WO2019227811A1 - Ultrafine transition-metal boride powder, and preparation method therefor and application thereof - Google Patents

Ultrafine transition-metal boride powder, and preparation method therefor and application thereof Download PDF

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WO2019227811A1
WO2019227811A1 PCT/CN2018/108947 CN2018108947W WO2019227811A1 WO 2019227811 A1 WO2019227811 A1 WO 2019227811A1 CN 2018108947 W CN2018108947 W CN 2018108947W WO 2019227811 A1 WO2019227811 A1 WO 2019227811A1
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powder
ultra
metal boride
transition metal
fine transition
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Chinese (zh)
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郭伟明
吴利翔
谭大旺
牛文彬
曾令勇
林华泰
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广东工业大学
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/02—Boron; Borides
    • C01B35/04—Metal borides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

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  • the invention belongs to the technical field of ultra-fine powders, and more particularly, relates to an ultra-fine transition metal boride (M 1-x Ta x B 2 ) powder, and a preparation method and application thereof.
  • M 1-x Ta x B 2 ultra-fine transition metal boride
  • the existing methods for preparing MB 2 powder mainly include the following methods: 1) Direct synthesis method: M elemental substance and elemental boron are mainly used for the compounding reaction.
  • the method has high purity of synthetic powder, and the synthesis conditions are relatively simple.
  • the raw materials are expensive, and the synthesized MB 2 powder has a coarse particle size and low activity, which is not conducive to sintering and post-processing of the powder.
  • High-temperature self-propagation method Although the traditional SHS method can obtain high-purity ZrB 2 powder, the residue is difficult to remove; the existing SHS method uses zirconium hydride and elemental boron as raw materials under argon atmosphere Synthetic, although powders with a particle size of less than 1 ⁇ m can be obtained. However, its heating rate and cooling rate are fast, and the reaction is not easy to complete, so there are many impurities, and its reaction process, product structure and performance are not easy to control. 3) Carbothermal reduction method: This method uses a carbothermal reduction method to mix ZrO 2 , B 4 C, and C powder in an inert atmosphere in an electric furnace and sinter.
  • This method is easy to produce ZrC impurities at high temperature and difficult to remove, so there are many residual impurities, complicated by-products, and low sintering activity.
  • Ceramic precursor cracking method using various ceramic precursors to react with metal oxides, metals, etc., and cracking at lower temperature pairs to synthesize transition metal borides.
  • Mechanical alloying method, liquid phase method, etc. not every method can synthesize a powder of MB 2 with a particle size smaller than 1 ⁇ m. Even for those preparation methods that can synthesize a particle size of less than 1 ⁇ m, the process is too complicated and the purity is not high.
  • CN201611021565.3 proposed a simple method for preparing ultra-fine powder
  • the inventor found through a large number of experiments that when the temperature of the second step in the patent is higher than 1800 ° C, the surface of the boride powder diffuses. Vigorous enhancement, with further increase in temperature, boride powders grow rapidly.
  • the main use of ultra-high temperature powder is as a spray material in the aerospace field such as hypersonic vehicles. At this time, the temperature is often higher than 1800 ° C. Therefore, the patent CN201611021565.3 is used in aerospace fields such as hypersonic vehicles Applications have great limitations. Based on the above background, it is necessary to find a simple process to prepare superfine MB 2 powder (particle size ⁇ 1 ⁇ m) that does not grow in high temperature environment (> 1800 ° C).
  • an ultra-fine transition metal boride (M 1-x Ta x B 2 ) powder is provided.
  • the M 1-x Ta x B 2 powder has a small particle size, a low degree of agglomeration, and good high temperature resistance.
  • Another object of the present invention is to provide a method for preparing the above ultrafine M 1-x Ta x B 2 powder.
  • the method has the advantages of simple preparation process, low cost, practicality, strong operability, and easy realization of large-scale production.
  • Another object of the present invention is to provide the application of the above-mentioned ultra-fine M 1-x Ta x B 2 powder.
  • the M 1-x Ta x B 2 powder has a particle diameter of 10 nm to 1 ⁇ m and an oxygen content of 0.1 to 2 wt%.
  • the molar ratio of MO 2 and B is 1: (2.5-5), and the molar ratio of Ta 2 O 5 and B is 1: (7.5-10).
  • the temperature for the first step of thermal insulation is 800 to 1200 ° C
  • the temperature for the second step of thermal insulation is 1300 to 2200 ° C.
  • the solvent is acetone or ethanol
  • the inert atmosphere is argon, helium, or neon.
  • the method for preparing the ultra-fine transition metal boride powder includes the following specific steps:
  • the MO 2 -Ta 2 O 5 -B mixed powder is placed in a graphite crucible, and the first step of heat preservation is performed under the pressure of less than 200 Pa or in an inert atmosphere to obtain M 1-x Ta x B 2 -B 2 O 3 powder;
  • the M 1-x Ta x B 2 -B 2 O 3 powder is further heated under the pressure of less than 200 Pa or in an inert atmosphere, and the second step of heat preservation is performed to obtain M 1-x Ta x B 2 powder.
