WO2021047592A1 - Cermet heating material and preparation method thereof - Google Patents

Cermet heating material and preparation method thereof Download PDF

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Publication number
WO2021047592A1
WO2021047592A1 PCT/CN2020/114514 CN2020114514W WO2021047592A1 WO 2021047592 A1 WO2021047592 A1 WO 2021047592A1 CN 2020114514 W CN2020114514 W CN 2020114514W WO 2021047592 A1 WO2021047592 A1 WO 2021047592A1
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Prior art keywords
powder
heating material
solid solution
cermet
ball
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PCT/CN2020/114514
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French (fr)
Chinese (zh)
Inventor
刘华臣
李丹
陈义坤
黄婷
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湖北中烟工业有限责任公司
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Publication of WO2021047592A1 publication Critical patent/WO2021047592A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24F—SMOKERS' REQUISITES; MATCH BOXES; SIMULATED SMOKING DEVICES
    • A24F47/00—Smokers' requisites not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds

Definitions

  • the present invention belongs to the field of ceramic matrix composite materials and powder metallurgy. More specifically, the present invention generally relates to a metal ceramic heating material and a preparation method thereof.
  • Cermet is a ceramic matrix composite material prepared by powder metallurgy technology with ceramics as the main hard phase and metal as the binding phase. Since cermet has both high toughness and processing technology of metal materials, high hardness and high chemical stability of ceramic materials, it is generally used to make cutting tools and thermoforming molds. In addition, the cermet has abundant reserves of the main components and the preparation process is relatively simple, so its production cost is low. However, the research on the properties of cermet materials mainly focuses on their mechanical properties, and there are no related reports on the research of electrical properties.
  • the purpose of the present invention is to provide a metal-ceramic heating material and a preparation method thereof against the shortcomings of poor consistency between commonly used PTC resistors and MCH ceramic heating elements and complex preparation processes, which can not only meet the electrical and structural characteristics of small heating elements, but also It can simplify the preparation process of the product to a greater extent and reduce the production cost.
  • the inventor of this patent found to a great surprise after a large number of experiments that the heating characteristics of a material under electrical conditions are largely determined by its electrical resistivity, and the main factors affecting the volume resistivity of composite materials are the material components. , Organizational structure and density, etc.; the main components of cermets are conductive metals and ceramic materials with a certain resistivity, and cermets are generally prepared by powder metallurgy, and their organization and density can be carried out by ball milling, pressing and sintering. Adjustment and control; therefore, the volume resistivity of the cermet can be adjusted through the preparation process, and its heating characteristics can also be guaranteed, thereby completing the present invention.
  • the present invention provides a cermet heating material, the cermet heating material comprises a hard phase ceramic solid solution and a binder phase metal, the hard phase ceramic solid solution is carbide, nitride And one or more solid solutions in borides, and the binder phase metal is one or more of Ni, Cr, Fe, and Co.
  • the porosity of the cermet heating material is 0.5%-20%, and the resistivity is 0.001-0.05 ⁇ cm.
  • the weight ratio of the hard phase to the binder phase is 1-20:1, more preferably 2-10:1.
  • the present invention also provides a method for preparing a cermet heating material, which includes the following steps:
  • the hard phase ceramic solid solution powder and the binder phase metal powder are ball milled in a ball mill, wherein the conditions of the ball milling include a ball-to-material ratio of 5-10:1, a rotation speed of 120-350rpm and a time of 24 -96h, the hard phase ceramic solid solution is one or more solid solutions of carbides, nitrides and borides, and the binder phase metal is one or more of Ni, Cr, Fe and Co;
  • Drying vacuum drying the obtained powder slurry, wherein the drying conditions include a temperature of 70-90°C;
  • Compression molding molding the granulated powder, wherein the molding conditions include a pressure of 200-400 MPa and a time of 0.5-5 min;
  • the obtained blank is sintered at a vacuum degree higher than 1 ⁇ 10 ⁇ 1 Pa, wherein the sintering conditions include a temperature of 1220 to 1450° C. and a time of 15 to 60 minutes.
  • the ball milling step further includes adding at least one of WC powder, Mo powder and graphite powder into the ball mill.
  • the weight percentage of each component in the ball milling step includes hard phase ceramic solid solution 31.00%-68.00%, binder phase metal 10.00%-20.00%, WC 11.00%-19.00% , Mo 5.00%-15.00% and graphite 0.50%-3.00%.
  • the method further includes a mixing step before the granulation step, and the mixing includes mixing the dried mixed powder with the forming agent.
  • the forming agent is molten paraffin, and more preferably, the volume fraction of the forming agent is 30.00%-60.00%.
  • the method further includes a debinding step after the compression molding step, and the debinding includes vacuum debinding the formed blank in a vacuum furnace.
  • the degreasing conditions include a vacuum degree higher than 1.00 Pa, a temperature of 150-220° C. and a time of 6-15 h.
  • the present invention also provides the use of the above-mentioned ceramic heating element or the ceramic heating element prepared by the above-mentioned method in a heater for a novel tobacco product.
  • the cermet heating material of the present invention and the cermet heating material prepared by the method of the present invention can not only meet the electrical and structural characteristics of small heating elements, but also simplify the production process of the product to a greater extent. reduce manufacturing cost.
  • the high-strength and toughness cermet prepared by the present invention has a hardness of 85.1-89.9HRA, a bending strength ⁇ 1600MPa, and a fracture toughness K IC ⁇ 8.0MPa ⁇ m 1/2 , so it also has good impact resistance and wear resistance. , High temperature red hardness, chemical stability and anti-adhesion.
  • Cermet is a material composed of ceramic and metal, or more specifically a composite material of ceramic and metal made by powder metallurgy. Cermet has the advantages of metal and ceramics. It has low density, high hardness, wear resistance, good thermal conductivity, and will not be brittle due to sudden cold or sudden heat. In addition, coating a layer of ceramic coating with good airtightness, high melting point and poor heat transfer performance on the metal surface can also prevent the metal or alloy from oxidizing or corroding at high temperatures. Cermet not only has the toughness, high thermal conductivity and good thermal stability of metal, but also has the characteristics of high temperature resistance, corrosion resistance and wear resistance of ceramics. At present, cermets are widely used in rockets, missiles, supersonic aircraft shells, and flame nozzles in combustion chambers.
  • solid solution refers to an alloy phase in which solute atoms dissolve into the solvent crystal lattice while still maintaining the solvent type, and usually a crystal composed of atoms or molecules of other substances dissolved in a chemical substance as the matrix. It is more common in alloys and silicate systems, and also exists in polyatomic substances.
  • the electrical, thermal, magnetic and other physical properties of solid solutions vary continuously with the composition, but generally they are not linear. The strength and hardness of the solid solution are often higher than the components, while the plasticity is lower.
  • the present invention provides a cermet heating material comprising a hard phase ceramic solid solution and a binder phase metal, and the hard phase ceramic solid solution is selected from carbides, nitrides, and borides.
  • the binder phase metal is one or more of Ni, Cr, Fe and Co.
  • the components used to synthesize composite materials are usually divided into refractory metal compounds (hard phase) and binder metal (binder phase), and during the process, the hard phase usually passes through the binder phase They are tightly bonded together to form a composite material, that is, the cermet heating material of the present invention.
  • the hard phase ceramic solid solution may be more specifically at least one of TiC, TiN, and Mo 2 FeB 2 , but is not limited thereto.
  • the performance of the cermet heating material can be adjusted to a certain extent, so that it can better satisfy the present invention.
  • the porosity of the cermet heating material is preferably 0.5%-20%, and the resistivity is preferably 0.001-0.05 ⁇ cm.
  • the porosity of the cermet heating material is such as 5%. Or 10%, and the resistivity is 0.004 ⁇ cm and so on.
  • the content of the hard phase and the binder phase there is no particular limitation on the content of the hard phase and the binder phase, and the content of the conventional hard phase and the binder phase in the field can be used, as long as they can stably form the cermet heating material, but in this case
  • the weight ratio of the hard phase to the binder phase is preferably 1-20:1, more preferably 2-10:1, such as 3:1.
