CN115283595A - Martensite antibacterial stainless steel outdoor knife and preparation method thereof - Google Patents
Martensite antibacterial stainless steel outdoor knife and preparation method thereof Download PDFInfo
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- CN115283595A CN115283595A CN202210953784.4A CN202210953784A CN115283595A CN 115283595 A CN115283595 A CN 115283595A CN 202210953784 A CN202210953784 A CN 202210953784A CN 115283595 A CN115283595 A CN 115283595A
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- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J5/00—Methods for forging, hammering, or pressing; Special equipment or accessories therefor
- B21J5/002—Hybrid process, e.g. forging following casting
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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
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F3/15—Hot isostatic pressing
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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
- B22F3/18—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers
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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
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- 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
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- C21D6/00—Heat treatment of ferrous alloys
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- 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
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- C21D6/04—Hardening by cooling below 0 degrees Celsius
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- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/18—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for knives, scythes, scissors, or like hand cutting tools
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- 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
- C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
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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
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
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- 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
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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
- B22F3/18—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers
- B22F2003/185—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers by hot rolling, below sintering temperature
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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
- B22F2003/247—Removing material: carving, cleaning, grinding, hobbing, honing, lapping, polishing, milling, shaving, skiving, turning the surface
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- 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
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/248—Thermal after-treatment
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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
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F2005/001—Cutting tools, earth boring or grinding tool other than table ware
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- 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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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P10/20—Recycling
Abstract
The invention discloses a martensite antibacterial stainless steel outdoor knife and a preparation method thereof, and relates to the technical field of stainless steel, wherein the outdoor knife is prepared from 3Cr13MoVCu4 powder as a raw material, and comprises the following components in percentage by mass: 0.28 to 0.38 percent of carbon, 12 to 14 percent of chromium, 0.5 to 1.0 percent of molybdenum, 0.2 to 0.3 percent of vanadium, 3.5 to 4.5 percent of copper, and the balance of iron and inevitable impurities, and is realized by powder metallurgy/hot isostatic pressing. The copper-containing stainless steel powder can be completely compact in a special environment of hot isostatic pressing at high temperature and high pressure, the prepared material has uniform tissue, fine grains and isotropy, and has high mechanical property and broad-spectrum antibacterial property after rolling and special heat treatment.
Description
Technical Field
The invention relates to the technical field of stainless steel, in particular to a martensite antibacterial stainless steel outdoor knife and a preparation method thereof.
Background
The martensitic stainless steel is stainless steel which contains more than 10.5% of element chromium by weight, can be obtained by a heat treatment (quenching and tempering) process, has corrosion resistance, high hardness, wear resistance and enough toughness, has good processing performance and is widely applied to the fields of steam turbine blades, tableware, hardware scissors, surgical instruments and the like.
The copper-containing martensitic stainless steel is a new material with integrated structure and function developed on the basis of common martensitic stainless steel, and the copper ions are continuously separated out from the stainless steel by utilizing special heat treatment, so that the copper-containing martensitic stainless steel has a strong broad-spectrum sterilization function and meets the requirements of the public on antibacterial and bactericidal products at present. The outdoor knife is a tool used for field activities of people, and is made of stainless steel endowed with antibacterial property, so that the field health level of people is greatly improved.
The common antibacterial stainless steel is prepared by casting and forging, has the characteristics of short production period and low price, but has the defects of non-uniform alloy components, easy segregation, coarse crystal grains and unstable performance.
Disclosure of Invention
The invention aims to provide a martensite antibacterial stainless steel outdoor knife and a preparation method thereof. The copper-containing stainless steel powder can be completely compact in a special environment of hot isostatic pressing at high temperature and high pressure, the prepared material has uniform tissue, fine grains and isotropy, and has high mechanical property and broad-spectrum antibacterial property after rolling and special heat treatment.