  • the particle diameters of the MO 2 powder, Ta 2 O 5 powder, and B powder in step S1 are all 0.01 to 5 ⁇ m.
  • the purity of the MO 2 powder, Ta 2 O 5 powder, and B powder in step S1 are all 90 to 100%.
  • the holding time in the first step in step S1 is 0.1 to 10 hours, and the holding time in the second step is 0.1 to 2 hours.
  • the present invention has the following beneficial effects:
  • the compatibility of the liquid phase formed by MB 2 and B 2 O 3 is changed.
  • the surface diffusion of MB 2 is suppressed to prevent the powder from growing at high temperature (> 1800 ° C), and the high-temperature stability of MB 2 is improved.
  • the prepared M 1-x Ta x B 2 powder has a small particle size, a low degree of agglomeration, and good high-temperature resistance. It still does not grow up at high temperatures above 1800 ° C.
  • the present invention prepares ultra-fine M 1-x Ta x B 2 powder through a simple two-step direct temperature rising process.
  • the preparation process is simple, low cost, practical, strong controllability, and easy to achieve large-scale production.
  • the TaB 2 phase formed by the reaction between the solid solution Ta 2 O 5 and the boron powder in the powder prepared by the present invention is also an ultra high temperature phase, which will not reduce the high temperature resistance of the prepared ultra high temperature ceramic powder.
  • FIG. 1 is a SEM photograph of Hf 0.95 Ta 0.05 B 2 powder prepared in Example 1.
  • FIG. 1 is a SEM photograph of Hf 0.95 Ta 0.05 B 2 powder prepared in Example 1.
  • FIG. 2 is a TEM photograph of the Hf 0.95 Ta 0.05 B 2 powder prepared in Example 1.
  • FIG. 2 is a TEM photograph of the Hf 0.95 Ta 0.05 B 2 powder prepared in Example 1.
  • FIG. 3 is a SEM photograph of Hf 0.95 Ta 0.05 B 2 powder prepared in Example 2.
  • the content of the present invention is further described below with reference to specific embodiments, but it should not be construed as limiting the present invention.
  • the technical means used in the embodiments are conventional means well known to those skilled in the art.
  • the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in the technical field.
  • HfO 2 , Ta 2 O 5 and B powders as powder raw materials.
  • the particle size distributions of HfO 2 , Ta 2 O 5 and B powders are 0.2 ⁇ m, 0.1 ⁇ m and 0.5 ⁇ m, respectively.
  • the HfO 2 -Ta 2 O 5 -B mixed powder is placed in a graphite crucible. In a graphite furnace, the pressure is lower than 200 Pa, heated to 1000 ° C. and held for 2 hours to obtain Hf 0.95 Ta 0.05 B. 2 -B 2 O 3 powder;
  • the obtained Hf 0.95 Ta 0.05 B 2 -B 2 O 3 powder was heated to 1500 ° C. and maintained for 1 hour under the condition that the air pressure was lower than 200 Pa to obtain ultra-fine Hf 0.95 Ta 0.05 B 2 powder.
  • Figures 1 and 2 show the SEM and TEM pictures of the prepared Hf 0.95 Ta 0.05 B 2 powder, respectively. As can be seen from Figures 1 and 2, the powder particle size is uniform, the average particle size is 50 nm, and the oxygen content is 0.1. wt%.
  • Embodiment 2 This embodiment is different from Embodiment 1 in that the second step of high-temperature insulation is 1800 ° C for 2 hours.
  • Example 3 is a SEM photograph of the obtained Hf 0.95 Ta 0.05 B 2 powder embodiment, seen from FIG. 3, the second step and the powder was heated to 1800 °C not grow significantly after the solution described TaB 2
  • the transition metal samarium boride powder can suppress the surface diffusion phenomenon of samarium boride, so that the samarium boride powder does not grow up rapidly at high temperature and enhance its high temperature stability. It is known through inspection and analysis that the average particle diameter of the Hf 0.95 Ta 0.05 B 2 powder prepared in this embodiment is 60 nm, and the oxygen content is 0.02 wt%.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the second step of high-temperature heat preservation is 2200 ° C for 1 hour.
  • the average particle diameter of the Hf 0.95 Ta 0.05 B 2 powder prepared in this embodiment is 80 nm, and the oxygen content is 0.01 wt%.
  • This embodiment is different from Example 1 in that the particle size distribution of the HfO 2 , Ta 2 O 5 and boron powder is 0.02 ⁇ m, 0.03 ⁇ m, and 0.02 ⁇ m; the first step is to heat to 950 ° C. And incubate for 1 hour. It is known through inspection and analysis that the average particle diameter of the Hf 0.95 Ta 0.05 B 2 powder prepared in this embodiment is 30 nm and the oxygen content is 0.15 wt%.
  • This embodiment is different from Example 1 in that the content x of the solid solution TaB 2 is 0.5 mol%.
