WO2019233076A1 - 一种铼掺杂的四硼化钨材料的制备方法 - Google Patents

一种铼掺杂的四硼化钨材料的制备方法 Download PDF

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WO2019233076A1
WO2019233076A1 PCT/CN2018/121025 CN2018121025W WO2019233076A1 WO 2019233076 A1 WO2019233076 A1 WO 2019233076A1 CN 2018121025 W CN2018121025 W CN 2018121025W WO 2019233076 A1 WO2019233076 A1 WO 2019233076A1
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powder
ball milling
sintering
energy ball
ball mill
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PCT/CN2018/121025
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English (en)
French (fr)
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龙莹
郑鑫
车金涛
黄路江
林华泰
王成勇
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • 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
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases

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  • the invention relates to the technical field of materials, and in particular, to a method for preparing an erbium-doped tungsten tetraboride material.
  • Superhard materials are widely used in cutting tools, wear-resistant coatings and abrasive materials due to their high hardness, good abrasion resistance, surface stability and other excellent characteristics. They play an irreplaceable role in industrial production and aerospace Role. Transition metal borides have high melting points, high hardness, and good chemical stability. Potential new superhard materials may exist. Among them, WB 4 , OsB 2 and ReB 2 are very successful examples, they are potential candidates to replace expensive superhard materials (such as diamond, cubic boron nitride, etc.) in a wide range of applications in the future.
  • tungsten tetraboride has a series of excellent properties such as excellent chemical inertness, friction resistance, wear resistance, and good neutron absorption. It can be used in tools, cutting tools and new shielding materials. Has high scientific research value and good application prospects. However, the hardness and thermal stability of the superhard materials of the prior art are not ideal.
  • the technical problem to be solved by the present invention is to provide a method for preparing erbium-doped tungsten tetraboride material.
  • the erbium-doped tungsten tetraboride material prepared by the method has high hardness and thermal stability. .
  • the invention provides a method for preparing erbium-doped tungsten tetraboride material, including:
  • the powder after high-energy ball milling is sintered to obtain an erbium-doped tungsten tetraboride material.
  • the molar ratio of the tungsten powder, boron powder, and hafnium powder is 1: x: 5, where 0 ⁇ x ⁇ 0.5.
  • the molar ratio of the tungsten powder, boron powder, and hafnium powder is 0.9: 0.1: 5.
  • the protective atmosphere is argon.
  • the apparatus for the high-energy ball milling is selected from the group consisting of a high-energy ball mill, a vibration ball mill, a planetary ball mill, a field-assisted ball mill, or an ion-assisted high-energy ball mill; the ball milling time is 1 to 40 hours.
  • the ball-to-material ratio of the high-energy ball mill is 3: 1 to 6: 1.
  • the ball-to-material ratio of the high-energy ball mill is 4: 1 to 5: 1.
  • the diameter of the grinding ball used in the high-energy ball milling is 11-12 mm.
  • the sintering method includes hot-pressing sintering, pressureless sintering, discharge plasma sintering, microwave sintering, or field-assisted sintering.
  • the sintering temperature is 1200 ° C to 1600 ° C, and the holding time is 1h to 2h.
  • the present invention provides a method for preparing erbium-doped tungsten tetraboride material, which includes: performing high-energy ball milling of tungsten powder, boron powder, and rhenium powder under a protective atmosphere; The powder was sintered to obtain an erbium-doped tungsten tetraboride material.
  • the invention first adopts a mechanochemical method to perform high-energy ball milling on powders mixed in a certain proportion at room temperature, and then densifies and sinters the ball-milled powder to obtain a erbium-doped tungsten tetraboride bulk material with a certain hardness.
  • the material prepared by the preparation method provided by the invention has good hardness and thermal stability, meanwhile, the equipment used is simple, the operability is strong, and the cost is low.
  • FIG. 1 is an XRD pattern of the powders obtained in Examples 1 to 3 of the present invention.
