-120 MPa, and the heat preservation temperature is 1000-1150 ℃.
Preferably, in the step (3), the pressure and temperature holding time of the hot isostatic pressing is 2-3 h.
Preferably, in step (3), the cooling is: cooling the mixture from the heat preservation temperature to 250 ℃ at the speed of 2-6 ℃/min, and then discharging the mixture from the furnace for air cooling.
Preferably, in the step (4), the rolling includes hot rolling and cold rolling, the hot rolling temperature is higher than 800 ℃, and the hot rolling is to heat the ingot and then roll the ingot with 15 to 35% of deformation.
Preferably, in step (4), the heating is: firstly, heating the billet to 750-850 ℃, preserving heat for 30-60 min, then heating to 1000-1150 ℃, preserving heat for 30-120 min.
Preferably, in the step (5), the annealing is spheroidizing annealing.
Preferably, the spheroidizing annealing is: firstly, heating the plate to 950-1050 ℃, preserving heat for 2-4 h, then cooling to 800-850 ℃ at 3-6 ℃/min, preserving heat for 2-4 h, and cooling along with the furnace.
Compared with the closest prior art, the technical scheme provided by the invention has the following excellent effects:
aiming at the defects of large structure, shrinkage, looseness, composition segregation, high cost, low efficiency and the like of stainless steel for knife and scissors prepared by traditional methods such as smelting, casting and the like, raw materials are smelted under vacuum, atomized to prepare powder under the inert protective atmosphere, a powder metallurgy method is adopted, a hot isostatic pressing technology is utilized, process parameters are reasonably controlled, the powder is the same as powder components, high in density (the relative density is close to 100%), good in uniformity, high in purity, high in tensile strength, good in plasticity and excellent in corrosion resistance, the blank of domestic high-end powder steel for knife and scissors is filled, domestic industry upgrading is supported, and international competitiveness of domestic knife and scissors industries is improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are included to illustrate an exemplary embodiment of the invention and not to limit the invention. Wherein:
FIG. 1 is a metallographic structure diagram (magnification: 5000) of stainless steel for scissors in example 1 of the present invention;
FIG. 2 is a metallographic structure diagram (magnification ×. 5000) of a stainless steel in comparative example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail below with reference to the accompanying drawings in conjunction with embodiments. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The methods employed in the production of metal powders can be broadly divided into four types: liquid metal atomization, chemical reaction, electrolytic deposition and mechanical pulverization. Of these four methods, the most widely used is liquid metal atomization. During atomization, liquid metal flow is crushed into small liquid drops by an atomizing medium flow and then solidified into powder particles.
The stainless steel for the knife and the scissors comprises the following components in percentage by weight: c:1.2 to 1.5% (e.g., 1.2%, 1.3%, 1.4%, 1.5%), si:0.3 to 0.6% (e.g., 0.3%, 0.4%, 0.5%, 0.6%), mn:0.3 to 0.6% (e.g., 0.3%, 0.4%, 0.5%, 0.6%), cr:12 to 16% (e.g., 12%, 13%, 14%, 15%, 16%), mo: 1.2-1.6% (e.g., 1.2%, 1.3%, 1.4%, 1.5%, 1.6%), V:2 to 4% (e.g., 2%, 2.5%, 3%, 3.5%, 4%), nb:0.4 to 0.7% (e.g., 0.3%, 0.4%, 0.5%, 0.6%, 0.7%), N:0.04 to 0.1% (e.g., 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%), S: less than or equal to 0.01 percent, P: less than or equal to 0.01 percent, O: less than or equal to 0.01 percent, and the balance of Fe and other inevitable impurities.
The functions of the respective main elements in the stainless steel for knives and scissors of the present invention are described in detail below.
Carbon (C), a main strengthening element, increases the material strength by interstitial solid solution strengthening. Increasing the carbon content can improve the tensile strength, edge retention and wear resistance of the material. Too high C content in the material easily causes precipitation of coarse carbides, which reduces the impact toughness of the material. According to different contents of Cr and C, gamma, alpha and Cr 7 C 3 、Cr 23 C 6 Controlling the equivalent phase, and controlling the carbon content in the material to be 1.2-1.5%.