In order to achieve the purpose, the invention provides the following scheme:
the martensite antibacterial stainless steel outdoor knife is prepared from 3Cr13MoVCu4 powder and comprises the following components in percentage by mass:
0.28 to 0.38 percent of carbon, 12 to 14 percent of chromium, 0.5 to 1.0 percent of molybdenum, 0.2 to 0.3 percent of vanadium, 3.5 to 4.5 percent of copper, and the balance of iron and inevitable impurities.
The martensite antibacterial stainless steel outdoor knife material prepared by the invention is isotropic, the hardness can exceed 50HRC after aging heat treatment, and the antibacterial rate of escherichia coli (E.coli) and staphylococcus aureus (S.aureus) is more than 99.5%.
A preparation method of the martensite antibacterial stainless steel outdoor knife comprises the following steps:
carrying out hot isostatic pressing treatment on the outer sheath die filled with 3Cr13MoVCu4 powder, then carrying out free forging and stamping to obtain an outdoor small knife blank, carrying out solid solution treatment and cryogenic treatment on the outdoor small knife blank, then carrying out high-temperature aging, grinding and edging to obtain the martensite antibacterial stainless steel outdoor knife.
The martensite antibacterial stainless steel outdoor knife is prepared by the steps of firstly adopting metal atomized powder to carry out hot isostatic pressing densification, then carrying out deformation processing to obtain a plate, preparing a knife blank in a stamping mode, and finally carrying out heat treatment to obtain excellent mechanical property and antibacterial property.
Preferably, the preparation method specifically comprises the following steps:
(1) Preparation of stainless steel atomized powder
Weighing graphite, chromium, molybdenum, vanadium, copper and iron according to the mass percentage of 0.28-0.38% of carbon, 12-14% of chromium, 0.5-1.0% of molybdenum, 0.2-0.3% of vanadium and 3.5-4.5% of copper, and the balance of iron, mixing, smelting to obtain alloy liquid, and cooling to obtain stainless steel atomized powder; preferably, metals such as iron, chromium, copper, molybdenum, vanadium and the like or alloy blocks and graphite are added into a crucible of the atomization equipment in proportion, the mixture is melted by medium-frequency induction heating to obtain alloy liquid, the alloy liquid is crushed into tiny liquid drops by high-pressure water, and the stainless steel atomized powder is obtained after cooling;
(2) Hot isostatic pressing of stainless steel atomized powder
Filling the stainless steel atomized powder into a metal sheath, compacting, heating, degassing, sealing, preferably welding, performing hot isostatic pressing densification, and removing the metal sheath by machining to obtain a hot isostatic pressing stainless steel blank;
(3) Hot isostatic pressing stainless steel blank deformation treatment and stamping
Heating and insulating the hot isostatic pressing stainless steel blank, then carrying out free forging, carrying out hot rolling after the thickness of the hot isostatic pressing stainless steel blank reaches a specified size, finally manufacturing a 3-4 mm thin plate, and stamping the thin plate into an outdoor small cutter blank with a machining allowance;
(4) Outdoor small knife blank heat treatment
And carrying out solid solution treatment and cryogenic treatment on the outdoor small knife blank, then carrying out high-temperature aging (obtaining excellent mechanical properties and antibacterial properties), and carrying out conventional grinding, edging and other processes to obtain the martensite antibacterial stainless steel outdoor small knife.
Preferably, the degassing temperature in the step (2) is 400 to 60 DEG0 ℃ and the vacuum degree of 10 -4 Pa, keeping for 15-40 min.
Preferably, the hot isostatic pressing temperature in the step (2) is 1080-1180 ℃, the pressure is 100-160 MPa, and the heat preservation and pressure maintaining time is 1.5-4 h.
Preferably, the heating temperature in the step (3) is 1050-1150 ℃.
Preferably, the solution treatment temperature in the step (4) is 1030-1100 ℃, and the holding time is 10-40 min.
Preferably, the temperature of the cryogenic treatment in the step (4) is-176 ℃, and the temperature is kept for 5-10 h.
Preferably, the high-temperature aging temperature in the step (4) is 400-700 ℃, and the heat preservation time is 4-15 h.