  • the present invention also provides a method for preparing a cermet heating material, which includes the following steps:
  • the hard phase ceramic solid solution powder and the binder phase metal powder are ball milled in a ball mill, wherein the conditions of the ball milling include a ball-to-material ratio of 5-10:1, a rotation speed of 120-350rpm and a time of 24 -96h, the hard phase ceramic solid solution is one or more solid solutions of carbides, nitrides and borides, and the binder phase metal is one or more of Ni, Cr, Fe and Co;
  • Drying vacuum drying the obtained powder slurry, wherein the drying conditions include a temperature of 70-90°C;
  • Compression molding molding the granulated powder, wherein the molding conditions include a pressure of 200-400 MPa and a time of 0.5-5 min;
  • the obtained blank is sintered at a vacuum degree higher than 1 ⁇ 10 ⁇ 1 Pa, wherein the sintering conditions include a temperature of 1220 to 1450° C. and a time of 15 to 60 minutes.
  • some additives or media commonly used in the field can be added in the ball milling process to achieve a better ball milling effect.
  • the ball milling step can also be included in the ball mill At least one of WC powder, Mo powder and graphite powder is added.
  • the hard phase ceramic solid solution and the binder phase metal are the same as the description of the hard phase ceramic solid solution and the binder phase metal in the cermet heating material part, so it will not be repeated here; and WC, Both Mo and graphite are common additive phases in powder metallurgy processes in this field, and can be used to enhance the excellent mechanical properties of the resulting material.
  • the inventors are very surprised to find that through the above-mentioned preparation method with various steps and various specific process parameters, the produced cermet heating material can not only meet the requirements of electrical and structural characteristics of small heating elements, but also better It greatly simplifies the preparation process of the product and reduces the production cost.
  • the ratio of each component in the ball milling step is not particularly limited, and those skilled in the art can adjust it according to specific needs.
  • the weight percentage of each component in the ball milling step preferably includes Hard phase ceramic solid solution 31.00%-68.00% (such as 35.00% or 45.00%, etc.), binder phase metal 10.00%-20.00% (such as 15%, etc.), WC 11.00%-19.00% (such as 15%, etc.), Mo 5.00%-15.00% (such as 10%, etc.) and graphite 0.50%-3.00% (such as 1% or 2%, etc.).
  • the steps of blending and degreasing can also be added to the preparation method of the present invention, so as to improve the powder molding performance of the product.
  • the method of the present invention also preferably includes a mixing step before the granulation step.
  • the mixing includes mixing the dried mixed powder with a forming agent. More preferably, the forming The agent is molten paraffin, and more preferably, the volume fraction of the forming agent is 30.00%-60.00% (for example, 40.00%-50.00%, etc.).
  • the method of the present invention also preferably includes a degreasing step after the compression molding step.
  • the degreasing includes vacuum degreasing the formed blank in a vacuum furnace.
  • the degreasing The conditions include a vacuum degree higher than 1.00 Pa, a temperature of 150-220°C (for example, 180°C or 200°C, etc.) and a time of 6-15h (for example, 10h, etc.).
  • the method of the present invention includes the following steps:
  • Ball milling the hard phase ceramic solid solution powder, binder phase metal powder, WC powder, Mo powder and graphite powder are ball milled in a ball mill, wherein the conditions of the ball milling include a ball-to-battery ratio of 5-10:1
  • the rotation speed is 120-350rpm and the time is 24-96h
  • the hard phase ceramic solid solution is one or more solid solutions of carbides, nitrides and borides
  • the binder phase metals are Ni, Cr, Fe and One or more of Co;
  • Drying vacuum drying the obtained powder slurry, wherein the drying conditions include a temperature of 70-90°C;
  • Glue blending mix the dried mixed powder with a forming agent, the forming agent is molten paraffin, and the volume fraction is 30.00%-60.00%
  • Compression molding molding the granulated powder, wherein the molding conditions include a pressure of 200-400 MPa and a time of 0.5-5 min;
  • Vacuum degreasing the formed blank in a vacuum furnace and the degreasing conditions include a vacuum degree higher than 1.00 Pa, a temperature of 150-220°C and a time of 6-15h; and
  • the defatted billet is sintered at a vacuum degree higher than 1 ⁇ 10 ⁇ 1 Pa, wherein the sintering conditions include a temperature of 1220 to 1450° C. and a time of 15 to 60 minutes.
  • the present invention also provides the use of the above-mentioned ceramic heating element or the ceramic heating element prepared by the above-mentioned method in a heater for a novel tobacco product.
  • the cermet heating material of the present invention and the cermet heating material prepared by the method of the present invention can not only meet the requirements of electrical and structural characteristics of small heating elements, but also simplify the preparation process of the product to a greater extent and reduce the production cost.
  • the high-strength and toughness cermet prepared by the present invention has a hardness of 85.1-89.9HRA, a bending strength ⁇ 1600MPa, and a fracture toughness K IC ⁇ 8.0MPa ⁇ m 1/2 , so it also has good impact resistance and wear resistance. , High temperature red hardness, chemical stability and anti-adhesion.
  • TiC powder, TiN powder, Ni powder, WC powder, Mo powder and graphite powder into a nylon ball milling tank according to the following mass fractions: 45%TiC-13%TiN-15%Ni-16%WC-10%Mo-1% C.
  • the grinding ball used is a cemented carbide ball; the ball milling medium is ethanol, and then it is placed on a planetary ball mill for ball milling, where the ball-to-battery ratio is 7:1, the rotating speed is 220 rpm, and the ball milling time is 48 hours; the ball mill powder is dried After mixing with 45% volume fraction of forming agent paraffin, granulation and sieving after mixing, the average particle size of the obtained powder is 1.5mm; then compression molding is carried out, where the pressing pressure is 300MPa and the holding time is 1min ; After forming, vacuum debinding the compact in a vacuum furnace, where the debinding temperature is 150°C, the holding time is 8h, and the heating rate is 0.3°C/min; the degreased compact is vacuum sintered, and the vacuum degree is 1 ⁇ 10 -2 Pa, sintering temperature is 1280 °C and holding time is 60 min.
  • Table 1 The performance details of the produced cermet heating materials are shown in Table 1.
  • TiC powder, TiN powder, Ni powder, WC powder, Mo powder and graphite powder into a nylon ball milling tank according to the following mass fractions: 47%TiC-16%TiN-10%Ni-16%WC-10%Mo-1% C.
  • the grinding ball used is a cemented carbide ball; the ball milling medium is ethanol, and then it is placed on a planetary ball mill for ball milling, where the ball-to-battery ratio is 5:1, the rotating speed is 120rpm, and the ball milling time is 96h; the ball milling powder is dried After mixing with 30% volume fraction of forming agent paraffin, granulation and sieving after mixing, the average particle size of the obtained powder is 1.6mm; then compression molding is carried out, where the pressing pressure is 200MPa and the holding time is 0.5 min; after forming, vacuum debinding the compact in a vacuum furnace, where the debinding temperature is 180°C, the holding time is 6h, and the heating rate is 0.3°C/min; the degreased compact is vacuum sintered, where the vacuum degree is 1 ⁇ 10 -2 Pa, sintering temperature is 1300°C and holding time is 60min.
  • Table 1 The performance details of the produced cermet heating materials are shown in Table 1.
  • TiC powder, Ni powder, Cr powder, Mo powder and graphite powder into a nylon ball milling tank in the following mass fractions: 12%TiC-66%WC-10%Ni-5%Cr-6%Mo-1%C, used
  • the grinding ball is a cemented carbide ball; the ball milling medium is ethanol, and then it is placed on a planetary ball mill for ball milling.