Silicon (Si) -can improve the oxidation resistance, corrosion resistance, tempering stability and strength of the material. However, when the Si content in the material is too high, embrittlement of the material is easily caused. Therefore, si is mainly used as a deoxidizer to enter the steel and the content of Si is controlled to be 0.3 to 0.6 percent.
Manganese (Mn) -is mainly used for removing oxygen and sulfur in the material, but when the Mn element added in the material is too much, the material can coarsen crystal grains, and the corrosion resistance is reduced. In conclusion, the Mn content is controlled to be 0.3-0.6%.
Chromium (Cr) -can increase the hardness, wear resistance, tensile strength of the material. Particularly, when the chromium content of more than or equal to 12 percent is added into the stainless steel, the high-temperature oxidation resistance and corrosion resistance of the material can be improved, but when the chromium content in the material is too high, the toughness of the material can be reduced. Therefore, it is controlled to 12 to 16%.
Molybdenum (Mo) -can improve the strength, hardness, and secondary hardening effect of the material, improve corrosion resistance, and maintain the strength of the material at high temperatures. However, addition of an excessive Mo content to stainless steel promotes the formation of delta ferrite and lowers the toughness of stainless steel, and is preferably 1.2 to 1.6%.
Vanadium (V) -can improve the wear resistance, hardenability and toughness of the material and keep the edge of the cutter sharp. However, too high a V content in the material significantly reduces the crack resistance of the steel. In addition, a coarse precipitated phase is likely to be formed, which affects the specularity of the material. Therefore, the preferable V content range: 2 to 4 percent.
Nb (niobium) -a strong carbide former element can improve hardness, wear resistance, corrosion resistance, and strength of stainless steel, but too much niobium addition may reduce ductility and toughness of the material. Therefore, the niobium content should be controlled in the range of 0.4 to 0.7%.
Nitrogen (N) -improves the strength of stainless steel by solid solution strengthening without excessively reducing the plasticity and toughness of the material. The nitrogen element is not easy to combine with the chromium element, and more free chromium is kept in the material, so that the corrosion resistance of the material is improved. Excessive addition of nitrogen will generate stable M x N-type nitrides and agglomeration are generated, and the polishing property of the material is reduced. Therefore, the nitrogen content should be controlled within the range of 0.04 to 0.1%.
Sulfur (S) -is generally considered a harmful element, easily forms non-metallic inclusions in the material, and reduces the toughness of the material; in order to reduce the adverse effect of the S element on the material, the S content in the material should be reduced as much as possible and controlled below 0.01%.
Phosphorus (P), a harmful element, can cause segregation at grain boundaries during steel ingot hot working, increasing material brittleness. The content of P is controlled to be below 0.01 percent, and the adverse effect of P on the toughness of the material is eliminated.
Oxygen (O) -oxygen is a harmful element in steel, and oxygen is mainly FeO, mnO and SiO in steel 2 And the content thereof should be controlled to 0.01% or less because the inclusion forms reduce the strength, plasticity, and pitting corrosion properties of the steel.