The invention discloses the following technical effects:
1. because the copper-containing stainless steel atomized powder can be completely compact in the special environment of high-temperature and high-pressure hot isostatic pressing, the prepared material has uniform tissue, fine and isotropic crystal grains, and copper elements are uniformly distributed on a matrix;
2. the material after rolling and solution heat treatment has high mechanical property, copper ions are evenly precipitated after aging treatment, so the material has better broad-spectrum antibacterial property than the material prepared by a casting and forging mode, and the antibacterial property is at least 5 percent higher under the same heat treatment condition. The produced outdoor knife has high sharpness and good durability, and is sanitary and healthy to use.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic diagram of a capsule structure for hot isostatic pressing, wherein 1 is a capsule sleeve with a bottom, 2 is a capsule cover, and 3 is an exhaust tube;
FIG. 2 is a scanning electron micrograph of 3Cr13MoVCu4 alloy powder of example 1;
fig. 3 is a scanning electron micrograph of the martensitic stainless steel outdoor knife prepared in example 1.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in the present disclosure, it is understood that each intervening value, to the upper and lower limit of that range, is also specifically disclosed. Every intervening value, to the extent any stated value or intervening value in a stated range, and any other stated or intervening value in a stated range, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. It is intended that the specification and examples be considered as exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The embodiment of the invention provides a martensite antibacterial stainless steel outdoor knife which is prepared from 3Cr13MoVCu4 powder as a raw material and comprises the following components in percentage by mass:
0.28 to 0.38 percent of carbon, 12 to 14 percent of chromium, 0.5 to 1.0 percent of molybdenum, 0.2 to 0.3 percent of vanadium, 3.5 to 4.5 percent of copper, and the balance of iron and inevitable impurities.
The martensite antibacterial stainless steel outdoor knife material prepared by the invention is isotropic, the hardness can exceed 50HRC after aging heat treatment, and the antibacterial rate of escherichia coli (E.coli) and staphylococcus aureus (S.aureus) is more than 99.5%.
The invention provides a preparation method of a martensite antibacterial stainless steel outdoor knife, which comprises the following steps:
carrying out hot isostatic pressing treatment on the outer sheath die filled with 3Cr13MoVCu4 powder, then carrying out free forging and stamping to obtain an outdoor small knife blank, carrying out solid solution treatment and cryogenic treatment on the outdoor small knife blank, then carrying out high-temperature aging, grinding and edging to obtain the martensite antibacterial stainless steel outdoor knife.
The martensite antibacterial stainless steel outdoor knife disclosed by the invention is characterized in that firstly, metal atomized powder is adopted for hot isostatic pressing densification, then, a plate is formed through deformation processing, a knife blank is manufactured through a stamping mode, and finally, the outdoor knife obtains excellent mechanical property and antibacterial property through heat treatment.
The preparation method of the martensite antibacterial stainless steel outdoor knife in the embodiment of the invention specifically comprises the following steps:
(1) Preparation of stainless steel atomized powder
Weighing graphite, chromium, molybdenum, vanadium, copper and iron according to the mass percentage of 0.28-0.38% of carbon, 12-14% of chromium, 0.5-1.0% of molybdenum, 0.2-0.3% of vanadium and 3.5-4.5% of copper, and the balance of iron, mixing, smelting to obtain alloy liquid, and cooling to obtain stainless steel atomized powder; preferably, metals such as iron, chromium, copper, molybdenum, vanadium and the like or alloy blocks and graphite are added into a crucible of atomizing equipment in proportion, the mixture is heated and smelted through medium-frequency induction to obtain alloy liquid, the alloy liquid is crushed into tiny liquid drops by high-pressure water, and stainless steel atomized powder is obtained after cooling, for example, the steps can be as follows: adding metal or alloy blocks of iron, chromium, copper, molybdenum and vanadium and graphite raw materials into a quartz crucible in a medium-frequency induction furnace of an atomizer according to a proportion, wherein the raw materials sequentially comprise the following chemical components in percentage by mass: 0.28 to 0.38 percent of carbon, 12 to 14 percent of chromium, 0.5 to 1.0 percent of molybdenum, 0.2 to 0.3 percent of vanadium, 3.5 to 4.5 percent of copper, and the balance of iron and inevitable impurities. Induction heating to 1650 ℃ melts the alloy. Rapidly pouring stainless steel liquid into a tundish, wherein the molten steel flows down through a liquid guide pipe at the bottom of the tundish, the molten steel is changed into dispersed fine liquid drops under the impact of high-pressure water, and the liquid drops are rapidly cooled and solidified to obtain 3Cr13MoVCu4 alloy powder, the atomization pressure is 100-120 MPa, and the powder is dehydrated, dried, screened and vacuum-packaged for later use;