  • the ball-to-battery ratio is 10:1, the rotating speed is 350rpm, and the ball milling time is 36h; Paraffin wax with a fraction of 60% forming agent is blended, granulated and sieved after blending, and the average particle size of the obtained powder is 2.0mm; then compression molding is performed, where the compression pressure is 400MPa and the pressure holding time is 2min; after molding vacuum degreased the compacts in a vacuum oven, wherein the binder burn out temperature is 220 deg.] C, holding time of 15H, and the temperature rise rate of 0.3 °C / min; green compacts degreased vacuum sintering, wherein a degree of vacuum of 1 ⁇ 10 - 2 Pa, sintering temperature is 1400°C and holding time is 15min.
  • Table 1 The performance details of the produced cermet heating materials are shown in Table 1.
  • Mo 2 FeB 2 powder, Fe powder and Mo powder into a nylon ball milling tank according to the following mass fractions: 63% Mo 2 FeB 2 -20% Fe-17% Mo, the grinding balls used are cemented carbide balls; the ball milling medium is ethanol , And then placed on a planetary ball mill for ball milling, where the ball-to-battery ratio is 7:1, the rotating speed is 230rpm, and the ball milling time is 48h; the ball mill powder is dried and mixed with 45% volume fraction of paraffin wax.
  • the average particle size of the obtained powder is 1.6mm; then it is compression molded, where the compression pressure is 200MPa and the pressure holding time is 0.5min; after the molding, the compact is vacuum degreasing in a vacuum furnace, The debinding temperature is 180°C, the holding time is 8h, and the heating rate is 0.3°C/min; the degreased compact is vacuum sintered, the vacuum degree is 1 ⁇ 10 -2 Pa, the sintering temperature is 1220°C and the holding time For 60min.
  • the performance details of the produced cermet heating materials are shown in Table 1.
  • the hardness of the cermet prepared by the method of the present invention does meet 85.1 ⁇ 89.9HRA, the bending strength is ⁇ 1600MPa, and the fracture toughness K IC ⁇ 8.0MPa ⁇ m 1/2 , so it has better The impact resistance, abrasion resistance, high temperature red hardness, chemical stability and adhesion resistance.
  • the resistivities of the materials prepared by the method of the present invention are all 0.001-0.05 ⁇ cm, and thus can also meet the requirements of electrical characteristics of small heating elements.

Abstract

The present invention provides a cermet heating material and preparation method thereof, wherein the cermet heating material contains a hard phase ceramic solid solution and a binder phase metal, the hard phase ceramic solid solution is one or more solid solutions of carbides, nitrides and borides, the binder phase metal is one or more of Ni, Cr, Fe and Co, the cermet heating material and the preparation method thereof can not only meet the requirements for the electrical and structural characteristics of the small heating body, and also simplify the preparation process of the product to a greater extent and reduce the production cost.

Description

一种金属陶瓷发热材料及其制备方法Metal ceramic heating material and preparation method thereof 技术领域Technical field
本发明属于陶瓷基复合材料和粉末冶金的领域，更具体地，本发明通常涉及一种金属陶瓷发热材料及其制备方法。The present invention belongs to the field of ceramic matrix composite materials and powder metallurgy. More specifically, the present invention generally relates to a metal ceramic heating material and a preparation method thereof.
背景技术Background technique
随着高端智能装备的不断发展，小型发热元器件的需求和应用领域不断扩大，目前市场上普遍使用的微小型发热器件主要为PTC电阻与MCH陶瓷材料。虽然一定程度上能满足各类设备的使用需求，然而还是存在着较多问题，比如PTC热敏电阻一致性差、互换性差、元件易老化及稳定性差等，而MCH陶瓷往往制备工艺复杂、成本较高，也存在着产品质量不均匀等问题，这些不足会导致下游设备成本高或者质量不稳定。因此急需开发一种低成本、工艺简单、可靠性高及可控性强的新型发热材料。With the continuous development of high-end intelligent equipment, the demand and application fields of small heating components continue to expand. At present, the micro-small heating devices commonly used in the market are mainly PTC resistors and MCH ceramic materials. Although it can meet the requirements of various types of equipment to a certain extent, there are still many problems, such as poor consistency of PTC thermistors, poor interchangeability, easy aging of components and poor stability, etc., while MCH ceramics often have complex preparation processes and cost Higher, there are also problems such as uneven product quality, these deficiencies will lead to high cost of downstream equipment or unstable quality. Therefore, there is an urgent need to develop a new type of heating material with low cost, simple process, high reliability and strong controllability.
金属陶瓷是一种以陶瓷为主要硬质相、金属为粘结相，采用粉末冶金工艺制备的陶瓷基复合材料。由于金属陶瓷兼具金属材料的高韧性与加工工艺性、陶瓷材料的高硬度和高化学稳定性，因此一般用来制作切削刀具及热成型模具。此外，金属陶瓷主要成分的储量丰富，制备工艺也较为简单，因此其制作成本较低。然而，关于金属陶瓷材料性能的研究主要集中在其力学性能上，而电学特性方面的研究未见相关报道。Cermet is a ceramic matrix composite material prepared by powder metallurgy technology with ceramics as the main hard phase and metal as the binding phase. Since cermet has both high toughness and processing technology of metal materials, high hardness and high chemical stability of ceramic materials, it is generally used to make cutting tools and thermoforming molds. In addition, the cermet has abundant reserves of the main components and the preparation process is relatively simple, so its production cost is low. However, the research on the properties of cermet materials mainly focuses on their mechanical properties, and there are no related reports on the research of electrical properties.
发明内容Summary of the invention
本发明的目的在于针对常用PTC电阻与MCH陶瓷发热体产品一致性差、制备工艺复杂等缺点，提供一种金属陶瓷发热材料及其制备方法，不仅能够满足小型发热体的电学及结构特性的要求，更能较大程度地简化产品的制备工艺，降低生产成本。The purpose of the present invention is to provide a metal-ceramic heating material and a preparation method thereof against the shortcomings of poor consistency between commonly used PTC resistors and MCH ceramic heating elements and complex preparation processes, which can not only meet the electrical and structural characteristics of small heating elements, but also It can simplify the preparation process of the product to a greater extent and reduce the production cost.
在现有技术的基础上，本专利的发明人经过大量试验非常惊奇地发现，材 料在电学条件下的发热特性很大程度决定于其电阻率，复合材料体积电阻率的影响因素主要有材料成分、组织结构及致密度等；金属陶瓷的主要成分为导电金属与具有一定电阻率的陶瓷材料，并且金属陶瓷一般采用粉末冶金方法制备，其组织与致密度可通过球磨、压制与烧结等过程进行调整与控制；因而金属陶瓷的体积电阻率可以通过制备工艺进行调控，其发热特性也得以保证，从而完成本发明。On the basis of the prior art, the inventor of this patent found to a great surprise after a large number of experiments that the heating characteristics of a material under electrical conditions are largely determined by its electrical resistivity, and the main factors affecting the volume resistivity of composite materials are the material components. , Organizational structure and density, etc.; the main components of cermets are conductive metals and ceramic materials with a certain resistivity, and cermets are generally prepared by powder metallurgy, and their organization and density can be carried out by ball milling, pressing and sintering. Adjustment and control; therefore, the volume resistivity of the cermet can be adjusted through the preparation process, and its heating characteristics can also be guaranteed, thereby completing the present invention.
为了实现上述目的，在一个方面，本发明提供了一种金属陶瓷发热材料，该金属陶瓷发热材料包含硬质相陶瓷固溶体和粘结相金属，所述硬质相陶瓷固溶体为碳化物、氮化物和硼化物中的一种或多种固溶体，所述粘结相金属为Ni、Cr、Fe和Co中的一种或多种。In order to achieve the above objective, in one aspect, the present invention provides a cermet heating material, the cermet heating material comprises a hard phase ceramic solid solution and a binder phase metal, the hard phase ceramic solid solution is carbide, nitride And one or more solid solutions in borides, and the binder phase metal is one or more of Ni, Cr, Fe, and Co.
在本发明的一个优选的实施方式中，所述金属陶瓷发热材料的孔隙率为0.5％-20％，电阻率为0.001-0.05Ω·cm。In a preferred embodiment of the present invention, the porosity of the cermet heating material is 0.5%-20%, and the resistivity is 0.001-0.05Ω·cm.