  • Example 5 is an EDS photograph of a sample of the powder prepared in Example 3 of the present invention after heat treatment at 1400 ° C for 2 hours;
  • Example 6 is an XRD diagram of a sample of the powder prepared in Example 1 of the present invention after heat treatment at 1200 ° C, 1250 ° C, and 1300 ° C for 2 hours;
  • FIG. 7 is an XRD pattern of a sample of the powder prepared in Example 3 of the present invention after heat treatment at 1200 ° C, 1300 ° C, and 1400 ° C for 2 hours.
  • the invention provides a method for preparing erbium-doped tungsten tetraboride material.
  • Those skilled in the art can learn from the content of this article and appropriately improve the process parameters. It should be particularly pointed out that all similar replacements and modifications are obvious to those skilled in the art, and they all belong to the protection scope of the present invention.
  • the method and application of the present invention have been described through the preferred embodiments. Obviously, relevant persons can make modifications or appropriate changes and combinations to the methods and applications herein without departing from the content, spirit, and scope of the present invention to implement and apply the present invention. Invention technology.
  • the invention provides a method for preparing erbium-doped tungsten tetraboride material, including:
  • the powder after high-energy ball milling is sintered to obtain an erbium-doped tungsten tetraboride material.
  • tungsten powder, boron powder, and hafnium powder are subjected to high-energy ball milling under a protective atmosphere.
  • the molar ratio of the tungsten powder, boron powder, and hafnium powder according to the present invention is preferably 1: x: 5 (0 ⁇ x ⁇ 0.5); more preferably, the molar ratio of the tungsten powder, boron powder, and hafnium powder is 0.9: 0.1: 5.
  • the present invention must satisfy the above-mentioned ratio range. According to the boride, excessive boron is added to the raw material powder, which easily leads to the existence of residual boron in the product and affects the hardness and density of the material.
  • the sources of the tungsten powder, boron powder, and hafnium powder are not limited, and they may be commercially available.
  • the protective atmosphere in the present invention is preferably argon; it may also be a vacuum condition.
  • the apparatus for high-energy ball milling is preferably selected from a high-energy ball mill, a vibrating ball mill, a planetary ball mill, a field-assisted ball mill, or an ion-assisted high-energy ball mill.
  • powder synthesis is preferably carried out by using a high-energy ball mill model 8000M of the United States SPEX Company.
  • Nano-scale WB2 powder with high surface energy is synthesized by high-energy ball milling at room temperature.
  • the ball-to-material ratio of the high-energy ball milling is preferably 3: 1 to 6: 1; more preferably 4: 1 to 5 : 1; most preferably 4: 1.
  • the number of tungsten carbide grinding balls used in the present invention is 4-6.
  • the diameter of the grinding balls used in the high-energy ball milling is preferably 11-12mm; more preferably 11.2mm.
  • the invention uses a high-speed high-energy ball mill to ball mill the powder, so that the hardness and thermal stability are better and the effect is better.
  • WB2 powder synthesized by high-energy ball milling at room temperature has high surface energy and powder particles It is thinner and can reach nanometer level.
  • the tungsten carbide ball mill tank containing the powder and the grinding ball was fixed on a high-energy ball mill.
  • the total ball milling time of the present invention is preferably from 1 to 40 hours; more preferably from 10 to 40 hours, and each ball mill is stopped for 1 hour and 20 minutes to prevent the engine from overheating.
  • the powder after high energy ball milling is preferably sintered in a glove box filled with argon gas to obtain an erbium-doped tungsten tetraboride material.
  • the ball-milled powder was pressed into a cylindrical thin sheet with a mold, and cold-isostatic pre-pressed molding at 250 MPa was used. It is then sintered into a block in a tube furnace under the protection of a vacuum or argon atmosphere.
  • the sintering method includes hot-pressing sintering, pressureless sintering, discharge plasma sintering, microwave sintering, or field-assisted sintering.
  • the sintering temperature is preferably 1200 ° C to 1600 ° C, and the holding time is 1h to 2h.
  • the invention By controlling the temperature and holding time in the sintering process, the invention obtains a relatively pure block material.
  • the WB 2 powder synthesized by high-energy ball milling is subjected to densification and sintering, and its main component is W 1-x Re x B 4 , which may contain a small amount of ReB 2 and WB 2 , and residual amorphous B.