The high-carbon high-chromium stainless steel for the scissors is prepared by the following method:
(1) Preparing high-purity metal powder: heating a stainless steel alloy material for a knife and a scissors in a vacuum chamber of atomizing equipment, melting and heating to 1550-1650 ℃ (for example 1550 ℃, 1600 ℃ and 1650 ℃), introducing nitrogen-containing inert gas into the melting chamber, introducing argon into the atomizing chamber, starting high-pressure atomizing gas after the gas pressure of the melting chamber and the gas pressure of the atomizing chamber are consistent, and atomizing molten steel flowing out of a tundish into powder, wherein the oxygen content of the prepared powder is 0.004-0.020%, the powder is mainly spherical, and the particle size of the powder is 0.006-0.35 mm;
(2) Powder purification and sieving: after the metal powder is prepared, the metal powder and the residues in the collection chamber are graded and sieved by a vacuum vibrating screen, the powder and the massive alloy residues are separated, massive non-metal impurities are removed, and then the powder is taken out for sheathing, degassing and sealing and welding;
(3) Hot isostatic pressing ingot making: filling powder into a metal sheath, placing the degassed sheath in a hot isostatic pressing device, applying 100-120 MPa (such as 100MPa, 110MPa and 120 MPa) pressure to the sheath in all directions by using argon as a pressurizing medium, applying 1000-1150 ℃ high temperature (such as 1000 ℃, 1050 ℃, 1100 ℃ and 1150 ℃) at the same time, keeping the temperature for 2-3 h (such as 2h, 2.2h, 2.4h, 2.6h, 2.8h and 3 h) under the action of the highest temperature and the highest pressure, cooling the temperature from the heat preservation temperature to 250 ℃ at the speed of 2-6 ℃/min, discharging the sheath out of a furnace, and carrying out air cooling to obtain a stainless steel billet for a cutter;
(4) Rolling: in order to reduce oxidation and decarburization in the preheating and rolling processes and eliminate surface and edge cracks, the ingot is coated with a metal sheath in the rolling preheating and rolling processes. Placing a stainless steel ingot which is cut by a knife before rolling in a heating furnace filled with inert gas protection, heating the stainless steel ingot to 750-850 ℃ (for example 750 ℃, 780 ℃, 800 ℃, 820 ℃, 840 ℃ and 850 ℃) at the heating rate of 8-12 ℃/min, keeping the temperature for 30-60 min (for example 30min, 40min, 50min and 60 min), continuing heating to 1000-1150 ℃ (for example 1000 ℃, 1050 ℃, 1100 ℃ and 1150 ℃) at the heating rate of 5-8 ℃/min, keeping the temperature for 30-120 min (for example 30min, 50min, 70min, 90min, 110min and 120 min), taking out of the furnace, rolling on a continuous rolling production line according to the deformation (for example 15%, 20%, 25%, 30% and 35%) of 15-35%, wherein the rolling comprises hot rolling and cold rolling, the whole hot rolling process is always kept at the temperature of more than 800 ℃ (for example, the initial rolling temperature of 1100 ℃, the final rolling temperature of 950 ℃, or the initial rolling temperature of 1000 ℃, the final rolling temperature of 850 ℃, or the initial rolling temperature of 1150 ℃, and the final rolling temperature of 950 ℃ to obtain a plate after cold rolling;
(5) And (3) heat treatment: and (5) carrying out heat treatment on the plate obtained in the step (4), specifically spheroidizing annealing treatment: the annealing temperature is 950-1050 ℃ (such as 950 ℃, 980 ℃, 1000 ℃, 1020 ℃ and 1050 ℃), the temperature is kept for 2-4 h (such as 2h, 2.5h, 3h, 3.2h, 3.4h, 3.6h, 3.8h and 4 h), the annealing temperature is cooled to 800-850 ℃ (800 ℃, 810 ℃, 820 ℃, 830 ℃, 840 ℃ and 850 ℃) at 3-6 ℃/min (such as 3 ℃/min, 4 ℃/min, 5 ℃/min and 6 ℃/min), the annealing temperature is kept for 2-4 h (such as 2h, 3h and 4 h), and the annealing temperature is cooled with a furnace. The spheroidizing annealing treatment is carried out on the plate coated with the metal sheath, so that the phenomena of oxidation, decarburization, carburization and the like are effectively reduced while the common heat treatment process is realized, and the powdered steel with a bright and clean surface can be obtained; the purpose of spheroidizing annealing is to precipitate carbon and metal elements in the steel in the form of spherical carbides, and uniformly distribute the carbon and the metal elements in a ferrite matrix, so that the hardness of the material can be sufficiently reduced, the plasticity can be improved, and the material is prepared for final heat treatment.
(6) Acid washing: and (4) pickling the plate subjected to spheroidizing annealing treatment, and removing the metal sheath coated on the surface of the steel plate.
The traditional method for preparing stainless steel for the knife scissors mainly adopts methods of smelting, casting and the like, the prepared stainless steel for the knife scissors has the defects of thick tissues, shrinkage cavity, looseness, component segregation and the like, and the strength, toughness, wear resistance and the like are difficult to meet the requirements of high-end cutters on the sharpness, durability and the like of materials. The key point of preparing the stainless steel for the knife and the scissors is the preparation of a powder metallurgy billet. Common powder metallurgy product hot consolidation methods include hot pressing, hot extrusion, hot isostatic pressing, hot forging, spark plasma sintering and the like. The powder metallurgy method is adopted, the hot isostatic pressing technology is utilized, the powder metallurgy steel with high density, high purity, high uniformity, high toughness and other excellent comprehensive properties is obtained, the blank of the powder steel for domestic high-end cutters is filled, the domestic industry upgrading is supported, and the international competitiveness of the domestic cutters is improved.