在本发明的一个优选的实施方式中，所述硬质相和粘结相的重量比为1-20：1，更优选为2-10：1。In a preferred embodiment of the present invention, the weight ratio of the hard phase to the binder phase is 1-20:1, more preferably 2-10:1.
在另一方面，本发明还提供了一种制备金属陶瓷发热材料的方法，其包括以下步骤：In another aspect, the present invention also provides a method for preparing a cermet heating material, which includes the following steps:
(1)球磨：将硬质相陶瓷固溶体粉和粘结相金属粉在球磨机中进行球磨，其中所述球磨的条件包括球料比为5-10：1、转速为120-350rpm和时间为24-96h，所述硬质相陶瓷固溶体为碳化物、氮化物和硼化物中的一种或多种固溶体，所述粘结相金属为Ni、Cr、Fe和Co中的一种或多种；(1) Ball milling: the hard phase ceramic solid solution powder and the binder phase metal powder are ball milled in a ball mill, wherein the conditions of the ball milling include a ball-to-material ratio of 5-10:1, a rotation speed of 120-350rpm and a time of 24 -96h, the hard phase ceramic solid solution is one or more solid solutions of carbides, nitrides and borides, and the binder phase metal is one or more of Ni, Cr, Fe and Co;
(2)烘干：将所得的粉末浆料进行真空烘干，其中所述烘干的条件包括温度为70-90℃；(2) Drying: vacuum drying the obtained powder slurry, wherein the drying conditions include a temperature of 70-90°C;
(3)造粒：将所得的混合物在造粒机中进行混合造粒，并然后进行过筛，使得所得粉末颗粒尺寸为0.2-2mm；(3) Granulation: the obtained mixture is mixed and granulated in a granulator, and then sieved, so that the obtained powder has a particle size of 0.2-2mm;
(4)模压成型：将造粒的粉料进行模压成型，其中所述模压的条件包括压力为200-400MPa和时间为0.5-5min；以及(4) Compression molding: molding the granulated powder, wherein the molding conditions include a pressure of 200-400 MPa and a time of 0.5-5 min; and
(5)烧结：将所得的胚料在高于1×10 -1Pa真空度下进行烧结，其中所述烧结的条件包括温度为1220-1450℃和时间为15-60min。 (5) Sintering: the obtained blank is sintered at a vacuum degree higher than 1×10 −1 Pa, wherein the sintering conditions include a temperature of 1220 to 1450° C. and a time of 15 to 60 minutes.
在本发明的一个优选的实施方式中，所述球磨步骤还包括在所述球磨机中加入WC粉、Mo粉和石墨粉中的至少一种。In a preferred embodiment of the present invention, the ball milling step further includes adding at least one of WC powder, Mo powder and graphite powder into the ball mill.
在本发明的一个优选的实施方式中，所述球磨步骤中各组分的重量百分比包括硬质相陶瓷固溶体31.00％-68.00％，粘结相金属10.00％-20.00％，WC 11.00％-19.00％，Mo 5.00％-15.00％和石墨0.50％-3.00％。In a preferred embodiment of the present invention, the weight percentage of each component in the ball milling step includes hard phase ceramic solid solution 31.00%-68.00%, binder phase metal 10.00%-20.00%, WC 11.00%-19.00% , Mo 5.00%-15.00% and graphite 0.50%-3.00%.
在本发明的一个优选的实施方式中，所述方法还包括在造粒步骤之前的掺胶步骤，所述掺胶包括将烘干的混合粉末与成形剂进行混合。In a preferred embodiment of the present invention, the method further includes a mixing step before the granulation step, and the mixing includes mixing the dried mixed powder with the forming agent.
在本发明的一个优选的实施方式中，所述成形剂为熔化态石蜡，更优选地，所述成形剂所占的体积分数为30.00％-60.00％。In a preferred embodiment of the present invention, the forming agent is molten paraffin, and more preferably, the volume fraction of the forming agent is 30.00%-60.00%.
在本发明的一个优选的实施方式中，所述方法还包括在模压成型步骤后的脱脂步骤，所述脱脂包括将成型的坯料在真空炉中进行真空脱脂。In a preferred embodiment of the present invention, the method further includes a debinding step after the compression molding step, and the debinding includes vacuum debinding the formed blank in a vacuum furnace.
在本发明的一个优选的实施方式中，所述脱脂的条件包括真空度高于1.00Pa，温度为150-220℃和时间为6-15h。In a preferred embodiment of the present invention, the degreasing conditions include a vacuum degree higher than 1.00 Pa, a temperature of 150-220° C. and a time of 6-15 h.
在另一方面，本发明还提供了上述陶瓷发热体或通过上述方法制备的陶瓷发热体在新型烟草制品用发热器中的用途。In another aspect, the present invention also provides the use of the above-mentioned ceramic heating element or the ceramic heating element prepared by the above-mentioned method in a heater for a novel tobacco product.
综上所述，本发明的金属陶瓷发热材料和通过本发明的方法制备的金属陶瓷发热材料不仅能够满足小型发热体的电学及结构特性的要求，更能较大程度地简化产品的制备工艺，降低生产成本。此外，本发明所制备的高强韧性金属陶瓷硬度为85.1～89.9HRA，抗弯强度≥1600MPa，断裂韧性K IC≥8.0MPa·m 1/2，因而还具有较好的抗冲击性、耐磨性、高温红硬性、化学稳定性和抗粘附性。 In summary, the cermet heating material of the present invention and the cermet heating material prepared by the method of the present invention can not only meet the electrical and structural characteristics of small heating elements, but also simplify the production process of the product to a greater extent. reduce manufacturing cost. In addition, the high-strength and toughness cermet prepared by the present invention has a hardness of 85.1-89.9HRA, a bending strength ≥1600MPa, and a fracture toughness K IC ≥8.0MPa·m 1/2 , so it also has good impact resistance and wear resistance. , High temperature red hardness, chemical stability and anti-adhesion.
具体实施方式detailed description
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。The specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and not to limit the present invention.
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间 可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the end values of each range, between the end values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges. These values The scope should be considered as specifically disclosed herein.
如本文所用，术语“金属陶瓷”是由陶瓷和金属组成的一种材料，或更具体地由粉末冶金方法制成的陶瓷与金属的复合材料。金属陶瓷兼有金属和陶瓷的优点，它密度小、硬度高、耐磨、导热性好，不会因为骤冷或骤热而脆裂。另外，在金属表面涂覆一层气密性好、熔点高、传热性能很差的陶瓷涂层，也能防止金属或合金在高温下氧化或腐蚀。金属陶瓷既具有金属的韧性、高导热性和良好的热稳定性，又具有陶瓷的耐高温、耐腐蚀和耐磨损等特性。目前，金属陶瓷广泛地应用于火箭、导弹、超音速飞机的外壳、燃烧室的火焰喷口等地方。As used herein, the term "cermet" is a material composed of ceramic and metal, or more specifically a composite material of ceramic and metal made by powder metallurgy. Cermet has the advantages of metal and ceramics. It has low density, high hardness, wear resistance, good thermal conductivity, and will not be brittle due to sudden cold or sudden heat. In addition, coating a layer of ceramic coating with good airtightness, high melting point and poor heat transfer performance on the metal surface can also prevent the metal or alloy from oxidizing or corroding at high temperatures. Cermet not only has the toughness, high thermal conductivity and good thermal stability of metal, but also has the characteristics of high temperature resistance, corrosion resistance and wear resistance of ceramics. At present, cermets are widely used in rockets, missiles, supersonic aircraft shells, and flame nozzles in combustion chambers.