  • the invention obtains a dense bulk material with W 1-x Re x B 4 as the main phase.
  • the invention adopts a mechanochemical method, and by controlling raw material components and chemical proportions, and process parameters, a mixed powder having a specific ratio, a high surface energy, and a fine to nanometer level is synthesized at room temperature.
  • the powder is densified.
  • erbium-doped tungsten tetraboride bulk materials with high density, certain composition and microstructure, and high hardness are prepared.
  • the invention further improves the hardness, strength and thermal stability, and has a series of excellent properties such as excellent chemical inertness, friction and wear resistance, and good neutron absorption effect, so as to meet the requirements of modern industries for Demand for hard materials.
  • the present invention can obtain a erbium-doped tungsten tetraboride bulk material without a sintering aid.
  • the invention provides a method for preparing erbium-doped tungsten tetraboride material, comprising: performing high-energy ball milling of tungsten powder, boron powder, and rhenium powder under a protective atmosphere; sintering the powder after high-energy ball milling to obtain erbium-doped Miscellaneous tungsten tetraboride material.
  • the invention first adopts a mechanochemical method to perform high-energy ball milling on powders mixed in a certain proportion at room temperature, and then densifies and sinters the ball-milled powder to obtain a erbium-doped tungsten tetraboride bulk material with a certain hardness.
  • the material prepared by the preparation method provided by the invention has good hardness and thermal stability, meanwhile, the equipment used is simple, the operability is strong, and the cost is low.
  • FIG. 1 is an XRD pattern of the powders prepared in Examples 1 to 3 of the present invention; it can be seen from FIG. 1 that when Re is not added, the ball is milled for 40 hours, and W is basically converted into WB 2 , and there is only one product of WB 2 ; when Re is added at 5% and 10% respectively, the same ball milling for 40h, only a small amount of W is converted to WB 2 , a large amount of W still exists in the form of a simple substance.
  • the powder after ball milling has a high surface energy. Since the amount of Re is too small, no single substance or compound of Re is shown in XRD.
  • Example 2 About 2 to 4 g of the powder prepared in Example 2 was taken, pressed into a thin sheet with a ⁇ 12 mm mold, and cold-isostatically pressed at 250 MPa for pre-forming. Then, under the protection of an argon gas atmosphere, sintered into a block in a tube furnace at 1200 ° C for two hours.
  • Example 2 About 2 to 4 g of the powder prepared in Example 2 was taken, pressed into a thin sheet with a ⁇ 12 mm mold, and cold-isostatically pressed at 250 MPa for pre-forming. Then, under the protection of an argon gas atmosphere, sintered into a block in a tube furnace at 1300 ° C for two hours.
  • Example 2 About 2 to 4 g of the powder prepared in Example 2 was taken, pressed into a thin sheet with a ⁇ 12 mm mold, and cold-isostatically pressed at 250 MPa for pre-forming. Then, under the protection of an argon atmosphere, in a tube furnace, it is sintered into a block by holding at 1400 ° C for two hours.
  • FIG. 2 is an XRD pattern of the samples prepared in Examples 4 to 6 of the present invention. It can be seen from Figure 2 that except for a very small amount of ReB 2 at 1200 ° C, the remaining products are all W 1-x Re x B 4 , but at 1300 ° C and 1400 ° C, except for the above two products, there is WB 2 build. Compared with 1300 °C, the content of WB 2 in the product increased slightly at 1400 °C.
  • the PDF card corresponding to WB 2 (P6 / mmm) generated by ball milling is 01-089-3928
  • the PDF card corresponding to WB 2 (P6 3 / mmc) generated by heat treatment is 01-073 -1244
  • the WB2 corresponding to the two PDF cards have a hexagonal structure, the cell sizes of the two are different.
  • Example 2 About 2-4 g of the powder obtained in Example 1 was pressed into a thin sheet with a ⁇ 12 mm mold, and cold isostatic pressing was used for pre-forming at 250 MPa. Then, under the protection of an argon atmosphere, in a tube furnace, it is sintered into a block by holding at 1400 ° C for two hours.
