CN116445830B - A creep-resistant high-thermal-conductivity graphene-modified high-speed steel material and a preparation method thereof - Google Patents

A creep-resistant high-thermal-conductivity graphene-modified high-speed steel material and a preparation method thereof Download PDF

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CN116445830B
CN116445830B CN202310376370.4A CN202310376370A CN116445830B CN 116445830 B CN116445830 B CN 116445830B CN 202310376370 A CN202310376370 A CN 202310376370A CN 116445830 B CN116445830 B CN 116445830B
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speed steel
steel material
graphene
ball milling
creep
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CN116445830A (en
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谢丰伟
袁紫仁
陈帅鹏
康希越
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Changsha Sharpen Advanced Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making 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%
    • C22C33/0285—Making 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%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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Abstract

The invention discloses a creep-resistant high-heat-conductivity graphene modified high-speed steel material and a preparation method thereof. Comprises the following elements in percentage by mass: 15-30% of Co, 10-20% of the total amount of Mo and W, less than 8% of W, 5-10% of Cr, 5-7% of Ni, 5-8% of Al, 1.5-2% of Si, 0.5-1% of V, 0.5-1% of Ta, 0.1-0.3% of Ce, 0.1-0.2% of Sc, 0.5-1.5% of graphene and the balance of iron. The material has the advantages that on the premise of ensuring the hardness of the material, the toughness and the thermal conductivity of the material under the high-temperature condition are greatly improved based on the synergistic effect of the intermetallic compound generated in situ and the graphene material, and the excellent high-temperature mechanical property is endowed to the material. The composite material is prepared by fully mixing raw materials and improving sintering activity through ultrasonic dispersion and high-energy ball milling, and a nanoscale intermetallic compound is generated under the synergistic effect of heat treatment in the subsequent process, so that a remarkable strengthening effect is obtained.

Description

Creep-resistant high-heat-conductivity graphene modified high-speed steel material and preparation method thereof
Technical Field
The invention relates to a high-speed steel material, in particular to a creep-resistant high-heat-conductivity graphene modified high-speed steel material and a preparation method thereof, and belongs to the field of special alloy preparation.
Background
With the vigorous development of industries such as home building materials, information photoelectricity, automobile industry and intelligent equipment, the 3D curved glass is paid attention to due to the unique optical properties, thermal stability properties, mechanical properties and the like. For example, in the field of smart phones, 3D curved glass is widely used in high-end models of mobile phones due to the characteristics of light weight, transparency, cleanliness, plump visual effect, better touch feeling, and the like, and related data show that the permeability of a 3D glass cover plate of a smart phone is rising year by year, and the market scale in the future is promising as large as about 27% in 2020. Meanwhile, 3C product design is like wearable intelligent product such as tablet computer, wear-type VR equipment, intelligent wrist-watch, and the application of 3D glass all appears in succession in scene such as accuse and portable panel board in the vehicle for market demand and precision requirement to 3D glass constantly improve, and then have driven the development of whole industry chain. However, the processing difficulty of the 3D curved glass is far higher than that of the common plane glass due to the special complex geometric dimension.
At present, the 3D curved glass is mainly prepared by cold working and hot forming technology, but the expensive equipment cost and long processing period of the cold working technology limit the application of the cold working technology in the civil demand field with small size and large yield. The widely used thermoforming technology is to perform pressure processing and rheological forming on the heated high-viscoelasticity state glass through a forming die, so as to prepare curved glass with high shape and dimensional accuracy. The thermoformed core device is a 3D hot-bending glass machine. The hot bending process can be summarized to provide a heat source for heating the heating pipe, and heat and pressure are transmitted into the glass sequentially through the heating plate, the vapor chamber and the mold, so that hot bending forming is completed. Obviously, the heating plate is an initial part for heat transfer and force transfer in the hot bending forming process, and the temperature control precision, temperature uniformity, force transfer uniformity and other performances determine the precision of the whole hot bending system and the hot bending products. However, the 310S stainless steel (or similar grade) heating plate adopted by the current hot bending equipment has the problems of low high-temperature hardness, low heat conductivity coefficient and large heat expansion coefficient. The heat conductivity coefficient of 310S at room temperature is only 12-15W/(m.k), the heat transfer rate is slow, the uniformity of a temperature field is limited, the burden of a heating tube is increased, compared with other parts of a heating system, the heat expansion coefficient of 310S is much higher than that of a soaking plate and a die which are fixedly integrated with the soaking plate, deformation is caused by mismatching of the heat expansion coefficient at high temperature, high plane precision is difficult to ensure when the soaking plate is used for a long time, meanwhile, the service hardness of 310S at the high temperature for a long time is extremely low, the hardness is as low as below 10HRC when the soaking plate is used at 600-900 ℃, and the material is extremely easy to soften to cause creep deformation. In summary, the 310S heating plate adds uncertainty and instability to the hot bending system, which cannot further improve the equipment accuracy and limit the production efficiency, however, other suitable alternative materials are not found in the industry. In addition, since the heater plate material is typically in service in high temperature environments above 600 ℃, i.e., material high temperature oxidation issues are also a concern. Therefore, there is a need for a new material for heating plates with high thermal conductivity, high Wen Jiangying degrees, low thermal expansion coefficient, and good oxidation resistance.