  • the average particle diameter of the Zr 0.995 Ta 0.005 B 2 powder prepared in this embodiment is 80 nm, and the oxygen content is 0.10 wt%.
  • This embodiment is different from Example 1 in that HfO 2 in the raw material is replaced with ZrO 2 .
  • the average particle diameter of the Zr 0.95 Ta 0.05 B 2 powder obtained in this embodiment is 70 nm and the oxygen content is 0.05 wt%.
  • Example 1 The difference between this embodiment and Example 1 is that the content x of the solid solution TaB 2 is 15 mol%, and the first step of heat preservation is heating to 1200 ° C. and holding for 1 hour.
  • the average particle diameter of the Hf 0.85 Ta 0.15 B 2 powder prepared in this embodiment is 60 nm, and the oxygen content is 0.05% by weight.

Abstract

Provided are an ultrafine transition-metal boride powder, and a preparation method therefor and an application thereof. The powder is prepared by: adding MO 2, Ta 2O 5, and B to a solvent and performing ball milling for mixing, drying the mixture to obtain a MO 2-Ta 2O 5-B mixed powder, then subjecting the mixed powder to first heat preservation at an air pressure of 200 Pa or below or in an inert atmosphere to obtain a M 1-xTa xB 2-B 2O 3 powder, continuously heating the powder at the same air pressure or in the same atmosphere, and subjecting the powder to second heat preservation to prepare a M 1-xTa xB 2 powder, wherein M is Zr or Hf, and x is 0.005-0.2. The prepared powder can be used in the field of ultra-high-temperature coatings, has low degree of agglomeration and good high temperature resistance, and does not grow at 1800°C or more. The preparation method significantly reduces the costs and has a simple process.

Description

一种超细过渡金属硼化物粉体及其制备方法和应用Ultrafine transition metal boride powder, preparation method and application thereof 技术领域Technical field
本发明属于超细粉体技术领域，更具体地，涉及一种超细过渡金属硼化物(M 1-xTa xB 2)粉体及其制备方法和应用。 The invention belongs to the technical field of ultra-fine powders, and more particularly, relates to an ultra-fine transition metal boride (M 1-x Ta x B 2 ) powder, and a preparation method and application thereof.
背景技术Background technique
过渡金属硼化物MB 2(M＝Zr，Hf)具有高的熔点、硬度、热稳定性和抗腐蚀性等优异的性能，广泛用于制作超高温结构材料、复合材料、薄膜材料，在机械加工、冶金矿产、航天航空等领域有重要的应用。 Transition metal boride MB 2 (M = Zr, Hf) has excellent properties such as high melting point, hardness, thermal stability, and corrosion resistance. It is widely used in the manufacture of ultra-high temperature structural materials, composite materials, and thin film materials. , Metallurgical minerals, aerospace and other fields have important applications.
目前，现有的制备MB 2粉体的方法主要有以下几种：1)直接合成法：主要利用M单质与单质硼进行化合反应。该方法合成粉末纯度高，合成条件比较简单。但原料昂贵，合成的MB 2粉末粒度粗大，活性低，不利于粉末的烧结以及后加工处理。2)高温自蔓延法：传统的SHS法虽然能够得到高纯度的ZrB 2粉体，但是残留物在其中难以除去；现有的SHS法是利用氢化锆和单质硼为原料，在氩气氛围下合成的，虽然可以获得粒径小于1μm的粉体。但是其升温速率及冷却速率很快，反应不易完全进行，因此杂质较多，且其反应过程、产物结构以及性能不易控制。3)碳热还原法：该方法是利用碳热还原法，将ZrO 2、B 4C、和C粉混合置于电炉中的惰性气氛下烧结。该方法在高温下易生产ZrC杂质，难以除去，所以残留杂质多，副产物复杂，烧结活性低。4)陶瓷前驱体裂解法：利用各种陶瓷前驱体与金属氧化物、金属等反应，在较低温对下裂解，合成出过渡金属硼化物。5)机械合金化法、液相法等。在以上众多制备方法中，并不是每一种方法都能合成粒径小于1μm的MB 2的粉体。即使对于那些能够合成粒径小于1μm的制备方法，也因为工艺太过于复杂，而且纯度不高。虽然，CN201611021565.3提出了一种简单方法制备超细粉体，但是本发明人通过大量的实验发现，当该专利中第二步保温的温度高于1800℃时，由于硼化物粉体表面扩散剧烈增强，随着温度的进一步提高，硼化物粉体发生迅速长大。然而，超高温粉体主要用途是作为高超音速飞行器等航空航天领域的喷涂材料，此时，往往承受的温度远高于1800℃，所以，CN201611021565.3这一专利在高超音速飞行器等航天航空领域应用具有极大的局限性。基于以上背景，很有必要寻找一种简单的工艺制备高温环境(＞1800℃)不长大的超细MB 2粉体(粒径≤1μm)。 At present, the existing methods for preparing MB 2 powder mainly include the following methods: 1) Direct synthesis method: M elemental substance and elemental boron are mainly used for the compounding reaction. The method has high purity of synthetic powder, and the synthesis conditions are relatively simple. However, the raw materials are expensive, and the synthesized MB 2 powder has a coarse particle size and low activity, which is not conducive to sintering and post-processing of the powder. 