  • Example 2 About 2 to 4 g of the powder obtained in Example 2 was pressed into a thin sheet with a ⁇ 12 mm mold, and cold isostatic pressing was used for pre-forming at 250 MPa. Then, under the protection of an argon atmosphere, in a tube furnace, it is sintered into a block by holding at 1400 ° C for two hours.
  • Example 3 About 2-4 g of the powder obtained in Example 3 was pressed into a sheet with a ⁇ 12 mm mold, and cold isostatic pressing was used for pre-pressing at 250 MPa. Then, under the protection of an argon atmosphere, in a tube furnace, it is sintered into a block by holding at 1400 ° C for two hours.
  • FIG. 3 is an XRD pattern of the samples prepared in Examples 7 to 9 of the present invention.
  • the product under the conditions of heat treatment temperature of 1400 ° C and holding for two hours, (1) when Re is not added, the product is mainly WB 2 and only a small amount of WB 4 is formed; (2) when 5% is added At Re and 10% Re, the products are mainly W 1-x Re x B 4 , while WB 2 is only present in a very small amount, and ReB 2 is also formed.
  • FIG. 5 is an EDS photograph of a sample of the powder prepared in Example 3 of the present invention after heat treatment at 1400 ° C for 2 hours.
  • Example 2 About 2-4 g of the powder obtained in Example 1 was pressed into a thin sheet with a ⁇ 12 mm mold, and cold isostatic pressing was used for pre-forming at 250 MPa. Then, under the protection of an argon gas atmosphere, sintered into a block in a tube furnace at 1200 ° C for two hours.
  • Example 2 About 2-4 g of the powder obtained in Example 1 was pressed into a thin sheet with a ⁇ 12 mm mold, and cold isostatic pressing was used for pre-forming at 250 MPa. Then in a tube furnace under the protection of an argon atmosphere, it is sintered into a block by holding at 1250 ° C for two hours.
  • Example 2 About 2-4 g of the powder obtained in Example 1 was pressed into a thin sheet with a ⁇ 12 mm mold, and cold isostatic pressing was used for pre-forming at 250 MPa. Then, under the protection of an argon gas atmosphere, sintered into a block in a tube furnace at 1300 ° C for two hours.
  • FIG. 6 is an XRD pattern of the powder prepared in Example 1 of the present invention after heat treatment at 1200 ° C., 1250 ° C., and 1300 ° C. for 2 hours.
  • the figure shows that there is only WB 4 in the sample at 1200 ° C, and a small number of peaks of WB 2 begin to appear at 1250 ° C.
  • WB 4 has completely disappeared and is replaced by WB 2 , that is, under the current experimental conditions.
  • the decomposition temperature of WB4 is about 1250 ° C.
  • Example 3 About 2-4 g of the powder obtained in Example 3 was pressed into a sheet with a ⁇ 12 mm mold, and cold isostatic pressing was used for pre-pressing at 250 MPa. Then, under the protection of an argon gas atmosphere, sintered into a block in a tube furnace at 1200 ° C for two hours.
  • Example 3 About 2 to 4 g of the powder obtained in Example 3 was pressed into a thin sheet with a ⁇ 12 mm mold, and cold isostatic pressing was used for pre-forming at 250 MPa. Then, under the protection of an argon gas atmosphere, sintered into a block in a tube furnace at 1300 ° C for two hours.
  • Example 15 is a repeat test of Example 9.
  • FIG. 7 is an XRD pattern of the powder prepared in Example 3 of the present invention after heat treatment at 1200 ° C., 1300 ° C., and 1400 ° C. for 2 hours.
  • the figure shows that the main phases are W 1-x Re x B 4 at 1200 ° C, 1300 ° C, and 1400 ° C, and there are a small number of WB 2 peaks at 1300 ° C and 1400 ° C. Comparing with Figure 6, it can be seen that in this experiment, Adding Re can improve the thermal stability of WB 4 .