如本文所用，术语“固溶体”是指溶质原子溶入溶剂晶格中而仍保持溶剂类型的合金相，且通常以一种化学物质为基体溶有其它物质的原子或分子所组成的晶体，在合金和硅酸盐系统中较多见，在多原子物质中亦存在。固溶体的电学、热学、磁学等物理性质随成分而连续变化，但一般都不是线性关系。固溶体的强度与硬度往往高于各组元，而塑性则较低。As used herein, the term "solid solution" refers to an alloy phase in which solute atoms dissolve into the solvent crystal lattice while still maintaining the solvent type, and usually a crystal composed of atoms or molecules of other substances dissolved in a chemical substance as the matrix. It is more common in alloys and silicate systems, and also exists in polyatomic substances. The electrical, thermal, magnetic and other physical properties of solid solutions vary continuously with the composition, but generally they are not linear. The strength and hardness of the solid solution are often higher than the components, while the plasticity is lower.
在一个方面，本发明提供了一种金属陶瓷发热材料，该金属陶瓷发热材料包含硬质相陶瓷固溶体和粘结相金属，所述硬质相陶瓷固溶体为碳化物、氮化物和硼化物中的一种或多种固溶体，所述粘结相金属为Ni、Cr、Fe和Co中的一种或多种。In one aspect, the present invention provides a cermet heating material comprising a hard phase ceramic solid solution and a binder phase metal, and the hard phase ceramic solid solution is selected from carbides, nitrides, and borides. One or more solid solutions, and the binder phase metal is one or more of Ni, Cr, Fe and Co.
在粉末冶金生产工艺中，用于合成复合材料的组分通常分为难熔金属化合物(硬质相)和粘结金属(粘结相)，并且在工艺进行期间，硬质相通常通过粘结相而紧密粘结在一起，从而共同形成复合材料，即本发明的金属陶瓷发热材料。在本发明的一些实施方式中，硬质相陶瓷固溶体可以更具体地为TiC、TiN和Mo 2FeB 2中的至少一种，但是不限于此。 In the powder metallurgy production process, the components used to synthesize composite materials are usually divided into refractory metal compounds (hard phase) and binder metal (binder phase), and during the process, the hard phase usually passes through the binder phase They are tightly bonded together to form a composite material, that is, the cermet heating material of the present invention. In some embodiments of the present invention, the hard phase ceramic solid solution may be more specifically at least one of TiC, TiN, and Mo 2 FeB 2 , but is not limited thereto.
根据本发明，为了使得本发明的金属陶瓷发热材料更能够满足小型发热体的电学及结构特性的要求，可以对金属陶瓷发热材料的性能进行一定的调控，从而使其能够更好地满足本发明的需求。因此，在本发明的一个实施方式中，金属陶瓷发热材料的孔隙率优选为0.5％-20％，电阻率优选为0.001-0.05Ω·cm，例如，金属陶瓷发热材料的孔隙率为如5％或10％，而电阻率为0.004Ω·cm等。According to the present invention, in order to enable the cermet heating material of the present invention to better meet the electrical and structural characteristics of small heating elements, the performance of the cermet heating material can be adjusted to a certain extent, so that it can better satisfy the present invention. Demand. Therefore, in one embodiment of the present invention, the porosity of the cermet heating material is preferably 0.5%-20%, and the resistivity is preferably 0.001-0.05Ω·cm. For example, the porosity of the cermet heating material is such as 5%. Or 10%, and the resistivity is 0.004Ω·cm and so on.
根据本发明，对硬质相和粘结相的含量没有特别限制，可以使用本领域中常规的硬质相和粘结相的含量，只要它们能够稳定形成金属陶瓷发热材料即可，但在本发明的一个实施方式中，硬质相和粘结相的重量比优选为1-20：1，更优选为2-10：1，例如3：1等。According to the present invention, there is no particular limitation on the content of the hard phase and the binder phase, and the content of the conventional hard phase and the binder phase in the field can be used, as long as they can stably form the cermet heating material, but in this case In an embodiment of the invention, the weight ratio of the hard phase to the binder phase is preferably 1-20:1, more preferably 2-10:1, such as 3:1.
在另一方面，本发明还提供了一种制备金属陶瓷发热材料的方法，其包括以下步骤：In another aspect, the present invention also provides a method for preparing a cermet heating material, which includes the following steps:
(1)球磨：将硬质相陶瓷固溶体粉和粘结相金属粉在球磨机中进行球磨，其中所述球磨的条件包括球料比为5-10：1、转速为120-350rpm和时间为24-96h，所述硬质相陶瓷固溶体为碳化物、氮化物和硼化物中的一种或多种固溶体，所述粘结相金属为Ni、Cr、Fe和Co中的一种或多种；(1) Ball milling: the hard phase ceramic solid solution powder and the binder phase metal powder are ball milled in a ball mill, wherein the conditions of the ball milling include a ball-to-material ratio of 5-10:1, a rotation speed of 120-350rpm and a time of 24 -96h, the hard phase ceramic solid solution is one or more solid solutions of carbides, nitrides and borides, and the binder phase metal is one or more of Ni, Cr, Fe and Co;
(2)烘干：将所得的粉末浆料进行真空烘干，其中所述烘干的条件包括温度为70-90℃；(2) Drying: vacuum drying the obtained powder slurry, wherein the drying conditions include a temperature of 70-90°C;
(3)造粒：将所得的混合物在造粒机中进行混合造粒，并然后进行过筛，使得所得粉末颗粒尺寸为0.2-2mm；(3) Granulation: the obtained mixture is mixed and granulated in a granulator, and then sieved, so that the obtained powder has a particle size of 0.2-2mm;
(4)模压成型：将造粒的粉料进行模压成型，其中所述模压的条件包括压力为200-400MPa和时间为0.5-5min；以及(4) Compression molding: molding the granulated powder, wherein the molding conditions include a pressure of 200-400 MPa and a time of 0.5-5 min; and
(5)烧结：将所得的胚料在高于1×10 -1Pa真空度下进行烧结，其中所述烧结的条件包括温度为1220-1450℃和时间为15-60min。 (5) Sintering: the obtained blank is sintered at a vacuum degree higher than 1×10 −1 Pa, wherein the sintering conditions include a temperature of 1220 to 1450° C. and a time of 15 to 60 minutes.
根据本发明，球磨过程中还可以加入本领域中常用的一些添加剂或介质以达到更好的球磨效果，例如，在本发明的一个实施方式中，所述球磨步骤还可以包括在所述球磨机中加入WC粉、Mo粉和石墨粉中的至少一种。According to the present invention, some additives or media commonly used in the field can be added in the ball milling process to achieve a better ball milling effect. For example, in one embodiment of the present invention, the ball milling step can also be included in the ball mill At least one of WC powder, Mo powder and graphite powder is added.
具体地，对于各个原料，硬质相陶瓷固溶体和粘结相金属与在金属陶瓷发热材料部分中关于硬质相陶瓷固溶体和粘结相金属的描述相同，因此在此不再赘述；而WC、Mo和石墨均为本领域的粉末冶金工艺中常见的添加相，可用于增强所得材料的优异力学性能。但是，发明人非常惊奇地发现，通过具有各个步骤及其中各种特定工艺参数的上述制备方法，所制得的金属陶瓷发热材料不仅能够满足小型发热体的电学及结构特性的要求，更能较大程度地简化产品的制备工艺，降低生产成本。Specifically, for each raw material, the hard phase ceramic solid solution and the binder phase metal are the same as the description of the hard phase ceramic solid solution and the binder phase metal in the cermet heating material part, so it will not be repeated here; and WC, Both Mo and graphite are common additive phases in powder metallurgy processes in this field, and can be used to enhance the excellent mechanical properties of the resulting material. However, the inventors are very surprised to find that through the above-mentioned preparation method with various steps and various specific process parameters, the produced cermet heating material can not only meet the requirements of electrical and structural characteristics of small heating elements, but also better It greatly simplifies the preparation process of the product and reduces the production cost.