2) High-temperature self-propagation method: Although the traditional SHS method can obtain high-purity ZrB 2 powder, the residue is difficult to remove; the existing SHS method uses zirconium hydride and elemental boron as raw materials under argon atmosphere Synthetic, although powders with a particle size of less than 1 μm can be obtained. However, its heating rate and cooling rate are fast, and the reaction is not easy to complete, so there are many impurities, and its reaction process, product structure and performance are not easy to control. 3) Carbothermal reduction method: This method uses a carbothermal reduction method to mix ZrO 2 , B 4 C, and C powder in an inert atmosphere in an electric furnace and sinter. This method is easy to produce ZrC impurities at high temperature and difficult to remove, so there are many residual impurities, complicated by-products, and low sintering activity. 4) Ceramic precursor cracking method: using various ceramic precursors to react with metal oxides, metals, etc., and cracking at lower temperature pairs to synthesize transition metal borides. 5) Mechanical alloying method, liquid phase method, etc. Among the above many preparation methods, not every method can synthesize a powder of MB 2 with a particle size smaller than 1 μm. Even for those preparation methods that can synthesize a particle size of less than 1 μm, the process is too complicated and the purity is not high. Although CN201611021565.3 proposed a simple method for preparing ultra-fine powder, the inventor found through a large number of experiments that when the temperature of the second step in the patent is higher than 1800 ° C, the surface of the boride powder diffuses. Vigorous enhancement, with further increase in temperature, boride powders grow rapidly. However, the main use of ultra-high temperature powder is as a spray material in the aerospace field such as hypersonic vehicles. At this time, the temperature is often higher than 1800 ° C. Therefore, the patent CN201611021565.3 is used in aerospace fields such as hypersonic vehicles Applications have great limitations. Based on the above background, it is necessary to find a simple process to prepare superfine MB 2 powder (particle size ≤1 μm) that does not grow in high temperature environment (> 1800 ° C).
发明内容Summary of the Invention
为了解决上述现有技术存在的不足和缺点，提供一种超细过渡金属硼化物(M 1-xTa xB 2)粉体。该M 1-xTa xB 2粉体粒径小，团聚度低，具有良好的耐高温性能。 In order to solve the above-mentioned shortcomings and disadvantages of the prior art, an ultra-fine transition metal boride (M 1-x Ta x B 2 ) powder is provided. The M 1-x Ta x B 2 powder has a small particle size, a low degree of agglomeration, and good high temperature resistance.
本发明的另一目的在于提供一种上述超细M 1-xTa xB 2粉体的制备方法。该方法制备工艺简单、成本低、实用，可操作性强，容易实现规模化生产。 Another object of the present invention is to provide a method for preparing the above ultrafine M 1-x Ta x B 2 powder. The method has the advantages of simple preparation process, low cost, practicality, strong operability, and easy realization of large-scale production.
本发明的再一目的在于提供上述超细M 1-xTa xB 2粉体的应用。 Another object of the present invention is to provide the application of the above-mentioned ultra-fine M 1-x Ta x B 2 powder.
本发明的目的通过下述技术方案来实现：The object of the present invention is achieved by the following technical solutions:
一种超细过渡金属硼化物粉体，所述超细过渡金属硼化物粉体是将MO 2，Ta 2O 5和B加入溶剂后进行球磨混合，干燥后得到MO 2-Ta 2O 5-B混合粉体，再将MO 2-Ta 2O 5-B混合粉体在气压低于200Pa或惰性气氛下进行第一步保温，得到M 1-xTa xB 2-B 2O 3粉体，将M 1-xTa xB 2-B 2O 3粉体在气压低于200Pa或惰性气氛下继续升温，进行第二步保温，制成M 1-xTa xB 2粉体，其中，M＝Zr或Hf，x为0.005～0.2。 An ultra-fine transition metal boride powder is obtained by adding MO 2 , Ta 2 O 5 and B to a solvent and performing ball milling and mixing to obtain MO 2 -Ta 2 O 5- B mixed powder, and then MO 2 -Ta 2 O 5 -B mixed powder is subjected to the first step of heat preservation under an air pressure of less than 200 Pa or an inert atmosphere to obtain M 1-x Ta x B 2 -B 2 O 3 powder , M 1-x Ta x B 2 -B 2 O 3 powder is further heated under the pressure of less than 200 Pa or in an inert atmosphere, and the second step of heat preservation is performed to prepare M 1-x Ta x B 2 powder, wherein, M = Zr or Hf, and x is 0.005 to 0.2.
优选地，所述M 1-xTa xB 2粉体的粒径为10nm～1μm，其氧含量0.1～2wt％。 Preferably, the M 1-x Ta x B 2 powder has a particle diameter of 10 nm to 1 μm and an oxygen content of 0.1 to 2 wt%.