Disclosure of Invention
Aiming at the problems existing in the prior art, the first aim of the invention is to provide a creep-resistant high-heat-conductivity graphene modified high-speed steel material, which is based on the synergistic effect among the components, and utilizes intermetallic compounds generated in situ and dispersed graphene to carry out synergistic reinforcement, so that the toughness, stability and heat conductivity of the material are greatly improved on the premise of ensuring the high-temperature hardness of the material.
The second aim of the invention is to provide a preparation method of the creep-resistant high-heat-conductivity graphene modified high-speed steel material, which comprises the steps of dispersing graphene in batches and performing high-energy ball milling, fully mixing the graphene with other metal raw materials, improving the sintering activity of the material, and promoting the uniform precipitation of nanoscale intermetallic compounds through heat treatment, so that the toughness of the material is improved.
The creep-resistant high-heat-conductivity graphene modified high-speed steel material comprises, by mass, 15-30% of Co, 10-20% of the total amount of Mo and W, less than 8% of W, 5-10% of Cr, 5-7% of Ni, 5-8% of Al, 1.5-2% of Si, 0.5-1% of V, 0.5-1% of Ta, 0.1-0.3% of Ce, 0.1-0.2% of Sc, 0.5-1.5% of graphene and the balance of iron.
The intermetallic compound in the creep-resistant high-heat-conductivity graphene modified high-speed steel material is generated in situ by Fe, co, mo, W, cr, al and other elements, and compared with a carbide reinforced phase in the traditional high-speed steel, the intermetallic compound is not easy to aggregate and overage at high temperature, and maintains a coherent/semi-coherent interface relation with an alpha-Fe matrix, so that the creep-resistant high-heat-conductivity graphene modified high-speed steel material has high-temperature strong hardness, excellent heat conductivity, smaller thermal expansion coefficient and better toughness. Meanwhile, a proper amount of graphene material is added into the intermetallic compound reinforced high-speed steel matrix, and the characteristics of high strength, high thermal conductivity and high stability of graphene are utilized, so that the toughness, thermal conductivity and oxidation resistance of the high-speed steel material are further enhanced.
The high-speed steel material comprises, by mass, 18-27% of Co, 13-18% of the total amount of Mo and W, and less than 6% of W, 7-10% of Cr, 5-7% of Ni, 6-8% of Al, 1.5-2% of Si, 0.5-1% of V, 0.5-1% of Ta, 0.1-0.3% of Ce, 0.1-0.2% of Sc, 1-1.5% of graphene and the balance of Fe, wherein the high-speed steel material comprises an in-situ strengthening phase composed of intermetallic compounds and high-dispersion graphene.
In the high-speed steel material provided by the invention, the addition amount of Mo and W elements is strictly controlled according to the requirements. Because of the higher melting point and higher specific gravity of W, when the W content is high, the sintering and heat treatment require higher temperatures, i.e., consume more energy and cost, and are also unfavorable for the light weight requirements.
As a preferred embodiment, the intermetallic compound is an intermetallic compound of type a 7B6 and/or type AB 2.
As a preferable scheme, the graphene is nickel-plated graphene.
According to the invention, nickel-plated graphene is used as a graphene raw material, so that the interaction between the nickel-plated graphene and iron at high temperature can be reduced to the greatest extent, the integrity of the graphene is ensured, and meanwhile, the interface wettability is good. In the composite high-speed steel material, on one hand, graphene inhibits grain growth and dislocation movement, so that the material is reinforced, the mechanical property is improved, and on the other hand, the heat conduction property of the whole material is enhanced through the extremely high heat conduction coefficient (about 5000W/(m.K)) of the graphene.
The invention also provides a preparation method of the creep-resistant high-heat-conductivity graphene modified high-speed steel material, which comprises the steps of dispersing graphene in a ball milling medium, adding residual metal element powder for continuous dispersion, and sequentially carrying out ball milling and drying with an auxiliary agent to obtain a mixture.
As a preferable scheme, the mixture is obtained by sieving, cold pressing, sintering and heat treatment in sequence.
As a preferable scheme, the dispersing mode is ultrasonic dispersing, and the condition is that the ultrasonic power is 100-200W and the time is 20-40 min. The preparation method provided by the invention can realize uniform dispersion of graphene raw materials and metal mixed powder, and obtain the graphene reinforced composite material with high density and uniform tissue distribution.
As a preferred scheme, the ball milling medium is at least one of water, ethanol, propanol and petroleum ether.
As a preferred embodiment, the ball milling medium is ethanol.