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Abstract

一种铼掺杂的四硼化钨材料的制备方法，包括：将钨粉、硼粉和铼粉在保护气氛下，进行高能球磨；将高能球磨后的粉末烧结，得到铼掺杂的四硼化钨材料。首先采用机械化学法在室温下对按一定比例混合的粉末进行高能球磨，再对球磨后的粉末进行致密化烧结，获得具有一定硬度的铼掺杂四硼化钨块体材料。

Description

一种铼掺杂的四硼化钨材料的制备方法 技术领域
本发明涉及材料技术领域，尤其是涉及一种铼掺杂的四硼化钨材料的制备方法。
背景技术
超硬材料因其具有高的硬度、良好的耐磨性、表面稳定性等优良特性，被广泛应用于切削刀具、耐磨涂层和研磨材料等，在工业生产和航空航天中发挥着不可替代的作用。过渡金属硼化物具有高熔点、高硬度和良好的化学稳定性，其中可能存在潜在的新型超硬材料。其中，WB 4、OsB 2和ReB 2都是很成功的例子，它们是未来在广泛的应用中替换昂贵的超硬材料(如金刚石、立方氮化硼等)的潜在候选者。
四硼化钨除了具有高硬度的优点外，还有优良的化学惰性、耐摩擦、耐磨损和良好的中子吸收效果等一系列优良性能，可以应用于刀具、切削工具和新型屏蔽材料，有很高的科研价值和良好的应用前景。但现有技术的超硬材料的硬度和热稳定性还不理想。
发明内容
有鉴于此，本发明要解决的技术问题在于提供一种铼掺杂的四硼化钨材料的制备方法，通过该方法制备得到的铼掺杂的四硼化钨材料的硬度和热稳定性高。
本发明提供了一种铼掺杂的四硼化钨材料的制备方法，包括：
将钨粉、硼粉和铼粉在保护气氛下，进行高能球磨；
将高能球磨后的粉末烧结，得到铼掺杂的四硼化钨材料。
优选的，所述钨粉、硼粉和铼粉的摩尔比为1∶x∶5，其中0＜x≤0.5。
优选的，所述钨粉、硼粉和铼粉的摩尔比为0.9∶0.1∶5。
优选的，所述保护气氛为氩气。
优选的，所述高能球磨的仪器选自高能球磨机、振动球磨机、行星式球磨机、场辅助球磨机或离子体辅助高能球磨机；所述球磨的时间为1～40h。
优选的，所述高能球磨的球料比为3∶1～6∶1。
优选的，所述高能球磨的球料比为4∶1～5∶1。
优选的，所述高能球磨使用的磨球的直径为11～12mm。
优选的，所述烧结方法包括热压烧结、无压烧结，放电等离子烧结、微波烧结或场辅助烧结。
优选的，所述烧结温度为1200℃～1600℃，保温时间为1h～2h。
与现有技术相比，本发明提供了一种铼掺杂的四硼化钨材料的制备方法，包括：将钨粉、硼粉和铼粉在保护气氛下，进行高能球磨；将高能球磨后的粉末烧结，得到铼掺杂的四硼化钨材料。本发明首先采用机械化学法在室温下对按一定比例混合的粉末进行高能球磨，再对球磨后的粉末进行致密化烧结，获得具有一定硬度的铼掺杂四硼化钨块体材料。本发明提出制备方法制备得到的材料硬度和热稳定性好，同时采用的设备简单，可操作性强，成本低。
附图说明
图1为本发明实施例1～3制得的粉末的XRD图；
图2为本发明实施例4～6制备得到的样品的XRD图；
图3本发明实施例7～9制备得到的样品的XRD图；
图4为本发明实施例7～9制备得到的样品的SEM照片；
图5本发明实施例3制备的的粉体在1400℃热处理保温2h后的样品的EDS照片；
图6为本发明实施例1制备的的粉体在1200℃、1250℃和1300℃热处理保温2h后的样品的XRD图；
图7为本发明实施例3制备的的粉体在1200℃、1300℃和1400℃热处理保温2h后的样品的XRD图。
具体实施方式