优选地，所述MO 2和B的摩尔比为1∶(2.5～5)，Ta 2O 5和B的摩尔比为1∶(7.5～10)。 Preferably, the molar ratio of MO 2 and B is 1: (2.5-5), and the molar ratio of Ta 2 O 5 and B is 1: (7.5-10).
优选地，所述第一步保温的温度为800～1200℃，所述第二步保温的温度为1300～2200℃。Preferably, the temperature for the first step of thermal insulation is 800 to 1200 ° C, and the temperature for the second step of thermal insulation is 1300 to 2200 ° C.
优选地，所述的溶剂为丙酮或乙醇，所述惰性气氛为氩气、氦气、氖气。Preferably, the solvent is acetone or ethanol, and the inert atmosphere is argon, helium, or neon.
所述的超细过渡金属硼化物粉体的制备方法，包括如下具体步骤：The method for preparing the ultra-fine transition metal boride powder includes the following specific steps:
S1.将Ta 2O 5粉体和MO 2粉体混合得到MO 2-Ta 2O 5混合粉体，再加入B粉再加入溶剂后进行球磨，干燥后得到MO 2-Ta 2O 5-B混合粉体； S1. Mixing Ta 2 O 5 powder and MO 2 powder to obtain MO 2 -Ta 2 O 5 mixed powder, adding powder B, adding solvent and performing ball milling, and drying to obtain MO 2 -Ta 2 O 5 -B Mixed powder
S2.再将MO 2-Ta 2O 5-B混合粉体置于石墨坩埚内，在气压低于200Pa或惰性气氛下进行第一步保温，得到M 1-xTa xB 2-B 2O 3粉体； S2. The MO 2 -Ta 2 O 5 -B mixed powder is placed in a graphite crucible, and the first step of heat preservation is performed under the pressure of less than 200 Pa or in an inert atmosphere to obtain M 1-x Ta x B 2 -B 2 O 3 powder;
S3.将M 1-xTa xB 2-B 2O 3粉体在气压低于200Pa或惰性气氛下继续升温，进行第二步保温，得到M 1-xTa xB 2粉体。 S3. The M 1-x Ta x B 2 -B 2 O 3 powder is further heated under the pressure of less than 200 Pa or in an inert atmosphere, and the second step of heat preservation is performed to obtain M 1-x Ta x B 2 powder.
优选地，步骤S1中所述MO 2粉、Ta 2O 5粉和B粉的粒径均为0.01～5μm。 Preferably, the particle diameters of the MO 2 powder, Ta 2 O 5 powder, and B powder in step S1 are all 0.01 to 5 μm.
优选地，步骤S1中所述MO 2粉、Ta 2O 5粉和B粉的纯度均为90～100％。 Preferably, the purity of the MO 2 powder, Ta 2 O 5 powder, and B powder in step S1 are all 90 to 100%.
优选地，步骤S1中所述第一步保温的时间为0.1～10h，第二步保温的时间为0.1～2h。Preferably, the holding time in the first step in step S1 is 0.1 to 10 hours, and the holding time in the second step is 0.1 to 2 hours.
所述的超细过渡金属硼化物粉体在超高温涂层领域中的应用。Application of the ultra-fine transition metal boride powder in the field of ultra-high temperature coating.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1.本发明在MB 2(M＝Zr或Hf)中固溶Ta 2O 5与B粉反应生成TaB 2，在改变MB 2与B 2O 3所形成液相的相容性，同时还通过抑制MB 2的表面扩散从而防止粉体的高温(＞1800℃)长大，提高了MB 2的高温稳定性，通过两步的低温保温和高温保温制备超细M 1-xTa xB 2(M＝Zr或Hf)粉体。制备的M 1-xTa xB 2粉体粒径小，团聚度低，具有良好的耐高温性能，在1800℃以上高温仍然不发生长大。 1. According to the present invention, in the MB 2 (M = Zr or Hf) solution of Ta 2 O 5 and B powder is reacted to form TaB 2. The compatibility of the liquid phase formed by MB 2 and B 2 O 3 is changed. The surface diffusion of MB 2 is suppressed to prevent the powder from growing at high temperature (> 1800 ° C), and the high-temperature stability of MB 2 is improved. Ultrafine M 1-x Ta x B 2 ( M = Zr or Hf) powder. The prepared M 1-x Ta x B 2 powder has a small particle size, a low degree of agglomeration, and good high-temperature resistance. It still does not grow up at high temperatures above 1800 ° C.
2.本发明通过简单的两步直接升温工艺制备超细M 1-xTa xB 2粉体，制备工艺简单、成本低、实用，可操控性强，容易实现规模化生产。 2. The present invention prepares ultra-fine M 1-x Ta x B 2 powder through a simple two-step direct temperature rising process. The preparation process is simple, low cost, practical, strong controllability, and easy to achieve large-scale production.