(2) Hot isostatic pressing of stainless steel atomized powder
Filling the stainless steel atomized powder into a metal sheath, compacting, heating, degassing, sealing, preferably welding and sealing, performing hot isostatic pressing densification, and removing the metal sheath through machining to obtain a hot isostatic pressing stainless steel blank; for example, this step may be: as shown in figure 1, a sheath cylinder 1 with a bottom and a sheath cover 2 with certain size and volume are welded by low carbon steel, and an exhaust pipe 3 is welded on the sheath cover. And weighing the atomized powder, putting the sheath cylinder 1 on a vibration table, and adding the raw material powder into the sheath while vibrating. After the addition is finished, the cover is covered by the sheath cover 2, and the welding is firm. Putting the whole sheath into a degassing heating furnace, connecting a vacuum pump with an exhaust pipe, vacuumizing, heating to 400-600 ℃, and ensuring that the vacuum degree reaches 10 -4 Pa, keeping for 15-40 min. Taking out the sheath and sealing the exhaust tube.
And (3) putting the sheath into a hot isostatic pressing device, and simultaneously heating and pressurizing, wherein the pressure medium is high-purity argon. Hot isostatic pressing with the highest temperature of 1080-1180 deg.c, pressure of 100-160 MPa and heat maintaining time of 1.5-4 hr. After the atomized powder is completely sintered and compact, cutting off the power, reducing the temperature and the pressure, opening the furnace when the furnace temperature reaches 100 ℃, taking out the sheath, cooling the sheath to room temperature in the air, and removing the sheath by a machining mode;
(3) Hot isostatic pressing stainless steel blank deformation treatment and stamping
Heating and preserving the heat of the hot isostatic pressing stainless steel blank, then carrying out free forging, carrying out multi-pass hot rolling after the specified thickness is achieved, carrying out final rolling at the heating temperature of 1050-1150 ℃ each time, finally manufacturing a 3-4 mm thin plate, and stamping the thin plate into an outdoor small cutter blank with a machining allowance;
(4) Outdoor small knife blank heat treatment
And carrying out solid solution treatment and subzero treatment on the outdoor small knife blank, then carrying out high-temperature aging (obtaining excellent mechanical properties and antibacterial properties), and carrying out conventional grinding, edging and other processes to obtain the martensite antibacterial stainless steel outdoor small knife.
In the embodiment of the invention, the degassing temperature in the step (2) is 400-600 ℃, and the vacuum degree reaches 10 -4 Pa, keeping for 15-40 min. In the degassing temperature, the gas adsorbed in the powder in the sheath can be completely removed, the gas adsorbed at the temperature higher than the degassing temperature is removed, the temperature rise is not practical, the cost is increased, the gas adsorbed in the powder at the temperature lower than the degassing temperature is difficult to remove, or the heat preservation time is only increased excessively, and the electric energy is wasted. The treatment time is too long, the gas is removed, the cost is increased, and the adsorbed gas cannot be completely removed after the treatment time is too short.
In the embodiment of the invention, the hot isostatic pressing temperature in the step (2) is 1080-1180 ℃, the pressure is 100-160 MPa, and the heat preservation and pressure maintaining time is 1.5-4 h. In the temperature range, the crystal grains are fine, the material is compact, the crystal grains become coarse and the performance is reduced when the temperature is higher than the temperature, the material is not compact when the temperature is lower than the temperature, and pores are formed in the material; the heat preservation time is too long, the crystal grains are large, electric energy is wasted, the time is too short, and the structure is not uniform; the pressure is too high, increases use cost, and equipment life reduces, and the pressure is low excessively, and the material is not compact, and the inside has the hole.