Example 1
The stainless steel for the knife and the scissors in the embodiment comprises the following components in percentage by weight: c:1.3%, si:0.4%, mn:0.4%, cr:13%, mo:1.2%, V:2.5%, nb:0.5%, N:0.05%, S: less than or equal to 0.01%, P: less than or equal to 0.01 percent, O:0.004%, and the balance of Fe and other inevitable impurities. The preparation method of the stainless steel for the scissors in the embodiment specifically comprises the following steps:
(1) Adding materials such as pure chromium, electrolytic manganese, ferromolybdenum, ferrovanadium, ferroniobium, siCa powder and the like into an atomizing equipment vacuum chamber according to designed steel components, heating to 1550 ℃ for melting, filling nitrogen into the melting chamber, filling argon into the atomizing chamber, starting high-pressure argon after the pressures of the melting chamber and the atomizing chamber are consistent, allowing molten steel to flow down through a sprue, and atomizing in high-pressure argon gas flow to obtain metal powder;
(2) Grading and sieving the metal powder and the residues by a vacuum vibration sieve of 200 meshes, separating the powder from large alloy residues, removing large non-metal impurities, taking out the powder, and performing sleeving, degassing and sealing welding;
(3) Placing metal powder in hot isostatic pressing equipment for pressing, specifically, filling the powder into a metal sheath, placing the degassed sheath in the hot isostatic pressing equipment, applying 120MPa pressure to each direction of the sheath by using argon as a pressurizing medium, applying 1150 ℃ temperature, and keeping the temperature for 2h; then cooling to 250 ℃ at the speed of 2 ℃/min, discharging and air cooling to obtain a stainless steel billet;
(4) Heating the billet obtained by hot isostatic pressing to 850 ℃ at the heating rate of 8 ℃/min, preserving heat for 30min, then continuously heating to 1130 ℃ at the heating rate of 5 ℃/min, preserving heat for 30min, then rolling according to 20% of deformation, wherein the initial rolling temperature is 1100 ℃, the final rolling temperature is 900 ℃, and then carrying out cold rolling to obtain a plate;
(5) Carrying out spheroidizing annealing treatment on the obtained plate, specifically comprising the following steps: firstly, heating the plate to 950 ℃, preserving heat for 4h, cooling to 850 ℃ at the speed of 3 ℃/min, preserving heat for 3h, and then slowly cooling to room temperature along with the furnace to obtain the powder steel.
Wherein SiCa powder is used as a deoxidizer and generates strong exothermic effect after being added into molten steel. Calcium is changed into calcium vapor in the molten steel, stirring effect is generated on the molten steel, nonmetal impurities can float upwards favorably, the calcium is relatively active and has strong affinity with oxygen, and the calcium preferentially reacts with the oxygen to remove the oxygen in the molten steel. After the silicon-calcium alloy is deoxidized, nonmetal impurities which have larger particles and are easy to float upwards are generated, and finally scum is removed to obtain relatively pure molten steel. Although silicon also has a deoxidizing effect, calcium is consumed firstly, then silicon is consumed, and finally, part of silicon is left to enter molten steel to be used as a constituent element of stainless steel.
The metallographic structure of the stainless steel for scissors prepared in this example is shown in fig. 1, and is determined by methods such as X-ray diffraction and back-scattered electron diffraction, and the like, and the matrix in the metallographic structure is ferrite and contains M 7 C 3 Type, M 23 C 6 30 to 40% of MCN type carbonitride, and the hardness after annealing is HRC21 to 24. In the phase change process, vanadium carbonitride is taken as a ferrite nucleation core, and the ferrite nucleation rate is influenced by the content of vanadium carbonitride; on the other hand, niobium carbonitride inhibits austenite recrystallization through deformation induction precipitation in austenite so as to achieve the purpose of refining ferrite grains, thereby influencing the fine-grain strengthening effect and further influencing the toughness of the material, wherein the average size of carbides is 0.8-1 μm, the maximum size of carbides is 1.5-2 μm, and the carbides are fine and uniformly distributed.