3.本发明制备的粉体中固溶Ta 2O 5与硼粉反应生成的TaB 2相也是一种超高温相，不会降低所制备超高温陶瓷粉体的耐高温性能。 3. The TaB 2 phase formed by the reaction between the solid solution Ta 2 O 5 and the boron powder in the powder prepared by the present invention is also an ultra high temperature phase, which will not reduce the high temperature resistance of the prepared ultra high temperature ceramic powder.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为实施例1中所制的Hf 0.95Ta 0.05B 2粉体的SEM照片。 FIG. 1 is a SEM photograph of Hf 0.95 Ta 0.05 B 2 powder prepared in Example 1. FIG.
图2为实施例1中所制的Hf 0.95Ta 0.05B 2粉体的TEM照片。 FIG. 2 is a TEM photograph of the Hf 0.95 Ta 0.05 B 2 powder prepared in Example 1. FIG.
图3为实施例2中所制的Hf 0.95Ta 0.05B 2粉体的SEM照片。 3 is a SEM photograph of Hf 0.95 Ta 0.05 B 2 powder prepared in Example 2. FIG.
具体实施方式Detailed ways
下面结合具体实施例进一步说明本发明的内容，但不应理解为对本发明的限制。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。The content of the present invention is further described below with reference to specific embodiments, but it should not be construed as limiting the present invention. Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in the technical field.
实施例1Example 1
1.选HfO 2、Ta 2O 5和B粉为粉体原料，HfO 2、Ta 2O 5和B粉的粒径分布分别为0.2μm、0.1μm和0.5μm，称取100mmol HfO 2中掺杂2.5mol％Ta 2O 5的HfO 2-Ta 2O 5混合粉体和393mmol单质B，以丙酮为溶剂，Si 3N 4球为球磨介质，在辊式球磨机上混合24小时，旋转蒸发干燥，得到HfO 2-Ta 2O 5-B混合粉体；其中，所述固溶的TaB 2的含量x为5mol％； 1. Select HfO 2 , Ta 2 O 5 and B powders as powder raw materials. The particle size distributions of HfO 2 , Ta 2 O 5 and B powders are 0.2 μm, 0.1 μm and 0.5 μm, respectively. Weigh 100 mmol of HfO 2 HfO 2 -Ta 2 O 5 mixed powder with 2.5 mol% Ta 2 O 5 and 393 mmol of simple substance B, using acetone as solvent, Si 3 N 4 ball as ball milling medium, mixing on roller mill for 24 hours, rotary evaporation and drying To obtain a HfO 2 -Ta 2 O 5 -B mixed powder; wherein the content x of the solid solution TaB 2 is 5 mol%;
2.再将HfO 2-Ta 2O 5-B混合粉体置于石墨坩埚内，在石墨炉炉中，在气压低于200Pa下，加热至1000℃并保温2小时，得到Hf 0.95Ta 0.05B 2-B 2O 3粉体； 2. The HfO 2 -Ta 2 O 5 -B mixed powder is placed in a graphite crucible. In a graphite furnace, the pressure is lower than 200 Pa, heated to 1000 ° C. and held for 2 hours to obtain Hf 0.95 Ta 0.05 B. 2 -B 2 O 3 powder;
3.将得到的Hf 0.95Ta 0.05B 2-B 2O 3粉体在气压低于200Pa的条件下，继续加热至1500℃并保温1小时，即得到超细Hf 0.95Ta 0.05B 2粉体。 3. The obtained Hf 0.95 Ta 0.05 B 2 -B 2 O 3 powder was heated to 1500 ° C. and maintained for 1 hour under the condition that the air pressure was lower than 200 Pa to obtain ultra-fine Hf 0.95 Ta 0.05 B 2 powder.
图1和图2分别表示所制得的Hf 0.95Ta 0.05B 2粉体的SEM和TEM照片，由图1和图2可见，粉体颗粒尺寸均匀，且平均粒径为50nm，氧含量为0.1wt％。 Figures 1 and 2 show the SEM and TEM pictures of the prepared Hf 0.95 Ta 0.05 B 2 powder, respectively. As can be seen from Figures 1 and 2, the powder particle size is uniform, the average particle size is 50 nm, and the oxygen content is 0.1. wt%.
实施例2Example 2
本实施例与实施例1的不同之处在于：所述第二步高温保温为1800℃保温2小时。This embodiment is different from Embodiment 1 in that the second step of high-temperature insulation is 1800 ° C for 2 hours.
图3为本实施例所制得的Hf 0.95Ta 0.05B 2粉体的SEM照片，从图3可知，第二步升温到1800℃粉体并不会明显长大，说明固溶TaB 2后的过渡金属硼化铪粉体可抑制硼化铪表面扩散现象，从而不出现硼化铪粉体在高温下迅速长大，增强其高温稳定性。经检测分析得知：本实施例制得的Hf 0.95Ta 0.05B 2粉体的平均粒径为60nm，氧含量为0.02wt％。 Example 3 is a SEM photograph of the obtained Hf 0.95 Ta 0.05 B 2 powder embodiment, seen from FIG. 3, the second step and the powder was heated to 1800 ℃ not grow significantly after the solution described TaB 2 The transition metal samarium boride powder can suppress the surface diffusion phenomenon of samarium boride, so that the samarium boride powder does not grow up rapidly at high temperature and enhance its high temperature stability. It is known through inspection and analysis that the average particle diameter of the Hf 0.95 Ta 0.05 B 2 powder prepared in this embodiment is 60 nm, and the oxygen content is 0.02 wt%.