As a preferable scheme, the ball milling mode is wet high-energy ball milling, and the conditions are that the ball-material ratio is 4-7:1, the rotating speed is 240-340 r/min and the time is 72-96 h under a protective atmosphere, and the protective atmosphere is high-purity nitrogen and/or high-purity argon.
As a preferable scheme, the addition amount of the carbon black accounts for 0.2-0.5% of the mass of the mixture.
In the present invention, carbon black is added to react with adsorbed oxygen during sintering to reduce the impurity oxygen content of the material on the one hand and to expose fresh atoms on the powder surface to increase the sintering driving force on the other hand, but it should be noted that carbon black is entirely consumed during sintering and does not participate in the formation of the final product.
As a preferred embodiment, the molding agent is at least one of paraffin wax, PEG, and PVB.
As a preferable scheme, the addition amount of the forming agent accounts for 3-6% of the mass of the mixture.
As a preferable scheme, the particle size of the material obtained by sieving the mixture is less than or equal to 40 meshes.
As a preferable scheme, the pressure of the cold pressing is 100-200 MPa.
As a preferred embodiment, the sintering is temperature programmed vacuum sintering.
As a preferable scheme, the sintering condition is that the temperature is raised from room temperature to 1300-1400 ℃ at 5-10 ℃ per min, the temperature is kept for 2-4 h, and the vacuum degree is less than or equal to 0.01Pa.
As a preferred embodiment, the heat treatment includes a solution treatment and an aging treatment.
As a preferable scheme, the solution treatment condition is that the solution treatment is carried out for 0.5-1.5 h at 1150-1250 ℃, and the solution treatment is carried out by gas quenching and cooling to room temperature.
As a preferable scheme, the aging treatment is carried out under the condition that the temperature is 700-1000 ℃ and the time is 3-5 h under the protection atmosphere, and the temperature is cooled to the room temperature along with the furnace. The aging treatment aims to promote the sufficiently and uniformly precipitated and grown nanoscale intermetallic compounds in the high-speed steel material, thereby improving the toughness and stability of the material.
Compared with the prior art, the invention has the following beneficial technical effects:
1) The high-speed steel material provided by the invention has the advantages that based on the synergistic effect among the components, intermetallic compounds generated in situ in the aging process have a coherent or semi-coherent relation with the matrix, the hardness of the material can be effectively enhanced, the added Cr, al and Si elements can form a compact oxide film structure with the Fe matrix, the high-temperature oxidation resistance of the material is further improved, the rare earth elements Ce and Sc can effectively adsorb impurities such as oxygen, sulfur and the like, the sintering is activated, and the grain boundary is purified, so that the high-temperature stability and the toughness of the material are effectively improved.
2) The high-speed steel material provided by the invention has the advantages that the room temperature peak hardness is 85-87HRA, the bending strength is 2800-3500MPa, the impact toughness is 10-15J/cm 2, the 700 ℃ heat conductivity coefficient is 45-50W/(m.K), the 800 ℃ high-temperature hardness is 81-83.5HRA, the 600 ℃ aging 200h hardness is 82-85HRA, and the thermal expansion coefficient is reduced by 20-30% compared with that of 310S stainless steel. Meanwhile, the high-speed steel can regulate and control the corresponding performance through a heat treatment process, for example, the impact toughness can be improved to 60-80J/cm 2 through high-temperature aging at 900 ℃ for 3 hours. Namely, the high-speed steel has the characteristics of high hardness, excellent heat conductivity, small heat expansion coefficient and the like, and can realize comprehensive performance optimization.
3) The high-speed steel material can quickly transfer the heat of the heating pipe, lighten the load power of the heating pipe, improve the overall service life of a heating system, has excellent dimensional stability in long-term high-temperature service, can keep high hardness and high strength, and reduces creep deformation, thereby improving the precision and the production efficiency of a hot bending system.
Drawings
FIG. 1 is a photograph of a microstructure of a scanning electron microscope of example 1;
FIG. 2 is a photograph of a microstructure of a comparative example 1.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to the following examples, but the embodiments of the present invention are not limited thereto.
The metal powder D50 has a granularity of 1-10 μm, and the Ce powder and Sc powder have a granularity of 200-400 meshes.
In the following cases, the ball milling media are all absolute ethyl alcohol, the consumption of the ball milling media is 0.8mL/g based on the raw material powder, and the ball milling rotating speed is 300r/min.
Example 1
(1) Ultrasonic dispersion of raw materials
Adding 1.4wt.% of nickel-plated graphene raw material into absolute ethyl alcohol, performing ultrasonic vibration for 30min (the ultrasonic power is 150W), adding the rest metal element and rare earth element powder weighed according to the proportion, and performing ultrasonic vibration for 30min together to obtain the uniformly dispersed mixed powder absolute ethyl alcohol solution.