Example 2
The stainless steel for the knife and the scissors in the embodiment comprises the following components in percentage by weight: c:1.2%, si:0.3%, mn:0.6%, cr:12%, mo:1.5%, V:2%, nb:0.7%, N:0.05%, S: less than or equal to 0.01 percent, P: less than or equal to 0.01 percent, O:0.004%, and the balance of Fe and other inevitable impurities. The preparation method of the stainless steel for the scissors in the embodiment specifically comprises the following steps:
(1) Adding materials such as pure chromium, electrolytic manganese, ferromolybdenum, ferrovanadium, ferroniobium, siCa powder and the like into an atomizing equipment vacuum chamber according to designed steel components, heating to 1600 ℃ for melting, filling nitrogen into the smelting chamber, filling argon into the atomizing chamber, starting high-pressure argon after the pressures of the smelting chamber and the atomizing chamber are kept consistent, allowing molten steel to flow down through a pouring gate, and atomizing in high-pressure argon gas flow to obtain metal powder;
(2) Grading and sieving the metal powder and the residues by a vacuum vibration sieve of 200 meshes, separating the powder from large alloy residues, removing large non-metal impurities, taking out the powder, and performing sleeving, degassing and sealing welding;
(3) Placing metal powder in hot isostatic pressing equipment for pressing, specifically, filling the powder into a metal sheath, placing the degassed sheath in the hot isostatic pressing equipment, applying 110MPa pressure to each direction of the sheath by using argon as a pressurizing medium, applying 1050 ℃ temperature, and keeping the temperature for 3 hours; then cooling to 250 ℃ at the speed of 4 ℃/min, discharging and air cooling to obtain a stainless steel billet;
(4) Heating the billet obtained by hot isostatic pressing to 800 ℃ at the heating rate of 10 ℃/min, preserving heat for 50min, then continuously heating to 1030 ℃ at the heating rate of 6 ℃/min, preserving heat for 80min, then rolling according to 15% of deformation, wherein the initial rolling temperature is 1000 ℃, the final rolling temperature is 850 ℃, and then cold rolling is carried out to obtain a plate;
(5) And carrying out spheroidizing annealing treatment on the obtained plate, which specifically comprises the following steps: firstly, heating the plate to 1000 ℃, preserving heat for 3h, cooling to 800 ℃ at the speed of 5 ℃/min, preserving heat for 2h, and then slowly cooling to room temperature along with the furnace to obtain the powder steel.
Example 3
The stainless steel for the knife and the scissors in the embodiment comprises the following components in percentage by weight: c:1.5%, si:0.6%, mn:0.3%, cr:16%, mo:1.6%, V:4%, nb:0.4%, N:0.1%, S: less than or equal to 0.01 percent, P: less than or equal to 0.01 percent, O:0.004%, and the balance of Fe and other inevitable impurities. The preparation method of the stainless steel for the scissors in the embodiment specifically comprises the following steps:
(1) Adding materials such as pure chromium, electrolytic manganese, ferromolybdenum, ferrovanadium, ferroniobium, siCa powder and the like into an atomizing equipment vacuum chamber according to designed steel components, heating to 1650 ℃ for melting, filling nitrogen into the melting chamber, filling argon into the atomizing chamber, starting high-pressure argon after the pressure of the melting chamber and the pressure of the atomizing chamber are consistent, allowing molten steel to flow down through a pouring gate, and atomizing in high-pressure argon airflow to obtain metal powder;
(2) Grading and sieving the metal powder and the residues by a vacuum vibration sieve of 200 meshes, separating the powder from large alloy residues, removing large non-metal impurities, taking out the powder, and performing sleeving, degassing and sealing welding;
(3) Placing metal powder in hot isostatic pressing equipment for pressing, specifically, filling the powder into a metal sheath, placing the degassed sheath in the hot isostatic pressing equipment, applying 100MPa pressure to each direction of the sheath by using argon as a pressurizing medium, applying the temperature of 1000 ℃, and preserving the heat for 2.5 hours; then cooling to 250 ℃ at the speed of 6 ℃/min, discharging and air cooling to obtain a stainless steel billet;
(4) Heating the billet obtained by hot isostatic pressing to 750 ℃ at the heating rate of 10 ℃/min, preserving heat for 60min, then continuously heating to 1180 ℃ at the heating rate of 8 ℃/min, preserving heat for 120min, then rolling according to 35% of deformation, wherein the initial rolling temperature is 1150 ℃, the final rolling temperature is 950 ℃, and then carrying out cold rolling to obtain a plate;
(5) Carrying out spheroidizing annealing treatment on the obtained plate, specifically comprising the following steps: firstly, heating the plate to 950 ℃, preserving heat for 4h, cooling to 850 ℃ at the speed of 3 ℃/min, preserving heat for 3h, and then slowly cooling to room temperature along with the furnace to obtain the powder steel.