实施例3Example 3
本实施例与实施例1的不同之处在于：所述第二步高温保温为2200℃保温1小时。The difference between this embodiment and Embodiment 1 is that the second step of high-temperature heat preservation is 2200 ° C for 1 hour.
经检测分析得知：本实施例制得的Hf 0.95Ta 0.05B 2粉体的平均粒径为80nm，氧含量为0.01wt％。 It is known through inspection and analysis that the average particle diameter of the Hf 0.95 Ta 0.05 B 2 powder prepared in this embodiment is 80 nm, and the oxygen content is 0.01 wt%.
实施例4Example 4
本实施例与实施例1的不同之处在于：所述HfO 2、Ta 2O 5和硼粉的粒径分布为0.02μm、0.03μm和0.02μm；所述第一步保温为加热至950℃并保温1小时。经检测分析得知：本实施例制得的Hf 0.95Ta 0.05B 2粉体的平均粒径为30nm，氧含量为0.15wt％。 This embodiment is different from Example 1 in that the particle size distribution of the HfO 2 , Ta 2 O 5 and boron powder is 0.02 μm, 0.03 μm, and 0.02 μm; the first step is to heat to 950 ° C. And incubate for 1 hour. It is known through inspection and analysis that the average particle diameter of the Hf 0.95 Ta 0.05 B 2 powder prepared in this embodiment is 30 nm and the oxygen content is 0.15 wt%.
实施例5Example 5
本实施例与实施例1的不同之处在于：所述固溶的TaB 2的含量x为0.5mol％。 This embodiment is different from Example 1 in that the content x of the solid solution TaB 2 is 0.5 mol%.
经检测分析得知：本实施例制得的Zr 0.995Ta 0.005B 2粉体的平均粒径为80nm，氧含量为0.10wt％。 It is known through inspection and analysis that the average particle diameter of the Zr 0.995 Ta 0.005 B 2 powder prepared in this embodiment is 80 nm, and the oxygen content is 0.10 wt%.
实施例6Example 6
本实施例与实施例1的不同之处在于：所述原料中HfO 2换成ZrO 2。 This embodiment is different from Example 1 in that HfO 2 in the raw material is replaced with ZrO 2 .
经检测分析得知：本实施例制得的Zr 0.95Ta 0.05B 2粉体的平均粒径为70nm，氧含量为0.05wt％。 It is learned through analysis that the average particle diameter of the Zr 0.95 Ta 0.05 B 2 powder obtained in this embodiment is 70 nm and the oxygen content is 0.05 wt%.
实施例7Example 7
本实施例与实施例1的不同之处在于：所述固溶的TaB 2的含量x为15mol％，所述第一步保温为加热至1200℃并保温1小时。 The difference between this embodiment and Example 1 is that the content x of the solid solution TaB 2 is 15 mol%, and the first step of heat preservation is heating to 1200 ° C. and holding for 1 hour.
经检测分析得知：本实施例制得的Hf 0.85Ta 0.15B 2粉体的平均粒径为60nm，氧含量为0.05wt％。 It is known through inspection and analysis that the average particle diameter of the Hf 0.85 Ta 0.15 B 2 powder prepared in this embodiment is 60 nm, and the oxygen content is 0.05% by weight.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合和简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above embodiment. Any other changes, modifications, substitutions, combinations, and combinations without departing from the spirit and principle of the present invention Simplified, all should be equivalent replacement methods, and all are included in the protection scope of the present invention.

Claims (10)

  1. 一种超细过渡金属硼化物粉体，其特征在于，所述超细过渡金属硼化物粉体是将MO 2，Ta 2O 5和B加入溶剂后进行球磨混合，干燥后得到MO 2-Ta 2O 5-B混合粉体，再将MO 2-Ta 2O 5-B混合粉体在气压低于200Pa或惰性气氛下进行第一步保温，得到M 1-xTa xB 2-B 2O 3粉体，将M 1-xTa xB 2-B 2O 3粉体在气压低于200Pa或惰性气氛下继续升温，进行第二步保温，制得M 1-xTa xB 2粉体，其中，M＝Zr或Hf，x为0.005～0.2。 An ultra-fine transition metal boride powder, characterized in that the ultra-fine transition metal boride powder is obtained by adding MO 2 , Ta 2 O 5 and B to a solvent, and performing ball milling and mixing to obtain MO 2 -Ta after drying. 2 O 5 -B mixed powder, and then MO 2 -Ta 2 O 5 -B mixed powder is subjected to the first step of heat preservation under an air pressure of less than 200 Pa or an inert atmosphere to obtain M 1-x Ta x B 2 -B 2 O 1 powder, the M 1-x Ta x B 2 -B 2 O 3 powder is further heated under the pressure of less than 200 Pa or in an inert atmosphere, and the second step of heat preservation is performed to obtain M 1-x Ta x B 2 powder Body, wherein M = Zr or Hf, and x is 0.005 to 0.2.