本发明提供了一种铼掺杂的四硼化钨材料的制备方法，本领域技术人员可以借鉴本文内容，适当改进工艺参数实现。特别需要指出的是，所有类似的替换和改动对本领域技术人员来说是显而易见的，它们都属于本发明保护的范围。本发明的方法及应用已经通过较佳实施例进行了描述，相关人员明显能在不脱离本发明内容、精神和范围内对本文的方法和应用进行改动或适当变更与组合，来实现和应用本发明技术。
本发明提供了一种铼掺杂的四硼化钨材料的制备方法，包括：
将钨粉、硼粉和铼粉在保护气氛下，进行高能球磨；
将高能球磨后的粉末烧结，得到铼掺杂的四硼化钨材料。
本发明首先将钨粉、硼粉和铼粉在保护气氛下，进行高能球磨。
本发明所述钨粉、硼粉和铼粉的摩尔比优选为1∶x∶5(0＜x≤0.5)；更优选的，所述钨粉、硼粉和铼粉的摩尔比为0.9∶0.1∶5。
本发明必须满足上述比例范围，根据所述的硼化物，原料粉末中加入过量的硼，容易导致产物中残余硼的存在从而影响材料的硬度和致密度。
本发明对于所述钨粉、硼粉和铼粉的来源不进行限定，市售的即可。
本发明所述保护气氛优选为氩气；还可以为真空的条件。
本发明所述高能球磨的仪器优选选自高能球磨机、振动球磨机、行星式球磨机、场辅助球磨机或离子体辅助高能球磨机。本发明优选采用美国SPEX公司型号为8000M的高能球磨机进行粉末合成。
在室温下利用高能球磨合成具有高的表面能的纳米级WB2粉末，在进行高能球磨时，所述高能球磨的球料比优选为3∶1～6∶1；更优选为4∶1～5∶1；最优选为4∶1。
本发明所用的碳化钨磨球为4～6个，所述高能球磨使用的磨球的直径优选为11～12mm；更优选为11.2mm。
本发明使用高转速的高能球磨对于所述粉体进行球磨，使得硬度和热稳定性更好，效果更好。
随着球磨时间的增加，WB2的含量逐渐增多，球磨后的混合粉末中可能含有没有反应完全的W和B粉；在室温下通过高能球磨合成的WB2粉末具有很高的表面能，而且粉末颗粒更加细，可达到纳米级。
将装有粉体和磨球的碳化钨球磨罐固定在高能球磨机上。本发明的球磨总时间优选为1～40h；更优选为10～40h，每球磨1h停机20min，以防止发动机过热。
本发明优选在充满氩气的手套箱中，将高能球磨后的粉末烧结，得到铼掺杂的四硼化钨材料。
将球磨后的粉末用模具压成圆柱形薄片，采用250MPa的冷等静压预压成型。然后在真空或者氩气气氛保护下，管式炉中，烧结成块体。
按照本发明，所述烧结方法包括热压烧结、无压烧结，放电等离子烧结、微波烧结或场辅助烧结。所述烧结温度优选为1200℃～1600℃，保温时间为1h～2h。
本发明通过控制烧结过程中温度和保温时间，获得物相较纯的的块体材料。
本发明采用高能球磨合成的WB 2粉末，经过致密化烧结以后，其主要成分为W 1-xRe xB 4，可能含有少量的ReB 2和WB 2，以及残余的非晶B。
本发明得到的是以W 1-xRe xB 4为主相的、致密的块体材料。
本发明采用机械化学法，通过控制原料成分和化学配比，以及工艺参数，在室温下合成具有特定比例、高表面能、细到纳米级的混合粉末；本发明采用烧结工艺对机械化学法合成的粉末进行致密化，通过调节和优化烧结工艺参数，制备具有高致密度、一定成分和微观结构、以及高硬度的铼掺杂四硼化钨块体材料。本发明在现有技术基础上，进一步提高硬度、强度和热稳定性，并具备优良的化学惰性、耐摩擦耐磨损和良好的中子吸收效果等一系列优良性能，以满足现代化工业对超硬材料的需求。本发明无需烧结助剂，即可得到铼掺杂四硼化钨块体材料。
本发明提供了一种铼掺杂的四硼化钨材料的制备方法，包括：将钨粉、硼粉和铼粉在保护气氛下，进行高能球磨；将高能球磨后的粉末烧结，得到铼掺杂的四硼化钨材料。本发明首先采用机械化学法在室温下对按一定比例混合的粉末进行高能球磨，再对球磨后的粉末进行致密化烧结，获得具有一定硬度的铼掺杂四硼化钨块体材料。本发明提出制备方法制备得到的材料硬度和热稳定性好，同时采用的设备简单，可操作性强，成本低。