(2) High-energy ball milling and mixing of raw materials
Adding 0.3wt.% of carbon black and 5wt.% of paraffin wax forming agent into the absolute ethanol solution of the mixed powder obtained in the step (1), and then putting the mixed powder and the absolute ethanol solution into a ball milling tank which can be filled with argon for protection for wet ball milling, wherein the ball milling medium is absolute ethanol, the dosage is 0.8mL/g, the ball-material ratio is 5:1, the ball milling rotating speed is 300r/min, and the ball milling time is 80h. And after ball milling, drying in a vacuum drying oven, wherein the temperature is set to 82 ℃ and the drying time is 5 hours.
(3) Compression molding
Sieving the dried mixed powder in the step (2) by 40 meshes, and then performing cold die pressing under 150MPa to obtain a pressed compact.
(4) Vacuum sintering
And (3) placing the pressed blank into a vacuum sintering furnace for vacuum sintering, controlling the vacuum degree to be less than 0.01Pa, heating the pressed blank from room temperature to the highest sintering temperature of 1350 ℃ at 8 ℃ per minute, preserving the heat for 3 hours, and cooling the pressed blank to room temperature along with the furnace to obtain the sintered blank.
(5) Heat treatment of
And placing the sintered blank in a vacuum quenching furnace for solution treatment, wherein the solution treatment temperature is 1220 ℃, the heat preservation time is 1h, and cooling to room temperature through gas quenching after the solution treatment. And then aging treatment is carried out in an atmosphere furnace which is filled with nitrogen for protection, wherein the aging temperature is 800 ℃ and the aging time is 4 hours. Thus obtaining the high-speed steel material for the heating plate of the hot bending glass machine.
Example 2
(1) Ultrasonic dispersion of raw materials
Adding 1.0wt.% of nickel-plated graphene raw material into absolute ethyl alcohol, performing ultrasonic vibration for 30min (the ultrasonic power is 150W), adding the rest metal element and rare earth element powder weighed according to the proportion, and performing ultrasonic vibration for 30min together to obtain a uniformly dispersed mixed powder absolute ethyl alcohol solution.
(2) High-energy ball milling and mixing of raw materials
Adding 0.4wt.% of carbon black and 5wt.% of paraffin wax forming agent into the absolute ethanol solution of the mixed powder obtained in the step (1), and then putting the mixed powder and the absolute ethanol solution into a ball milling tank which can be filled with argon for protection for wet ball milling, wherein the ball milling medium is absolute ethanol, the dosage is 0.8mL/g, the ball-material ratio is 5:1, the ball milling rotating speed is 300r/min, and the ball milling time is 80h. And after ball milling, drying in a vacuum drying oven, wherein the temperature is set to 82 ℃ and the drying time is 5 hours.
(3) Compression molding
Sieving the dried mixed powder in the step (2) by 40 meshes, and then performing cold die pressing under 150MPa to obtain a pressed compact.
(4) Vacuum sintering
And (3) placing the pressed blank in a vacuum sintering furnace for vacuum sintering, controlling the vacuum degree to be less than 0.01Pa, heating from room temperature to the highest sintering temperature of 1330 ℃ at 8 ℃ per min, preserving the heat for 3h, and cooling to room temperature along with the furnace to obtain a sintered blank.
(5) Heat treatment of
And placing the sintered blank in a vacuum quenching furnace for solution treatment, wherein the solution treatment temperature is 1210 ℃, the heat preservation time is 1h, and cooling to room temperature through gas quenching after the solution treatment. And then aging treatment is carried out in an atmosphere furnace which is filled with nitrogen for protection, wherein the aging temperature is 800 ℃ and the aging time is 4 hours. Thus obtaining the high-speed steel material for the heating plate of the hot bending glass machine.
Example 3
(1) Ultrasonic dispersion of raw materials
Adding 0.5wt.% nickel-plated graphene raw material into absolute ethyl alcohol, performing ultrasonic vibration for 30min (the ultrasonic power is 150W), adding the rest metal element and rare earth element powder weighed according to the proportion, and performing ultrasonic vibration for 30min together to obtain the uniformly dispersed mixed powder absolute ethyl alcohol solution.
(2) High-energy ball milling and mixing of raw materials
Adding 0.3wt.% of carbon black and 5wt.% of paraffin wax forming agent into the absolute ethanol solution of the mixed powder obtained in the step (1), and then putting the mixed powder into a ball milling tank which can be filled with argon for protection for wet ball milling, wherein the ball milling medium is absolute ethanol, the dosage is 0.8mL/g, the ball-material ratio is 5:1, the ball milling rotating speed is 300r/min, and the ball milling time is 85h. And after ball milling, drying in a vacuum drying oven, wherein the temperature is set to 82 ℃ and the drying time is 5 hours.
(3) Compression molding
Sieving the dried mixed powder in the step (2) by 40 meshes, and then performing cold die pressing under 150MPa to obtain a pressed compact.