  2. 根据权利要求1所述的超细M 1-xTa xB 2粉体，其特征在于，所述M 1-xTa xB 2粉体的粒径为10nm～1μm，其氧含量为0.1～2wt％。 The ultra-fine M 1-x Ta x B 2 powder according to claim 1, wherein the M 1-x Ta x B 2 powder has a particle diameter of 10 nm to 1 μm and an oxygen content of 0.1 to 2wt%.
  3. 根据权利要求1所述的超细过渡金属硼化物粉体，其特征在于，所述MO 2和B的摩尔比为1∶(2.5～5)，Ta 2O 5和B的摩尔比为1∶(7.5～10)。 The ultra-fine transition metal boride powder according to claim 1, wherein the molar ratio of MO 2 and B is 1: (2.5-5), and the molar ratio of Ta 2 O 5 and B is 1: (7.5 to 10).
  4. 根据权利要求1所述的超细过渡金属硼化物粉体，其特征在于，所述第一步保温的温度为800～1200℃，所述第二步保温的温度为1300～2200℃。The ultra-fine transition metal boride powder according to claim 1, wherein the temperature for the first step of holding temperature is 800 to 1200 ° C, and the temperature for the second step of holding temperature is 1300 to 2200 ° C.
  5. 根据权利要求1所述的超细过渡金属硼化物粉体，其特征在于，所述的溶剂为丙酮或乙醇，所述惰性气氛为氩气、氦气、氖气。The ultra-fine transition metal boride powder according to claim 1, wherein the solvent is acetone or ethanol, and the inert atmosphere is argon, helium, or neon.
  6. 一种根据权利要求1-5任一项所述的超细过渡金属硼化物粉体的制备方法，其特征在于，包括如下具体步骤：A method for preparing an ultra-fine transition metal boride powder according to any one of claims 1-5, comprising the following specific steps:
    S1.将Ta 2O 5粉体和MO 2粉体混合得到MO 2-Ta 2O 5混合粉体，再加入B粉再加入溶剂后进行球磨，干燥后得到MO 2-Ta 2O 5-B混合粉体； S1. Mixing Ta 2 O 5 powder and MO 2 powder to obtain MO 2 -Ta 2 O 5 mixed powder, adding powder B, adding solvent and performing ball milling, and drying to obtain MO 2 -Ta 2 O 5 -B Mixed powder
    S2.再将MO 2-Ta 2O 5-B混合粉体置于石墨坩埚内，在气压低于200Pa或惰性气氛下进行第一步保温，得到M 1-xTa xB 2-B 2O 3粉体； S2. The MO 2 -Ta 2 O 5 -B mixed powder is placed in a graphite crucible, and the first step of heat preservation is performed under the pressure of less than 200 Pa or in an inert atmosphere to obtain M 1-x Ta x B 2 -B 2 O 3 powder;
    S3.将M 1-xTa xB 2-B 2O 3粉体在气压低于200Pa或惰性气氛下继续升温，进行第二步保温，得到M 1-xTa xB 2粉体。 S3. The M 1-x Ta x B 2 -B 2 O 3 powder is further heated under the pressure of less than 200 Pa or in an inert atmosphere, and the second step of heat preservation is performed to obtain M 1-x Ta x B 2 powder.
  7. 根据权利要求6所述的超细过渡金属硼化物粉体的制备方法，其特征在于，步骤S1中所述MO 2粉、Ta 2O 5粉和B粉的粒径均为0.01～5μm。 The method for preparing ultra-fine transition metal boride powder according to claim 6, wherein the particle diameters of the MO 2 powder, Ta 2 O 5 powder, and B powder in step S1 are all 0.01 to 5 μm.
  8. 根据权利要求6所述的超细过渡金属硼化物粉体的制备方法，其特征在于，步骤S1中所述MO 2粉、Ta 2O 5粉和B粉的纯度均为90～100％。 The method for preparing ultra-fine transition metal boride powder according to claim 6, wherein the purity of the MO 2 powder, the Ta 2 O 5 powder, and the B powder in step S1 are all 90 to 100%.
  9. 根据权利要求6所述的超细过渡金属硼化物粉体的制备方法，其特征在于，步骤S1中所述第一步保温的时间为0.1～10h，第二步保温的时间为0.1～2h。The method for preparing ultra-fine transition metal boride powder according to claim 6, characterized in that, in the step S1, the holding time in the first step is 0.1 to 10 hours, and the holding time in the second step is 0.1 to 2 hours.
  10. 权利要求1-5任一项所述的超细过渡金属硼化物粉体在超高温涂层领域中的应用。The application of the ultra-fine transition metal boride powder according to any one of claims 1 to 5 in the field of ultra-high temperature coatings.
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