为了进一步说明本发明，以下结合实施例对本发明提供的一种铼掺杂的四硼化钨材料的制备方法进行详细描述。
实施例1
(1)采用高能球磨机进行球磨，在充满氩气的手套箱中，将高纯的钨粉(W)与硼粉(B)按化学计量比1∶5混合配料，添加碳化钨磨球六个，尺寸为11.20mm，球与混合粉末的质量之比为4∶1。
(2)将装有粉体和磨球的碳化钨球磨罐固定在高能球磨机上。每球磨1h停机20min(防止发动机过热)。
(3)球磨时间为40h。
实施例2
(1)采用高能球磨机进行球磨，在充满氩气的手套箱中，将高纯的钨粉(W)、铼粉(Re)与硼粉(B)按化学计量比0.95∶0.05∶5混合配料，添加碳化钨磨球六个，尺寸为11.20mm，球与混合粉末的质量之比为4∶1。
(2)将装有粉体和磨球的碳化钨球磨罐固定在高能球磨机上。每球磨1h停机20min(防止发动机过热)。
(3)球磨时间为40h。
实施例3
(1)采用高能球磨机进行球磨，在充满氩气的手套箱中，将高纯的钨粉(W)、铼粉(Re)与硼粉(B)按化学计量比0.9∶0.1∶5混合配料，添加碳化钨磨球六个，尺寸为11.20mm，球与混合粉末的质量之比为4∶1。
(2)将装有粉体和磨球的碳化钨球磨罐固定在高能球磨机上。每球磨1h停机20min(防止发动机过热)。
(3)球磨时间为40h。
结果如图1所示，其中，图1为本发明实施例1～3制得的粉末的XRD图；从图1中可以看出，当未添加Re时，球磨40h，W基本全部转化为WB 2，并有且仅有WB 2这一种产物；当分别添加5％和10％的Re时，同样球磨40h，只有少量的W转化为WB 2，大量的W仍以单质的形式存在。但在球磨40h过程中，由于磨球和粉体、粉体和粉体，以及粉体和球磨罐之间的剧烈碰撞，使得球磨后的粉具有很高的表面能。由于Re的量太少，所以XRD中并未显示Re的单质或化合物。
实施例4
取实施例2制备得到的粉末约2～4g，用Φ12mm模具压成薄片，采用250MPa的冷等静压预压成型。然后氩气气氛保护下，管式炉中，在1200℃时保温两小时烧结成块体。
实施例5
取实施例2制备得到的粉末约2～4g，用Φ12mm模具压成薄片，采用250MPa的冷等静压预压成型。然后氩气气氛保护下，管式炉中，在1300℃时保温两小时烧结成块体。
实施例6
取实施例2制备得到的粉末约2～4g，用Φ12mm模具压成薄片，采用250MPa的冷等静压预压成型。然后氩气气氛保护下，管式炉中，在1400℃时保温两小时烧结成块体。
结果如图2所示，其中，图2为本发明实施例4～6制备得到的样品的XRD图。从图2中可以看出，1200℃时除极少量的ReB 2外，其余产物全部为W 1-xRe xB 4，但在1300℃和1400℃时除去以上两种产物外，还有WB 2生成。相较与1300℃，1400℃时产物中WB 2含量还略有提高。和球磨生成的WB 2对比可发现，球磨生成的WB 2(P6/mmm)对应的PDF卡片为01-089-3928，热处理生成的WB 2(P6 3/mmc)对应的PDF卡片为01-073-1244，虽然两张PDF卡片对应的WB2都是六方结构，但二者的晶胞尺寸不同，前者尺寸是a＝3.02、b＝3.02、c＝3.05；后者则是a＝2.9831、b＝2.9831、c＝13.8790。
由图可以看出，添加了Re后WB 4的热稳定性得以提高，同时也提高了WB 4的硬度。
实施例7