In the embodiment of the invention, the heating temperature in the step (3) is 1050-1150 ℃. The material has good plasticity and is easy to deform in the temperature range, and the material has poor plasticity and is easy to crack during rolling when the temperature is lower than the temperature. When the temperature exceeds this temperature, an overheat phenomenon occurs, the plasticity of the material is deteriorated, internal cracks are likely to occur during rolling, and the degree of oxidation during processing is increased.
In the embodiment of the invention, the solution treatment temperature in the step (4) is 1030-1100 ℃, and the holding time is 10-40 min. In the temperature range, the austenite grains of the stainless steel are fine, the alloy elements can be dissolved in austenite, when the temperature is higher than the temperature, the austenite grains are coarse, excessive carbides are dissolved, the hardness is reduced, when the temperature is lower than the temperature, the stainless steel matrix can not be completely austenitized, and the content of martensite is reduced in the subsequent cooling process; over time, coarse austenite grains, excessive carbide dissolution, reduced hardness, over-short time, incomplete austenitization and non-uniform structure.
In the embodiment of the invention, the temperature of the cryogenic treatment in the step (4) is-176 ℃ (176 ℃ below zero), and the temperature is kept for 5-10 h. Too long time, long equipment occupation time, low productivity, too short time, incomplete martensite transformation and more retained austenite content.
In the embodiment of the invention, the high-temperature aging temperature in the step (4) is 400-700 ℃, and the heat preservation time is 4-15 h. In the temperature range, more copper ions can be separated out from the matrix, the antibacterial performance is good, the higher hardness of the material can be ensured, the antibacterial performance is improved and the hardness is reduced when the temperature is exceeded, and less copper ions are separated out from the matrix and the antibacterial performance is low when the temperature is lower than the temperature; the time is too long, the hardness of the material is reduced, the time is too short, less copper ions are separated out, and the antibacterial performance is low. If step (4) is not performed, the knife has little antimicrobial properties.
In the embodiments of the present invention, the steps of dehydrating, drying, sieving, and vacuum packaging the powder are conventional operation means in the art, and are not the focus of the present invention, and are not described herein again.
The method for welding the jacketed cylinder with the bottom by using the low-carbon steel in the embodiment of the invention is also a conventional operation means in the field, is not the focus of the invention, and is not described herein again.
In the embodiment of the invention, the outdoor knife is prepared by the processes of grinding, edging and the like of the knife blank by conventional operation means in the field, and the process is not the key point of the invention and is not described herein again.
Example 1
The raw materials are added into a quartz crucible in a medium-frequency induction furnace of an atomizer according to the mass percentage in sequence as follows: graphite 0.2813 percent of chromium, 0.5 percent of molybdenum, 0.2 percent of vanadium, 3.5 percent of copper and the balance of iron. Induction heating to 1650 ℃ to melt the alloy, rapidly pouring the stainless steel liquid into a drain ladle, flowing down along a liquid guide pipe, changing the molten steel into dispersed fine liquid drops under the impact of high-pressure water, rapidly cooling and solidifying to obtain 3Cr13MoVCu4 alloy powder, wherein the atomization pressure is 100MPa, the powder is dehydrated, dried, screened and vacuum-packaged for later use, the scanning electron microscope image of the 3Cr13MoVCu4 alloy powder is shown in figure 2, the atomized powder is spherical, ellipsoidal or rod-shaped, a small amount of powder is adhered to a plurality of particles, and the total powder flowability is good; a sheath with a bottom and with the internal dimension of phi 200mm multiplied by 500mm is welded by mild steel (the structural schematic diagram of the sheath is shown in