根据本发明，对球磨步骤中各组分的比例没有特别限制，本领域技术人员可以根据特定的需要进行调节，而在本发明的一个实施方式中，球磨步骤中各组分的重量百分比优选包括硬质相陶瓷固溶体31.00％-68.00％(例如35.00％或45.00％等)，粘结相金属10.00％-20.00％(例如15％等)，WC 11.00％-19.00％(例如15％等)，Mo 5.00％-15.00％(例如10％等)和石墨0.50％-3.00％(例如1％或2％等)。According to the present invention, the ratio of each component in the ball milling step is not particularly limited, and those skilled in the art can adjust it according to specific needs. In an embodiment of the present invention, the weight percentage of each component in the ball milling step preferably includes Hard phase ceramic solid solution 31.00%-68.00% (such as 35.00% or 45.00%, etc.), binder phase metal 10.00%-20.00% (such as 15%, etc.), WC 11.00%-19.00% (such as 15%, etc.), Mo 5.00%-15.00% (such as 10%, etc.) and graphite 0.50%-3.00% (such as 1% or 2%, etc.).
根据本发明，在本发明的制备方法中还可以加入掺胶和脱脂的步骤，从而提高产品的粉末成型性能。在一个优选的实施方式中，本发明的方法还优选地包括在造粒步骤之前的掺胶步骤，所述掺胶包括将烘干的混合粉末与成形剂进行混合，更优选地，所述成形剂为熔化态石蜡，还更优选地，所述成形剂所占的体积分数为30.00％-60.00％(例如40.00％-50.00％等)。在另一个优选的实施方式中，本发明的方法还优选地包括在模压成型步骤后的脱脂步骤，所述脱脂包括将成型的坯料在真空炉中进行真空脱脂，更优选地，所述脱脂的条件包括真空度高于1.00Pa，温度为150-220℃(例如180℃或200℃等)和时间为6-15h(例如10h等)。According to the present invention, the steps of blending and degreasing can also be added to the preparation method of the present invention, so as to improve the powder molding performance of the product. In a preferred embodiment, the method of the present invention also preferably includes a mixing step before the granulation step. The mixing includes mixing the dried mixed powder with a forming agent. More preferably, the forming The agent is molten paraffin, and more preferably, the volume fraction of the forming agent is 30.00%-60.00% (for example, 40.00%-50.00%, etc.). In another preferred embodiment, the method of the present invention also preferably includes a degreasing step after the compression molding step. The degreasing includes vacuum degreasing the formed blank in a vacuum furnace. More preferably, the degreasing The conditions include a vacuum degree higher than 1.00 Pa, a temperature of 150-220°C (for example, 180°C or 200°C, etc.) and a time of 6-15h (for example, 10h, etc.).
因此，在本发明的一个更优选的实施方式中，本发明的方法包括以下步骤：Therefore, in a more preferred embodiment of the present invention, the method of the present invention includes the following steps:
(1)球磨：将硬质相陶瓷固溶体粉、粘结相金属粉、WC粉、Mo粉和石墨粉在球磨机中进行球磨，其中所述球磨的条件包括球料比为5-10：1、转速为120-350rpm和时间为24-96h，所述硬质相陶瓷固溶体为碳化物、氮化物和硼化物中的一种或多种固溶体，所述粘结相金属为Ni、Cr、Fe和Co中的一种或多种；(1) Ball milling: the hard phase ceramic solid solution powder, binder phase metal powder, WC powder, Mo powder and graphite powder are ball milled in a ball mill, wherein the conditions of the ball milling include a ball-to-battery ratio of 5-10:1 The rotation speed is 120-350rpm and the time is 24-96h, the hard phase ceramic solid solution is one or more solid solutions of carbides, nitrides and borides, and the binder phase metals are Ni, Cr, Fe and One or more of Co;
(2)烘干：将所得的粉末浆料进行真空烘干，其中所述烘干的条件包括温度为70-90℃；(2) Drying: vacuum drying the obtained powder slurry, wherein the drying conditions include a temperature of 70-90°C;
(3)掺胶：将烘干的混合粉末与成形剂进行混合，所述成形剂为熔化态石蜡，且所占的体积分数为30.00％-60.00％(3) Glue blending: mix the dried mixed powder with a forming agent, the forming agent is molten paraffin, and the volume fraction is 30.00%-60.00%
(4)造粒：将掺胶的混合物在造粒机中进行混合造粒，并然后进行过筛，使得所得粉末颗粒尺寸为0.2-2mm；(4) Granulation: mix and granulate the blended mixture in a granulator, and then sieving, so that the resulting powder has a particle size of 0.2-2mm;
(5)模压成型：将造粒的粉料进行模压成型，其中所述模压的条件包括压 力为200-400MPa和时间为0.5-5min；(5) Compression molding: molding the granulated powder, wherein the molding conditions include a pressure of 200-400 MPa and a time of 0.5-5 min;
(6)将成型的坯料在真空炉中进行真空脱脂，所述脱脂的条件包括真空度高于1.00Pa，温度为150-220℃和时间为6-15h；以及(6) Vacuum degreasing the formed blank in a vacuum furnace, and the degreasing conditions include a vacuum degree higher than 1.00 Pa, a temperature of 150-220°C and a time of 6-15h; and
(7)烧结：将脱脂的胚料在高于1×10 -1Pa真空度下进行烧结，其中所述烧结的条件包括温度为1220-1450℃和时间为15-60min。 (7) Sintering: the defatted billet is sintered at a vacuum degree higher than 1×10 −1 Pa, wherein the sintering conditions include a temperature of 1220 to 1450° C. and a time of 15 to 60 minutes.
在另一方面，本发明还提供了上述陶瓷发热体或通过上述方法制备的陶瓷发热体在新型烟草制品用发热器中的用途。In another aspect, the present invention also provides the use of the above-mentioned ceramic heating element or the ceramic heating element prepared by the above-mentioned method in a heater for a novel tobacco product.
本发明的金属陶瓷发热材料和通过本发明的方法制备的金属陶瓷发热材料不仅能够满足小型发热体的电学及结构特性的要求，更能较大程度地简化产品的制备工艺，降低生产成本。此外，本发明所制备的高强韧性金属陶瓷硬度为85.1～89.9HRA，抗弯强度≥1600MPa，断裂韧性K IC≥8.0MPa·m 1/2，因而还具有较好的抗冲击性、耐磨性、高温红硬性、化学稳定性和抗粘附性。 The cermet heating material of the present invention and the cermet heating material prepared by the method of the present invention can not only meet the requirements of electrical and structural characteristics of small heating elements, but also simplify the preparation process of the product to a greater extent and reduce the production cost. In addition, the high-strength and toughness cermet prepared by the present invention has a hardness of 85.1-89.9HRA, a bending strength ≥1600MPa, and a fracture toughness K IC ≥8.0MPa·m 1/2 , so it also has good impact resistance and wear resistance. , High temperature red hardness, chemical stability and anti-adhesion.
以下将通过实施例对本发明进行详细描述。Hereinafter, the present invention will be described in detail through examples.
实施例1Example 1
将TiC粉、TiN粉、Ni粉、WC粉、Mo粉和石墨粉按以下质量分数投入尼龙球磨罐中：45％TiC-13％TiN-15％Ni-16％WC-10％Mo-1％C，所用磨球为硬质合金球；球磨介质为乙醇，然后置于行星式球磨机上进行球磨，其中球料比为7：1，转速为220rpm，并且球磨时间为48h；将球磨粉末烘干后与体积分数45％的成形剂石蜡进行掺胶，掺胶后进行造粒与过筛，所得粉料平均粒径为1.5mm；随后进行模压成型，其中压制压力为300MPa且保压时间为1min；成型后在真空炉中对压坯进行真空脱脂，其中脱脂温度为150℃，保温时间为8h，并且升温速度为0.3℃/min；对脱脂后的压坯进行真空烧结，其中真空度为1×10 -2Pa，烧结温度为1280℃且保温时间为60min。所制得的金属陶瓷发热材料的性能详情见表1。 Put TiC powder, TiN powder, Ni powder, WC powder, Mo powder and graphite powder into a nylon ball milling tank according to the following mass fractions: 45%TiC-13%TiN-15%Ni-16%WC-10%Mo-1% C. The grinding ball used is a cemented carbide ball; the ball milling medium is ethanol, and then it is placed on a planetary ball mill for ball milling, where the ball-to-battery ratio is 7:1, the rotating speed is 220 rpm, and the ball milling time is 48 hours; the ball mill powder is dried After mixing with 45% volume fraction of forming agent paraffin, granulation and sieving after mixing, the average particle size of the obtained powder is 1.5mm; then compression molding is carried out, where the pressing pressure is 300MPa and the holding time is 1min ; After forming, vacuum debinding the compact in a vacuum furnace, where the debinding temperature is 150°C, the holding time is 8h, and the heating rate is 0.3°C/min; the degreased compact is vacuum sintered, and the vacuum degree is 1 ×10 -2 Pa, sintering temperature is 1280 ℃ and holding time is 60 min. The performance details of the produced cermet heating materials are shown in Table 1.