(4) Vacuum sintering
And (3) placing the pressed blank in a vacuum sintering furnace for vacuum sintering, controlling the vacuum degree to be less than 0.01Pa, heating the pressed blank from room temperature to the highest sintering temperature of 1300 ℃ at 8 ℃ per minute, preserving the heat for 3 hours, and cooling the pressed blank to the room temperature along with the furnace to obtain the sintered blank.
(5) Heat treatment of
And (3) placing the sintered blank in a vacuum quenching furnace for solution treatment, wherein the solution treatment temperature is 1190 ℃, the heat preservation time is 1h, and cooling to room temperature through gas quenching after the solution treatment. And then aging treatment is carried out in an atmosphere furnace which is filled with nitrogen for protection, wherein the aging temperature is 750 ℃ and the aging time is 4 hours. Thus obtaining the high-speed steel material for the heating plate of the hot bending glass machine.
Example 4
(1) Ultrasonic dispersion of raw materials
Adding 1.5wt.% of nickel-plated graphene raw material into absolute ethyl alcohol, performing ultrasonic vibration for 30min (the ultrasonic power is 150W), adding the rest metal element and rare earth element powder weighed according to the proportion, and performing ultrasonic vibration for 30min together to obtain the uniformly dispersed mixed powder absolute ethyl alcohol solution.
(2) High-energy ball milling and mixing of raw materials
Adding 0.3wt.% of carbon black and 5wt.% of paraffin wax forming agent into the absolute ethanol solution of the mixed powder obtained in the step (1), and then putting the mixed powder and the absolute ethanol solution into a ball milling tank which can be filled with argon for protection for wet ball milling, wherein the ball milling medium is absolute ethanol, the dosage is 0.8mL/g, the ball-material ratio is 5:1, the ball milling rotating speed is 300r/min, and the ball milling time is 80h. And after ball milling, drying in a vacuum drying oven, wherein the temperature is set to 82 ℃ and the drying time is 5 hours.
(3) Compression molding
Sieving the dried mixed powder in the step (2) by 40 meshes, and then performing cold die pressing under 150MPa to obtain a pressed compact.
(4) Vacuum sintering
And (3) placing the pressed blank in a vacuum sintering furnace for vacuum sintering, controlling the vacuum degree to be less than 0.01Pa, heating the pressed blank from room temperature to the highest sintering temperature 1380 ℃ at 8 ℃ per minute, preserving the heat for 3 hours, and cooling the pressed blank to the room temperature along with the furnace to obtain the sintered blank.
(5) Heat treatment of
And placing the sintered blank in a vacuum quenching furnace for solution treatment, wherein the solution treatment temperature is 1270 ℃, the heat preservation time is 1h, and cooling to room temperature through gas quenching after the solution treatment. And then aging treatment is carried out in an atmosphere furnace which is filled with nitrogen for protection, wherein the aging temperature is 850 ℃ and the aging time is 4 hours. Thus obtaining the high-speed steel material for the heating plate of the hot bending glass machine.
Example 5
(1) Ultrasonic dispersion of raw materials
Adding 0.9wt.% of nickel-plated graphene raw material into absolute ethyl alcohol, performing ultrasonic vibration for 30min (the ultrasonic power is 150W), adding the rest metal element and rare earth element powder weighed according to the proportion, and performing ultrasonic vibration for 30min together to obtain the uniformly dispersed mixed powder absolute ethyl alcohol solution.
(2) High-energy ball milling and mixing of raw materials
Adding 0.3wt.% of carbon black and 5wt.% of paraffin wax forming agent into the absolute ethanol solution of the mixed powder obtained in the step (1), and then putting the mixed powder and the absolute ethanol solution into a ball milling tank which can be filled with argon for protection for wet ball milling, wherein the ball milling medium is absolute ethanol, the dosage is 0.8mL/g, the ball-material ratio is 5:1, the ball milling rotating speed is 300r/min, and the ball milling time is 80h. And after ball milling, drying in a vacuum drying oven, wherein the temperature is set to 82 ℃ and the drying time is 5 hours.
(3) Compression molding
Sieving the dried mixed powder in the step (2) by 40 meshes, and then performing cold die pressing under 150MPa to obtain a pressed compact.
(4) Vacuum sintering
And (3) placing the pressed blank into a vacuum sintering furnace for vacuum sintering, controlling the vacuum degree to be less than 0.01Pa, heating the pressed blank from room temperature to the highest sintering temperature of 1350 ℃ at 8 ℃ per minute, preserving the heat for 3 hours, and cooling the pressed blank to room temperature along with the furnace to obtain the sintered blank.
(5) Heat treatment of
And placing the sintered blank in a vacuum quenching furnace for solution treatment, wherein the solution treatment temperature is 1200 ℃, the heat preservation time is 1h, and cooling to room temperature through gas quenching after the solution treatment. And then aging treatment is carried out in an atmosphere furnace which is filled with nitrogen for protection, wherein the aging temperature is 800 ℃ and the aging time is 4 hours. Thus obtaining the high-speed steel material for the heating plate of the hot bending glass machine.