figure 1 and comprises a sheath cylinder 1 with a bottom, a sheath cover 2 and an exhaust tube 3 welded on the sheath cover). The raw material powder was added to the packing sleeve 1 while shaking on a shaking table. After the addition is finished, the cover is covered by the sheath cover 2, and the welding is firm. Putting the sheath into a degassing furnace, heating and vacuumizing. When the temperature is raised to 400 ℃, the vacuum degree reaches 10 -4 Pa, keeping for 30min, taking out the sheath, and sealing the exhaust tube 3. And (4) moving the sheath into a hot isostatic pressing device, and simultaneously heating and pressurizing, wherein the pressure medium is high-purity argon. Hot isostatic pressing at the maximum temperature of 1100 ℃, the pressure of 120MPa, and heat preservation and pressure maintaining time of 2h. And after the atomized powder is completely sintered and compact, taking out the sheath, and removing the sheath by a machining mode. Heating the blank to 1050 ℃ for heat preservation, carrying out free forging, carrying out multi-pass rolling on a rolling mill after the thickness of the blank reaches 50mm, wherein the final rolling temperature is not lower than 900 ℃ each time, finally manufacturing a 3-4 mm thin plate, and stamping the thin plate into an outdoor small cutter blank with a certain processing allowance; the temperature for carrying out solution treatment on the outdoor small cutter blank is 1030 ℃, and the holding time is 20min; carrying out cryogenic treatment at-176 ℃, and keeping the temperature for 5 hours; the aging temperature is 500 ℃, and the heat preservation time is 6h. Finally, the martensite antibacterial stainless steel outdoor knife with antibacterial property is processed by the outdoor knife blank through the processes of grinding, edging and the like, and a scanning electron microscope photo is shown in figure 3.
Example 2
The raw materials are added into a quartz crucible in a medium-frequency induction furnace of an atomizer according to the weight percentage in sequence as follows: 0.30% of graphite, 12% of chromium, 0.6% of molybdenum, 0.3% of vanadium, 4.0% of copper and the balance of iron. Induction heating to 1650 ℃ melted the alloy. Rapidly pouring stainless steel liquid into a drain ladle, flowing down along a liquid guide pipe, changing the molten steel into dispersed fine liquid drops under the high-pressure water impact, rapidly cooling and solidifying to obtain 3Cr13MoVCu4 alloy powder, wherein the atomization pressure is 110MPa, and the powder is dehydrated, dried, screened and vacuum-packaged for later use; the capsule was dimensioned as in example 1, and powder was added to the capsule while shaking on a shaking table. After the addition is finished, the cover is covered by a sheath cover, and the welding is firm. Putting the sheath into a degassing furnace, heating and vacuumizing. When the temperature is raised to 450 ℃, the vacuum degree reaches 10 -4 And Pa, keeping for 25min, taking out the sheath, and sealing the exhaust tube. And (4) moving the sheath into a hot isostatic pressing device, and simultaneously heating and pressurizing, wherein the pressure medium is high-purity argon. Hot isostatic pressing at the highest temperature of 1080 ℃, the pressure of 115MPa and the heat preservation and pressure maintaining time of 3h. After the atomized powder is completely sintered and compact, the sheath is taken out, and the sheath is removed by a machining mode. Heating the blank to 1080 ℃ for heat preservation, carrying out free forging, carrying out multi-pass rolling on a rolling mill after reaching the specified thickness dimension, wherein the final rolling temperature is not lower than 900 ℃ each time, finally preparing a 3-4 mm thin plate, and stamping the thin plate into an outdoor small cutter blank with a certain processing allowance; the temperature for carrying out solution treatment on the outdoor small cutter blank is 1090 ℃, and the holding time is 15min; performing cryogenic treatment at-176 ℃, and keeping the temperature for 8 hours; the aging temperature is 540 ℃, and the heat preservation time is 4h. And finally, processing the outdoor small knife blank into the martensite antibacterial stainless steel outdoor small knife with antibacterial property through the processes of grinding, edging and the like.