Comparative example 1
The stainless steel of the comparative example comprises the following components in percentage by weight: c:1.3%, si:0.4%, mn:0.4%, cr:13%, mo:1.2%, V:2.5%, nb:0.5%, N:0.05%, S: less than or equal to 0.01 percent, P: less than or equal to 0.01 percent, O:0.004%, and the balance of Fe and other inevitable impurities.
The stainless steel of this comparative example was prepared by a method different from that of example 1 in that: the processes of smelting, casting and forging are adopted to obtain the ingot, and the rolling and the subsequent heat treatment processes are the same as those in the embodiment 1 and are not described again.
The smelting, casting and forging process comprises the following specific steps:
(1) Smelting: adding materials such as pure chromium, electrolytic manganese, ferromolybdenum, ferrovanadium, ferroniobium, siCa and the like into an induction furnace, heating to 1550-1650 ℃, smelting into molten steel, and removing dross on the surface of the molten steel;
(2) Refining: adding molten steel to a refining furnace for refining, adding slag materials such as lime and fluorite into the furnace, heating the slag materials by utilizing an upper electrode of a steel ladle, introducing argon into the steel ladle from the bottom of the steel ladle, and refining for 15-20 min after all the slag materials are molten to remove gas and nonmetal impurities in the molten steel. The temperature of the molten steel is in the range of 1550-1600 ℃ for casting;
(3) Ingot casting: adopting an ingot mould to cast a steel ingot, cooling the steel ingot to 200 ℃, and demoulding to obtain a billet;
(4) Forging: forging the cast billet, wherein the size of the forged billet is suitable for hot rolling; the preheating temperature for forging the billet is 1100-1200 ℃, after the forging is finished, the billet is placed in heat-preservation cotton or sand-buried slow cooling, cooled to 200-300 ℃ and air-cooled.
The metallographic structure of the stainless steel for scissors of the comparative example is shown in FIG. 2 and determined by X-ray diffraction, back-scattered electron diffraction and other methods, and the matrix in the metallographic structure is ferrite and contains M 7 C 3 Type, M 23 C 6 The carbide type and MCN type carbonitride, wherein the maximum carbide size is 6.1 μm, the average carbide size is 0.5 μm, the carbide is coarse, and the phenomena of carbide segregation, shrinkage cavity and the like exist.
Comparative example 2
No nitrogen element is added into the chemical components of the stainless steel of the comparative example, and the hot isostatic pressing ingot making, rolling and subsequent heat treatment processes are the same as those in the example 1 and are not repeated.
The stainless steel for the knife and the scissors of the comparative example comprises the following components in percentage by weight: c:1.3%, si:0.4%, mn:0.4%, cr:13%, mo:1.2%, V:2.5%, nb:0.5%, S: less than or equal to 0.01 percent, P: less than or equal to 0.01 percent, O:0.004%, and the balance of Fe and other inevitable impurities.
The preparation method of the stainless steel for the scissors of the comparative example specifically comprises the following steps:
(1) Adding pure chromium, electrolytic manganese, ferromolybdenum, ferrovanadium, ferroniobium, siCa powder and other materials into an atomizing equipment vacuum chamber according to the designed steel components, heating to 1650 ℃ for melting, filling argon into a smelting chamber and an atomizing chamber, starting high-pressure argon after the pressure of the smelting chamber and the pressure of the atomizing chamber are consistent, and atomizing molten steel in the high-pressure argon flow through a pouring gate to obtain metal powder.