Comparative example 1
This comparative example is identical to the preparation process employed in example 1, except for the ingredients.
Comparative example 2
This comparative example is identical to the preparation process employed in example 1, except for the ingredients.
Comparative example 3
This comparative example is identical to the preparation process employed in example 1, except for the ingredients.
Comparative example 4
This comparative example is identical to the preparation process employed in example 1, except for the ingredients.
Comparative example 5
(1) Ultrasonic dispersion of raw materials
Adding 1.4wt.% of nickel-plated graphene raw material into absolute ethyl alcohol, performing ultrasonic vibration for 30min (the ultrasonic power is 150W), adding the rest metal element and rare earth element powder weighed according to the proportion, and performing ultrasonic vibration for 30min together to obtain the uniformly dispersed mixed powder absolute ethyl alcohol solution.
(2) High-energy ball milling and mixing of raw materials
Adding 0.3wt.% of carbon black and 5wt.% of paraffin wax forming agent into the absolute ethanol solution of the mixed powder obtained in the step (1), and then putting the mixed powder and the absolute ethanol solution into a ball milling tank which can be filled with argon for protection for wet ball milling, wherein the ball milling medium is absolute ethanol, the dosage is 0.8mL/g, the ball-material ratio is 5:1, the ball milling rotating speed is 300r/min, and the ball milling time is 80h. And after ball milling, drying in a vacuum drying oven, wherein the temperature is set to 82 ℃ and the drying time is 5 hours.
(3) Compression molding
Sieving the dried mixed powder in the step (2) by 40 meshes, and then performing cold die pressing under 150MPa to obtain a pressed compact.
(4) Vacuum sintering
And (3) placing the pressed blank in a vacuum sintering furnace for vacuum sintering, controlling the vacuum degree to be less than 0.01Pa, heating the pressed blank from room temperature to the highest sintering temperature of 1250 ℃ at 8 ℃ per minute, preserving the heat for 3 hours, and cooling the pressed blank to room temperature along with the furnace to obtain the sintered blank.
(5) Heat treatment of
And placing the sintered blank in a vacuum quenching furnace for solution treatment, wherein the solution treatment temperature is 1200 ℃, the heat preservation time is 1h, and cooling to room temperature through gas quenching after the solution treatment. And then aging treatment is carried out in an atmosphere furnace which is filled with nitrogen for protection, wherein the aging temperature is 800 ℃ and the aging time is 4 hours. Thus obtaining the high-speed steel material for the heating plate of the hot bending glass machine.
Comparative example 6
(1) High-energy ball milling and mixing of raw materials
The metal powder, the rare earth powder, the nickel-plated graphene raw material, 0.3wt.% of carbon black and 5wt.% of paraffin wax forming agent which are additionally added are put into a ball milling tank which can be filled with argon for wet ball milling according to the proportion, the ball milling medium is absolute ethyl alcohol, the dosage is 0.8mL/g, the ball-material ratio is 5:1, the ball milling rotating speed is 300r/min, and the ball milling time is 80h. And after ball milling, drying in a vacuum drying oven, wherein the temperature is set to 82 ℃ and the drying time is 5 hours.
(2) Compression molding
Sieving the dried mixed powder in the step (2) by 40 meshes, and then performing cold die pressing under 150MPa to obtain a pressed compact.
(3) Vacuum sintering
And (3) placing the pressed blank into a vacuum sintering furnace for vacuum sintering, controlling the vacuum degree to be less than 0.01Pa, heating the pressed blank from room temperature to the highest sintering temperature of 1350 ℃ at 8 ℃ per minute, preserving the heat for 3 hours, and cooling the pressed blank to room temperature along with the furnace to obtain the sintered blank.
(5) Heat treatment of
And placing the sintered blank in a vacuum quenching furnace for solution treatment, wherein the solution treatment temperature is 1220 ℃, the heat preservation time is 1h, and cooling to room temperature through gas quenching after the solution treatment. And then aging treatment is carried out in an atmosphere furnace which is filled with nitrogen for protection, wherein the aging temperature is 800 ℃ and the aging time is 4 hours. Thus obtaining the high-speed steel material for the heating plate of the hot bending glass machine.
The raw material composition ratios in examples and comparative examples provided by the present invention are shown in table 1.
As the mechanical properties of the high-speed steel material are related to the heat treatment process, the peak aging process is adopted for uniform comparison to compare the room temperature hardness, the bending strength and the impact toughness, and the high-temperature hardness is a hardness value tested in real time at 800 ℃ for 20 min. Table 2 shows the results of the performance tests of the examples and the comparative examples.
Table 1 the mass percentages (wt.%) of the components of the examples and comparative examples
Co Mo W Cr Al Ni Si V Ta Ce Sc Graphene Fe
Example 1 25 15 3 9 8 7 1.8 0.7 0.5 0.2 0.2 1.4 Bal.