Example 3
The raw materials are added into a quartz crucible in a medium-frequency induction furnace of an atomizer according to the mass percentage in sequence as follows: 0.35% of graphite, 14% of chromium, 0.6% of molybdenum, 0.25% of vanadium, 4.5% of copper and the balance of iron. Induction heating to 1650 ℃ melted the alloy. Rapidly pouring the stainless steel liquid into a drain ladle, flowing down along a liquid guide pipe, changing the liquid steel into dispersed fine liquid drops under the impact of high-pressure water, and rapidly cooling and solidifying to obtain 3Cr13MoVCu4 alloy powderAnd the atomization pressure is 120MPa. Dehydrating, drying, sieving and vacuum packaging the powder for later use; the capsule was dimensioned as in example 1, and powder was added to the capsule while shaking on a shaking table. After the addition is finished, the cover is covered by a sheath cover, and the welding is firm. Putting the sheath into a degassing furnace, heating and vacuumizing. When the temperature is raised to 500 ℃, the vacuum degree reaches 10 -4 And Pa, keeping for 20min, taking out the sheath, and sealing the exhaust tube. And (4) moving the sheath into a hot isostatic pressing device, and simultaneously heating and pressurizing, wherein the pressure medium is high-purity argon. Hot isostatic pressing at the maximum temperature of 1150 ℃, the pressure of 110MPa and the heat preservation and pressure maintaining time of 3h. And after the atomized powder is completely sintered and compact, taking out the sheath, and removing the sheath by a machining mode. Heating the blank to 1150 ℃, preserving heat, performing free forging, performing multi-pass rolling on a rolling mill after the blank reaches the specified thickness dimension, wherein the final rolling temperature is not lower than 900 ℃ each time, finally manufacturing a 3-4 mm thin plate, and stamping the thin plate into an outdoor small cutter blank with a certain processing allowance; the temperature for carrying out solid solution treatment on the outdoor small cutter blank is 1080 ℃, and the holding time is 25min; carrying out cryogenic treatment at-176 ℃, and keeping the temperature for 10 hours; the aging temperature is 450 ℃, and the heat preservation time is 14h. And finally, processing the outdoor small knife blank into the martensite antibacterial stainless steel outdoor small knife with antibacterial property by the processes of grinding, edging and the like.
Example 4
The difference from example 3 is only that the raw materials of the 3Cr13MoVCu4 alloy powder are as follows: 0.38% of graphite, 12% of chromium, 1.0% of molybdenum, 0.2% of vanadium, 3.8% of copper and the balance of iron.
The martensitic antimicrobial stainless steel outdoor knife prepared in examples 1 to 4 was subjected to performance tests, wherein the bending strength was as per national standard GB/T3851-2015, the antimicrobial rate was as per japanese industrial standard JIS Z2801, and the sharpness test was as per standard ISO 8442-5 2004, and the results are shown in table 1.
TABLE 1
As can be seen from table 1, the martensite antibacterial stainless steel knife prepared by the method of the present invention has excellent mechanical properties, usability and antibacterial properties, and the antibacterial rate to escherichia coli (e.coli) and staphylococcus aureus (s.aureus) is above 99.6%.
Comparative example 1
The difference from example 3 is that the high temperature aging treatment is not performed in step (4).
Comparative example 2
The only difference from example 3 is that the solution treatment and the cryogenic treatment are not performed in step (4).
Comparative example 3
The difference from example 3 is that the 3Cr13MoVCu4 alloy powder is prepared into a green body by a non-hot isostatic pressing method, which comprises the following steps: the same chemical composition raw materials as in example 3 were subjected to 1550 ℃ melting and electroslag remelting to prepare a blade body blank, and the subsequent deformation processing and heat treatment processes were the same as in example 3, wherein the blade body blank was subjected to 900 ℃ annealing.
Comparative example 4
The only difference from example 3 is that the hot isostatic pressing temperature is 1300 ℃.
The outdoor knives prepared in comparative examples 1 to 4 were tested for their performance according to the same test standard as in example 1, and the results are shown in table 2.