Comparative example 3
Comparative example 3 differs from example 1 in that: the hot isostatic pressing ingot making, rolling and subsequent heat treatment processes are the same as those in example 1 and are not described again.
The stainless steel for the knife and the scissors of the comparative example comprises the following components in percentage by weight: c:1.3%, si:0.4%, mn:0.4%, cr:13%, mo:1.2%, V:2.5%, nb:0.5%, N:0.2%, S: less than or equal to 0.01%, P: less than or equal to 0.01 percent, O:0.004%, and the balance of Fe and other inevitable impurities.
The preparation method of the stainless steel for the scissors in the embodiment specifically comprises the following steps:
(1) Adding pure chromium, electrolytic manganese, ferromolybdenum, ferrovanadium, ferroniobium, siCa powder and other materials into an atomizing device vacuum chamber according to the designed steel components, heating to 1550 ℃ for melting, filling nitrogen into the melting chamber, filling argon into the atomizing chamber, starting high-pressure argon after the pressures of the melting chamber and the atomizing chamber are consistent, enabling the molten steel to flow down through a pouring gate, and atomizing in high-pressure argon airflow to obtain the metal powder.
Examples of the experiments
The components of ingots prepared in examples 1 to 3 and comparative examples 1 to 3 of the present invention were measured by standard methods in GB/T11170-2008 "atomic emission spectrometry for measuring the content of multiple elements in stainless steel", GB/T20123-2006 "infrared absorption method after combustion in high frequency induction furnace for measuring the total carbon and sulfur content in steel", and GB/T20124-2006 "inert gas melting thermal conductivity method for measuring the nitrogen content in steel", and the measurement results are shown in Table 1.
TABLE 1 chemical composition (wt%) of ingots prepared in inventive examples 1 to 3 and comparative examples 1 to 3
Material C Si Mn Cr Mo V Nb N O S、P
Example 1 1.28 0.38 0.41 13.1 1.22 2.48 0.47 0.045 0.005 ≤0.01
Example 2 1.18 0.29 0.61 11.9 1.51 2.1 0.69 0.041 0.0038 ≤0.01
Example 3 1.49 0.61 0.29 16.1 1.59 3.9 0.41 0.097 0.0041 ≤0.01
Comparative example 1 1.2 0.5 0.3 15 1.4 3 0.6 0.04 0.008 ≤0.01
Comparative example 2 1.28 0.38 0.41 13.1 1.22 2.48 0.47 0 0.008 ≤0.01
Comparative example 3 1.28 0.38 0.41 13.1 1.22 2.48 0.47 0.2 0.005 ≤0.01
Note: (1) The rightmost column in the table indicates that the amounts of S, P are within this range, respectively;
(2) The parts not listed in the table are Fe and other unavoidable impurities.
As can be seen from the chemical composition analysis in Table 1, compared with the conventional melting and casting process, the composition of the ingot prepared by the hot isostatic pressing technology is closer to the design composition, and the ingot prepared by the conventional melting and casting process has the composition segregation problem to a certain extent.
The room temperature tensile property test was performed on the powdered steels prepared in example 1 and comparative examples 1 to 3 of the present invention by using the standard method of GB/T228.1-2010 "metal material tensile test", and the test results are shown in table 2.
TABLE 2 tensile Properties at Room temperature of steels prepared in example 1 of the present invention and comparative examples 1 to 3
Figure BDA0002917227380000121
The room temperature impact toughness test was performed on the powder steels prepared in example 1 and comparative examples 1 to 3 of the present invention by the standard method of GB/T229-2007 "metallic material charpy pendulum impact test method", and the test results are shown in table 3.
TABLE 3 test results of room temperature impact Properties of steels prepared in inventive example 1 and comparative examples 1 to 3
Material Impact energy absorption (KV) at room temperature 2 /J)
Example 1 9.2
Comparative example 1 10.1
Comparative example 2 12.4
Comparative example 3 7
The powder steels prepared in example 1 and comparative examples 1 to 3 of the present invention were tested for room temperature pitting performance by the standard method of GB/T17899-1999 stainless steel pitting potential measuring method, and the test results are shown in Table 4.