Example 2 21 12 2 7 6 7 1.6 0.6 0.6 0.2 0.2 1.0 Bal.
Example 3 15 9 1 5 5 6 1.5 0.5 0.5 0.1 0.1 0.5 Bal.
Example 4 27 13 4 10 7 7 2 0.8 0.8 0.3 0.2 1.5 Bal.
Example 5 18 10 5 8 7 7 1.7 0.5 0.6 0.2 0.2 0.9 Bal.
Comparative example 1 25 15 3 9 8 7 1.8 0.7 0.5 0.2 0.2 0 Bal.
Comparative example 2 25 15 3 9 8 7 1.8 0.7 0.5 0.2 0.2 2.0 Bal.
Comparative example 3 21 12 2 7 6 7 1.6 0.6 0.6 0 0 1.0 Bal.
Comparative example 4 25 15 3 13 10 10 1.8 0.7 0.5 0.2 0.2 1.4 Bal.
Comparative example 5 25 15 3 9 8 7 1.8 0.7 0.5 0.2 0.2 1.4 Bal.
Comparative example 6 25 15 3 9 8 7 1.8 0.7 0.5 0.2 0.2 1.4 Bal.
Table 2 results of the performance tests of examples and comparative examples
As can be seen from the performance results of Table 2, the high-speed steel material prepared by the embodiment of the invention has excellent high-temperature hardness and tempering resistance, i.e. can maintain excellent tissue and dimensional stability when applied at high temperature, compared with the conventional powder high-speed steel ASP30 and 310S stainless steel, and meanwhile, the large heat conductivity coefficient can accelerate heat transfer, thereby being beneficial to reducing energy consumption in the hot bending process and improving the heating uniformity of glass. Namely, compared with the original heating plate material 310S stainless steel, the high-speed steel material prepared by the material composition and the preparation method can improve the production precision and the production efficiency, and has great application prospect. And compared with the comparative examples in the material composition range or the process range, the performance is reduced due to the defects of unreasonable composition design, uneven mixing, low sintering density and the like.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.

Claims (8)

1.一种抗蠕变高导热石墨烯改性高速钢材料，其特征在于：包含以下质量百分比元素：Co 15~30%，Mo和W的总量为10~20%且W含量＜8%，Cr 5~10%，Ni 5~7%，Al 5~8%，Si 1.5~2%，V0.5~1%，Ta 0.5~1%，Ce 0.1~0.3%，Sc 0.1~0.2%，石墨烯为0.5~1.5%，余量为铁；所述高速钢材料由金属间化合物和高分散石墨烯构成的原位强化相；1. A creep-resistant high-thermal-conductivity graphene-modified high-speed steel material, characterized in that it contains the following elements by mass percentage: Co 15-30%, the total amount of Mo and W is 10-20% and the W content is less than 8%, Cr 5-10%, Ni 5-7%, Al 5-8%, Si 1.5-2%, V0.5-1%, Ta 0.5-1%, Ce 0.1-0.3%, Sc 0.1-0.2%, graphene is 0.5-1.5%, and the balance is iron; the high-speed steel material is an in-situ strengthening phase composed of intermetallic compounds and highly dispersed graphene; 所述金属间化合物为A7B6型和/或AB2型金属间化合物；The intermetallic compound is an A7B6 type and/or AB2 type intermetallic compound ; 所述高速钢材料的制备过程为：将石墨烯分散于球磨介质中，加入剩余金属元素粉末继续分散，再与助剂依次经球磨和干燥，得混合料；将混合料依次经筛分、冷压、烧结和热处理，即得。The preparation process of the high-speed steel material is as follows: dispersing graphene in a ball milling medium, adding the remaining metal element powder to continue dispersing, and then ball milling and drying with an auxiliary agent in sequence to obtain a mixture; and screening, cold pressing, sintering and heat treating the mixture in sequence to obtain the mixture. 2. 根据权利要求1所述的一种抗蠕变高导热石墨烯改性高速钢材料，其特征在于：所述高速钢材料包含以下质量百分比元素：Co 18~27%，Mo与W的总量 13~18%且W含量＜6%，Cr7~10%，Ni 5~7%，Al 6~8%，Si 1.5~2%，V 0.5~1%，Ta 0.5~1%，Ce 0.1~0.3%，Sc 0.1-0.2%，石墨烯为1~1.5%，余量为Fe。2. The creep-resistant and highly thermally conductive graphene-modified high-speed steel material according to claim 1, characterized in that the high-speed steel material comprises the following elements in mass percentage: Co 18-27%, the total amount of Mo and W 13-18% and the W content is less than 6%, Cr 7-10%, Ni 5-7%, Al 6-8%, Si 1.5-2%, V 0.5-1%, Ta 0.5-1%, Ce 0.1-0.3%, Sc 0.1-0.2%, graphene 1-1.5%, and the balance is Fe. 3.根据权利要求1所述的一种抗蠕变高导热石墨烯改性高速钢材料，其特征在于：所述分散方式为超声分散，其条件为：超声功率为100~200W，时间为20~40min；所述球磨介质为水、乙醇、丙醇和石油醚中的至少一种。