实施例2Example 2
将TiC粉、TiN粉、Ni粉、WC粉、Mo粉和石墨粉按以下质量分数投入尼龙球磨罐中：47％TiC-16％TiN-10％Ni-16％WC-10％Mo-1％C，所用磨球为硬质合金球；球磨介质为乙醇，然后置于行星式球磨机上进行球磨，其中球料比为5： 1，转速为120rpm，并且球磨时间为96h；将球磨粉末烘干后与体积分数30％的成形剂石蜡进行掺胶，掺胶后进行造粒与过筛，所得粉料平均粒径为1.6mm；随后进行模压成型，其中压制压力为200MPa且保压时间为0.5min；成型后在真空炉中对压坯进行真空脱脂，其中脱脂温度为180℃，保温时间为6h，并且升温速度为0.3℃/min；对脱脂后的压坯进行真空烧结，其中真空度为1×10 -2Pa，烧结温度为1300℃且保温时间为60min。所制得的金属陶瓷发热材料的性能详情见表1。 Put TiC powder, TiN powder, Ni powder, WC powder, Mo powder and graphite powder into a nylon ball milling tank according to the following mass fractions: 47%TiC-16%TiN-10%Ni-16%WC-10%Mo-1% C. The grinding ball used is a cemented carbide ball; the ball milling medium is ethanol, and then it is placed on a planetary ball mill for ball milling, where the ball-to-battery ratio is 5:1, the rotating speed is 120rpm, and the ball milling time is 96h; the ball milling powder is dried After mixing with 30% volume fraction of forming agent paraffin, granulation and sieving after mixing, the average particle size of the obtained powder is 1.6mm; then compression molding is carried out, where the pressing pressure is 200MPa and the holding time is 0.5 min; after forming, vacuum debinding the compact in a vacuum furnace, where the debinding temperature is 180°C, the holding time is 6h, and the heating rate is 0.3°C/min; the degreased compact is vacuum sintered, where the vacuum degree is 1×10 -2 Pa, sintering temperature is 1300℃ and holding time is 60min. The performance details of the produced cermet heating materials are shown in Table 1.
实施例3Example 3
将TiC粉、Ni粉、Cr粉、Mo粉和石墨粉按以下质量分数投入尼龙球磨罐中：12％TiC-66％WC-10％Ni-5％Cr-6％Mo-1％C，所用磨球为硬质合金球；球磨介质为乙醇，然后置于行星式球磨机上进行球磨，其中球料比为10：1，转速为350rpm，并且球磨时间为36h；将球磨粉末烘干后与体积分数60％的成形剂石蜡进行掺胶，掺胶后进行造粒与过筛，所得粉料平均粒径为2.0mm；随后进行模压成型，其中压制压力为400MPa且保压时间为2min；成型后在真空炉中对压坯进行真空脱脂，其中脱脂温度为220℃，保温时间为15h，并且升温速度为0.3℃/min；对脱脂后的压坯进行真空烧结，其中真空度为1×10 -2Pa，烧结温度为1400℃且保温时间15min。所制得的金属陶瓷发热材料的性能详情见表1。 Put TiC powder, Ni powder, Cr powder, Mo powder and graphite powder into a nylon ball milling tank in the following mass fractions: 12%TiC-66%WC-10%Ni-5％Cr-6％Mo-1％C, used The grinding ball is a cemented carbide ball; the ball milling medium is ethanol, and then it is placed on a planetary ball mill for ball milling. The ball-to-battery ratio is 10:1, the rotating speed is 350rpm, and the ball milling time is 36h; Paraffin wax with a fraction of 60% forming agent is blended, granulated and sieved after blending, and the average particle size of the obtained powder is 2.0mm; then compression molding is performed, where the compression pressure is 400MPa and the pressure holding time is 2min; after molding vacuum degreased the compacts in a vacuum oven, wherein the binder burn out temperature is 220 deg.] C, holding time of 15H, and the temperature rise rate of 0.3 ℃ / min; green compacts degreased vacuum sintering, wherein a degree of vacuum of 1 × 10 - 2 Pa, sintering temperature is 1400℃ and holding time is 15min. The performance details of the produced cermet heating materials are shown in Table 1.
实施例4Example 4
将Mo 2FeB 2粉、Fe粉和Mo粉按以下质量分数投入尼龙球磨罐中：63％Mo 2FeB 2-20％Fe-17％Mo，所用磨球为硬质合金球；球磨介质为乙醇，然后置于行星式球磨机上进行球磨，其中球料比为7：1，转速为230rpm，并且球磨时间为48h；将球磨粉末烘干后与体积分数45％的成形剂石蜡进行掺胶，掺胶后进行造粒与过筛，所得粉料平均粒径为1.6mm；随后进行模压成型，其中压制压力为200MPa且保压时间为0.5min；成形后在真空炉中对压坯进行真空脱脂，其中脱脂温度为180℃，保温时间为8h，并且升温速度为0.3℃/min；对脱脂后的压坯进行真空烧结，其中真空度为1×10 -2Pa，烧结温度为1220℃且保温时间为60min。所制得的金属陶瓷发热材料的性能详情见表1。 Put Mo 2 FeB 2 powder, Fe powder and Mo powder into a nylon ball milling tank according to the following mass fractions: 63% Mo 2 FeB 2 -20% Fe-17% Mo, the grinding balls used are cemented carbide balls; the ball milling medium is ethanol , And then placed on a planetary ball mill for ball milling, where the ball-to-battery ratio is 7:1, the rotating speed is 230rpm, and the ball milling time is 48h; the ball mill powder is dried and mixed with 45% volume fraction of paraffin wax. After the glue is granulated and sieved, the average particle size of the obtained powder is 1.6mm; then it is compression molded, where the compression pressure is 200MPa and the pressure holding time is 0.5min; after the molding, the compact is vacuum degreasing in a vacuum furnace, The debinding temperature is 180°C, the holding time is 8h, and the heating rate is 0.3°C/min; the degreased compact is vacuum sintered, the vacuum degree is 1×10 -2 Pa, the sintering temperature is 1220°C and the holding time For 60min. The performance details of the produced cermet heating materials are shown in Table 1.
实施例5Example 5
将TiC粉、TiN粉、NiCr合金粉、WC粉、Mo粉和石墨粉按以下质量分数投入尼龙球磨罐中：45％TiN-10％TiC-18％NiCr-16％WC-10％Mo-1％C，所用磨球为硬质合金球；球磨介质为乙醇，然后置于行星式球磨机上进行球磨，其中球料比为7：1，转速为230rpm，并且球磨时间为48h；将球磨粉末烘干后与体积分数45％的成形剂石蜡进行掺胶，掺胶后进行造粒与过筛，所得粉料平均粒径为1.7mm；随后进行模压成型，其中压制压力为200MPa且保压时间为1min；成形后在真空炉中对压坯进行真空脱脂，其中脱脂温度为180℃，保温时间为6h，并且升温速度为0.3℃/min；对脱脂后的压坯进行真空烧结，其中真空度为1×10 -2Pa，烧结温度为1300℃且保温时间为60min。所制得的金属陶瓷发热材料的性能详情见表1。 Put TiC powder, TiN powder, NiCr alloy powder, WC powder, Mo powder and graphite powder into a nylon ball milling tank according to the following mass fractions: 45%TiN-10%TiC-18%NiCr-16%WC-10%Mo-1 %C, the grinding ball used is a cemented carbide ball; the ball milling medium is ethanol, and then placed on a planetary ball mill for ball milling, where the ball-to-battery ratio is 7:1, the rotation speed is 230rpm, and the milling time is 48h; the ball mill powder is dried After drying, it is blended with paraffin wax with a volume fraction of 45%. After blending, granulation and sieving are performed. The average particle size of the powder obtained is 1.7mm. Then it is compression molded, where the pressing pressure is 200MPa and the holding time is 1min; After forming, vacuum debinding the compact in a vacuum furnace, where the debinding temperature is 180°C, the holding time is 6h, and the heating rate is 0.3°C/min; the degreased compact is vacuum sintered, where the vacuum degree is 1×10 -2 Pa, sintering temperature is 1300℃ and holding time is 60min. The performance details of the produced cermet heating materials are shown in Table 1.