TABLE 2
As can be seen from Table 2, comparative example 1, which has a very low antibacterial efficiency compared to example 3 due to the absence of high temperature aging treatment, can be used as a general knife with the hardness, bending strength and sharpness being maintained or slightly increased; comparative example 2 is not subjected to solid solution treatment and cold treatment, the knife material is not subjected to quench hardening treatment, the plasticity is good, but the hardness and sharpness are low, copper element is not dissolved into a matrix, the antibacterial rate is less than 50%, and the material cannot be used as a cutter; comparative example 3, the material prepared by the casting and forging method has hardness, strength and sharpness lower than those of the material prepared by hot isostatic pressing due to coarse grains, uneven structure, segregation of copper components and the like, and the antibacterial rate is only 91%; comparative example 4, too high hot isostatic pressing temperature resulted in coarse material grains, increased brittleness, sharply decreased hardness, bending strength and sharpness, and only maintained high level of antibacterial property.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (9)
1. The martensite antibacterial stainless steel outdoor knife is characterized in that the raw material is 3Cr13MoVCu4 powder and comprises the following components in percentage by mass:
0.28 to 0.38 percent of carbon, 12 to 14 percent of chromium, 0.5 to 1.0 percent of molybdenum, 0.2 to 0.3 percent of vanadium, 3.5 to 4.5 percent of copper, and the balance of iron and inevitable impurities.
2. A method of making the martensitic stainless steel outdoor knife of claim 1, comprising the steps of:
carrying out hot isostatic pressing treatment on the outer sheath die filled with 3Cr13MoVCu4 powder, then carrying out free forging, rolling and stamping to obtain an outdoor small knife blank, carrying out solid solution treatment and cryogenic treatment on the outdoor small knife blank, then carrying out high-temperature aging, grinding and edging to obtain the martensite antibacterial stainless steel outdoor knife.
3. The preparation method according to claim 2, comprising the following steps:
(1) Preparation of stainless steel atomized powder
Weighing graphite, chromium, molybdenum, vanadium, copper and iron according to the mass percent of 0.28-0.38% of carbon, 12-14% of chromium, 0.5-1.0% of molybdenum, 0.2-0.3% of vanadium, 3.5-4.5% of copper and the balance of iron, smelting to obtain alloy liquid, and cooling to obtain stainless steel atomized powder;
(2) Hot isostatic pressing of stainless steel atomized powder
Filling the stainless steel atomized powder into a metal sheath, compacting, heating, degassing, sealing, performing hot isostatic pressing, and removing the metal sheath to obtain a hot isostatic pressing stainless steel blank;
(3) Hot isostatic pressing stainless steel blank deformation treatment and stamping
Heating and insulating the hot isostatic pressing stainless steel blank, then carrying out free forging, carrying out hot rolling after the thickness of the hot isostatic pressing stainless steel blank reaches a specified size, finally manufacturing a 3-4 mm thin plate, and stamping the thin plate into an outdoor small cutter blank with a machining allowance;
(4) Outdoor small knife blank heat treatment
And carrying out solid solution treatment and subzero treatment on the outdoor small knife blank, then carrying out high-temperature aging, grinding and edging to obtain the martensite antibacterial stainless steel outdoor small knife.
4. The preparation method according to claim 3, wherein the degassing temperature in the step (2) is 400-600 ℃ and the vacuum degree reaches 10 -4 Pa, keeping for 15-40 min.
5. The preparation method of claim 3, wherein the hot isostatic pressing temperature in the step (2) is 1080-1180 ℃, the pressure is 100-160 MPa, and the holding time is 1.5-4 h.
6. The method according to claim 3, wherein the heating temperature in the step (3) is 1050 to 1150 ℃.
7. The method according to claim 3, wherein the solution treatment temperature in the step (4) is 1030 to 1100 ℃ and the holding time is 10 to 40min.
8. The method according to claim 3, wherein the temperature of the cryogenic treatment in step (4) is-176 ℃ and the temperature is kept for 5-10 h.
9. The preparation method according to claim 3, wherein the high temperature aging temperature in the step (4) is 400-700 ℃, and the holding time is 4-15 h.
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