3. The creep-resistant and highly thermally conductive graphene-modified high-speed steel material according to claim 1 is characterized in that: the dispersion method is ultrasonic dispersion, and the conditions are: the ultrasonic power is 100-200 W, and the time is 20-40 min; the ball milling medium is at least one of water, ethanol, propanol and petroleum ether. 4.根据权利要求3所述的一种抗蠕变高导热石墨烯改性高速钢材料，其特征在于：所述球磨介质为乙醇；所述球磨方式为湿法高能球磨，其条件为：在保护气氛下，球料比为4~7：1，转速为240~340r/min，时间为72~96h；所述保护气氛为高纯氮气和/或高纯氩气。4. A creep-resistant and highly thermally conductive graphene-modified high-speed steel material according to claim 3, characterized in that: the ball milling medium is ethanol; the ball milling method is wet high-energy ball milling, and the conditions are: under a protective atmosphere, the ball-to-material ratio is 4~7:1, the rotation speed is 240~340r/min, and the time is 72~96h; the protective atmosphere is high-purity nitrogen and/or high-purity argon. 5.根据权利要求1所述的一种抗蠕变高导热石墨烯改性高速钢材料，其特征在于：所述助剂包括炭黑和成型剂，所述炭黑的添加量占混合料质量百分比的0.2~0.5%；所述成型剂为石蜡、PEG和PVB中的至少一种；所述成型剂的添加量占混合料质量百分比的3~6%。5. The creep-resistant and highly thermally conductive graphene-modified high-speed steel material according to claim 1 is characterized in that: the additives include carbon black and a molding agent, the carbon black is added in an amount of 0.2-0.5% by mass of the mixture; the molding agent is at least one of paraffin, PEG and PVB; the molding agent is added in an amount of 3-6% by mass of the mixture. 6.根据权利要求1所述的一种抗蠕变高导热石墨烯改性高速钢材料，其特征在于：所述混合料筛分所得物料的粒径为≤40目；所述冷压的压力为100~200MPa。6. The creep-resistant and highly thermally conductive graphene-modified high-speed steel material according to claim 1 is characterized in that the particle size of the material obtained by screening the mixture is ≤40 mesh; and the cold pressing pressure is 100~200MPa. 7.根据权利要求1所述的一种抗蠕变高导热石墨烯改性高速钢材料，其特征在于：所述烧结为程序升温真空烧结，所述烧结条件为：以5~10℃/min从室温升温至1300~1400℃，保温2~4h，真空度≤0.01Pa。7. The creep-resistant and highly thermally conductive graphene-modified high-speed steel material according to claim 1 is characterized in that: the sintering is programmed temperature rising vacuum sintering, and the sintering conditions are: heating from room temperature to 1300~1400°C at 5~10°C/min, keeping warm for 2~4h, and vacuum degree ≤0.01Pa. 8.根据权利要求1所述的一种抗蠕变高导热石墨烯改性高速钢材料，其特征在于：所述热处理包括固溶处理和时效处理；所述固溶处理的条件为：在1150~1250℃下，保温0.5~1.5h，气淬冷却至室温；所述时效处理的条件为：在保护气氛下，温度为700~1000℃，时间为3~5h，随炉冷却至室温。8. The creep-resistant and highly thermally conductive graphene-modified high-speed steel material according to claim 1 is characterized in that: the heat treatment includes solution treatment and aging treatment; the conditions of the solution treatment are: at 1150-1250°C, keep warm for 0.5-1.5h, and cool to room temperature by gas quenching; the conditions of the aging treatment are: under a protective atmosphere, the temperature is 700-1000°C, the time is 3-5h, and the furnace is cooled to room temperature.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109554628A (en) * 2018-11-23 2019-04-02 中国航发北京航空材料研究院 The preparation method of graphene composite high speed tool steel
CN114574788A (en) * 2022-01-19 2022-06-03 长沙市萨普新材料有限公司 High-speed steel and preparation method and application thereof

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US20180318922A1 (en) * 2015-11-06 2018-11-08 Innomaq 21, S.L. Method for the economic manufacturing of metallic parts
CN111101074A (en) * 2018-10-26 2020-05-05 青海民族大学 In-situ carbide particle-embedded 3D amorphous alloy network reinforced boron steel-based composite material and preparation method thereof
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109554628A (en) * 2018-11-23 2019-04-02 中国航发北京航空材料研究院 The preparation method of graphene composite high speed tool steel
CN114574788A (en) * 2022-01-19 2022-06-03 长沙市萨普新材料有限公司 High-speed steel and preparation method and application thereof

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