TABLE 4 test results of room temperature pitting corrosion properties of steels prepared in inventive example 1 and comparative examples 1 to 3
Material Pitting potential at room temperature (V mu sSCE)
Example 1 -0.19
Comparative example 1 -0.25
Comparative example 2 -0.37
Comparative example 3 -0.15
Comparing the properties of the high-carbon high-chromium stainless steel for knife and scissors in the embodiment 1 and the stainless steel in the comparative example, it can be seen that the stainless steel for knife and scissors prepared by the traditional methods of smelting, casting and the like has the defects of large structure, shrinkage cavity, looseness, component segregation, high cost, low efficiency and the like, and the powder metallurgy method is adopted, the hot isostatic pressing technology is utilized, and the process parameters are reasonably controlled, so that the stainless steel for knife and scissors is the powder steel which has the same components as powder, high density (relative density is close to 100%), good uniformity, high purity, high tensile strength, good plasticity and excellent corrosion resistance, namely the stainless steel for knife and scissors is excellent in mechanical property and process property.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made to the present invention by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. The stainless steel for the knife scissors is characterized by comprising the following components in percentage by weight: c:1.2 to 1.5%, si:0.3 to 0.6%, mn:0.3 to 0.6%, cr:12 to 16%, mo: 1.2-1.6%, V:2 to 4%, nb:0.4 to 0.7%, N:0.04 to 0.1%, S: less than or equal to 0.01 percent, P: less than or equal to 0.01 percent, O: less than or equal to 0.01 percent, and the balance of Fe and other inevitable impurities;
the stainless steelTensile strength R at room temperature m 850-1100 MPa, room-temperature plastic elongation strength R p0.2 700-800 MPa, elongation A after room temperature break of 9-12%, impact absorption energy KV at room temperature 2 8 to 14J;
the stainless steel for the knife scissors is prepared by the method comprising the following steps of:
(1) Taking raw materials according to the designed components, smelting under the vacuum condition, alloying under the protection of nitrogen-containing inert gas in a smelting chamber, and preparing metal powder by utilizing high-pressure argon atomization;
(2) Removing impurities from the alloy powder, sieving, and taking undersize;
(3) Carrying out hot isostatic pressing treatment on the alloy powder treated in the step (2), and cooling to obtain a billet;
(4) Heating and rolling the billet obtained in the step (3) to obtain a plate;
(5) Annealing and pickling the plate obtained in the step (4);
in the step (3), the hot isostatic pressure is 100-120 MPa, and the heat preservation temperature is 1000-1150 ℃;
in the step (4), the heating is as follows: firstly, heating a billet to 750-850 ℃, preserving heat for 30-60 min, then heating to 1000-1150 ℃, preserving heat for 30-120 min; the rolling comprises hot rolling and cold rolling, wherein the hot rolling temperature is higher than 800 ℃, and the hot rolling is to heat a billet and then roll the billet by 15-35% of deformation;
in the step (5), the annealing is spheroidizing annealing, and the spheroidizing annealing is as follows: firstly, heating the plate to 950-1050 ℃, preserving heat for 2-4 h, then cooling to 800-850 ℃ at 3-6 ℃/min, preserving heat for 2-4 h, and furnace cooling.
2. The stainless steel for knives and scissors according to claim 1, wherein the nitrogen-containing inert gas is nitrogen or a mixture of nitrogen and argon in step (1).
3. The stainless steel for knives and scissors according to claim 1, wherein the temperature for melting in step (1) is 1550 to 1650 ℃.
4. The stainless steel for knives and scissors according to claim 1, wherein in the step (1), the oxygen content of the alloy powder is 0.004 to 0.02%.
5. The stainless steel for knives and scissors according to claim 4, wherein the alloy powder has a spherical shape and a particle size of 0.006 to 0.35mm.
6. The stainless steel for knives and scissors according to claim 1, wherein the pressure and temperature holding time of the hot isostatic pressing is 2 to 3 hours.
7. The stainless steel for knives and scissors according to any one of claims 1 to 6, wherein in the step (3), the cooling is: cooling the mixture from the heat preservation temperature to 250 ℃ at the speed of 2-6 ℃/min, and then discharging the mixture from the furnace for air cooling.
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