表1Table 1
Figure PCTCN2020114514-appb-000001
Figure PCTCN2020114514-appb-000001
通过表1中的结果可以看出，通过本发明的方法制备的金属陶瓷硬度确实满足85.1～89.9HRA，抗弯强度≥1600MPa，断裂韧性K IC≥8.0MPa·m 1/2，因而具有较好的抗冲击性、耐磨性、高温红硬性、化学稳定性和抗粘附性。此外，通过本发明的方法制得的材料的电阻率均为0.001-0.05Ω·cm，因而也同样能够满足小型发热体的电学特性的要求。 It can be seen from the results in Table 1 that the hardness of the cermet prepared by the method of the present invention does meet 85.1～89.9HRA, the bending strength is ≥1600MPa, and the fracture toughness K IC ≥8.0MPa·m 1/2 , so it has better The impact resistance, abrasion resistance, high temperature red hardness, chemical stability and adhesion resistance. In addition, the resistivities of the materials prepared by the method of the present invention are all 0.001-0.05 Ω·cm, and thus can also meet the requirements of electrical characteristics of small heating elements.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention. These simple modifications All belong to the protection scope of the present invention.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征， 在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。In addition, it should be noted that the various specific technical features described in the foregoing specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention provides various possible combinations. The combination method will not be explained separately.
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。In addition, various different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (11)

  1. 一种金属陶瓷发热材料，其中，所述金属陶瓷发热材料包含硬质相陶瓷固溶体和粘结相金属，所述硬质相陶瓷固溶体为碳化物、氮化物和硼化物中的一种或多种固溶体，所述粘结相金属为Ni、Cr、Fe和Co中的一种或多种。A cermet heating material, wherein the cermet heating material comprises a hard phase ceramic solid solution and a binder phase metal, and the hard phase ceramic solid solution is one or more of carbides, nitrides and borides Solid solution, the binder phase metal is one or more of Ni, Cr, Fe and Co.
  2. 根据权利要求1所述的金属陶瓷发热材料，其中，所述金属陶瓷发热材料的孔隙率为0.5％-20％，电阻率为0.001-0.05Ω·cm。The cermet heating material according to claim 1, wherein the porosity of the cermet heating material is 0.5%-20%, and the resistivity is 0.001-0.05 Ω·cm.
  3. 根据权利要求1所述的金属陶瓷发热材料，其中，所述硬质相和粘结相的重量比为1-20：1，优选为2-10：1。The cermet heating material according to claim 1, wherein the weight ratio of the hard phase to the binder phase is 1-20:1, preferably 2-10:1.
  4. 一种制备金属陶瓷发热材料的方法，其包括以下步骤：A method for preparing a cermet heating material, which includes the following steps:
    (1)球磨：将硬质相陶瓷固溶体粉和粘结相金属粉在球磨机中进行球磨，其中所述球磨的条件包括球料比为5-10：1、转速为120-350rpm和时间为24-96h，所述硬质相陶瓷固溶体为碳化物、氮化物和硼化物中的一种或多种固溶体，所述粘结相金属为Ni、Cr、Fe和Co中的一种或多种；(1) Ball milling: the hard phase ceramic solid solution powder and the binder phase metal powder are ball milled in a ball mill, wherein the conditions of the ball milling include a ball-to-material ratio of 5-10:1, a rotation speed of 120-350rpm and a time of 24 -96h, the hard phase ceramic solid solution is one or more solid solutions of carbides, nitrides and borides, and the binder phase metal is one or more of Ni, Cr, Fe and Co;
    (2)烘干：将所得的粉末浆料进行真空烘干，其中所述烘干的条件包括温度为70-90℃；(2) Drying: vacuum drying the obtained powder slurry, wherein the drying conditions include a temperature of 70-90°C;
    (3)造粒：将所得的混合物在造粒机中进行混合造粒，并然后进行过筛，使得所得粉末颗粒尺寸为0.2-2mm；(3) Granulation: the obtained mixture is mixed and granulated in a granulator, and then sieved, so that the obtained powder has a particle size of 0.2-2mm;
    (4)模压成型：将造粒的粉料进行模压成型，其中所述模压的条件包括压力为200-400MPa和时间为0.5-5min；以及(4) Compression molding: molding the granulated powder, wherein the molding conditions include a pressure of 200-400 MPa and a time of 0.5-5 min; and
    (5)烧结：将所得的胚料在高于1×10 -1Pa真空度下进行烧结，其中所述烧结的条件包括温度为1220-1450℃和时间为15-60min。 (5) Sintering: the obtained blank is sintered at a vacuum degree higher than 1×10 −1 Pa, wherein the sintering conditions include a temperature of 1220 to 1450° C. and a time of 15 to 60 minutes.
  5. 根据权利要求4所述的方法，其中，所述球磨步骤还包括在所述球磨机中加入WC粉、Mo粉和石墨粉中的至少一种。The method according to claim 4, wherein the ball milling step further comprises adding at least one of WC powder, Mo powder and graphite powder in the ball mill.
  6. 根据权利要求5所述的方法，其中，所述球磨步骤中各组分的重量百分比包括硬质相陶瓷固溶体31.00％-68.00％，粘结相金属10.00％-20.00％，WC11.00％-19.00％，Mo 5.00％-15.00％和石墨0.50％-3.00％。The method according to claim 5, wherein the weight percentage of each component in the ball milling step comprises 31.00%-68.00% of the hard phase ceramic solid solution, 10.00%-20.00% of the binder phase metal, and 11.00%-19.00 of the WC %, Mo 5.00%-15.00% and graphite 0.50%-3.00%.
  7. 根据权利要求4所述的方法，其还包括在造粒步骤之前的掺胶步骤，所述掺胶包括将烘干的混合粉末与成形剂进行混合。4. The method according to claim 4, further comprising a mixing step before the granulation step, the mixing including mixing the dried mixed powder with the forming agent.
  8. 根据权利要求7所述的方法，其中，所述成形剂为熔化态石蜡，优选地，所述成形剂所占的体积分数为30.00％-60.00％。The method according to claim 7, wherein the forming agent is molten paraffin, and preferably, the volume fraction of the forming agent is 30.00%-60.00%.
  9. 根据权利要求4所述的方法，其还包括在模压成型步骤后的脱脂步骤，所述脱脂包括将成型的坯料在真空炉中进行真空脱脂。The method according to claim 4, further comprising a degreasing step after the compression molding step, the degreasing comprising vacuum degreasing the formed blank in a vacuum furnace.
  10. 根据权利要求9所述的方法，其中，所述脱脂的条件包括真空度高于1.00Pa，温度为150-220℃和时间为6-15h。The method according to claim 9, wherein the degreasing conditions include a vacuum degree higher than 1.00 Pa, a temperature of 150-220°C and a time of 6-15h.
  11. 权利要求1至3中任一项所述的陶瓷发热体或通过权利要求4至10中任一项所述的方法制备的陶瓷发热体在新型烟草制品用发热器中的用途。Use of the ceramic heating element according to any one of claims 1 to 3 or the ceramic heating element prepared by the method according to any one of claims 4 to 10 in a heater for a new type of tobacco product.
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