取实施例1得到的粉末约2-4g，用Φ12mm模具压成薄片，采用250MPa的冷等静压预压成型。然后氩气气氛保护下，管式炉中，在1400℃时保温两小时烧结成块体。
实施例8
取实施例2得到的粉末约2-4g，用Φ12mm模具压成薄片，采用250MPa的冷等静压预压成型。然后氩气气氛保护下，管式炉中，在1400℃时保温两小时烧结成块体。
实施例9
取实施例3得到的粉末约2-4g，用Φ12mm模具压成薄片，采用250MPa的冷等静压预压成型。然后氩气气氛保护下，管式炉中，在1400℃时保温两小时烧结成块体。
结果如图3所示，图3为本发明实施例7～9制备得到的样品的XRD图。从图3中可以看出，在热处理温度为1400℃并保温两小时的条件下，(1)未添加Re时，产物主要为WB 2，只有少量的WB 4生成；(2)当添加5％Re和10％Re时，产物主要为W 1-xRe xB 4，而WB 2只有极少量存在，同时还有ReB 2 生成。
图4为本发明实施例7～9制备得到的样品的SEM照片；具体为：W 1-xRe xB 5(x＝0、0.05、0.1)的粉体球磨40h后在1400℃热处理保温2h后的SEM照片，其中A是x＝0时的SEM图片、B是x＝0.05时的SEM图片、C是x＝0.1时的SEM图片。
图5本发明实施例3制备的的粉体在1400℃热处理保温2h后的样品的EDS照片。
实施例10
取实施例1得到的粉末约2-4g，用Φ12mm模具压成薄片，采用250MPa的冷等静压预压成型。然后氩气气氛保护下，管式炉中，在1200℃时保温两小时烧结成块体。
实施例11
取实施例1得到的粉末约2-4g，用Φ12mm模具压成薄片，采用250MPa的冷等静压预压成型。然后氩气气氛保护下，管式炉中，在1250℃时保温两小时烧结成块体。
实施例12
取实施例1得到的粉末约2-4g，用Φ12mm模具压成薄片，采用250MPa的冷等静压预压成型。然后氩气气氛保护下，管式炉中，在1300℃时保温两小时烧结成块体。
结果如图6所示，图6为本发明实施例1制备的的粉体在1200℃、1250℃和1300℃热处理保温2h后的样品的XRD图。图中显示在1200℃时样品中只有WB 4，在1250℃时开始出现少量的WB 2的峰，到1300℃时WB 4已经完全消失，取而代之的是WB 2，也就是说在当前实验条件下WB4的分解温度约为1250℃。
实施例13
取实施例3得到的粉末约2-4g，用Φ12mm模具压成薄片，采用250MPa的冷等静压预压成型。然后氩气气氛保护下，管式炉中，在1200℃时保温两小时烧结成块体。
实施例14
取实施例3得到的粉末约2-4g，用Φ12mm模具压成薄片，采用250MPa 的冷等静压预压成型。然后氩气气氛保护下，管式炉中，在1300℃时保温两小时烧结成块体。
实施例15
实施例15是实施例9的重复试验。
结果如图6所示，图7为本发明实施例3制备的的粉体在1200℃、1300℃和1400℃热处理保温2h后的样品的XRD图。图中显示，1200℃、1300℃和1400℃时主相都是W 1-xRe xB 4，在1300℃和1400℃时有少量的WB 2的峰，对比于图6可知，本实验中添加Re可以提高WB 4的热稳定性。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (10)

  1. 一种铼掺杂的四硼化钨材料的制备方法，包括：
    将钨粉、硼粉和铼粉在保护气氛下，进行高能球磨；
    将高能球磨后的粉末烧结，得到铼掺杂的四硼化钨材料。
  2. 根据权利要求1所述的制备方法，其特征在于，所述钨粉、硼粉和铼粉的摩尔比为1∶x∶5，其中0＜x≤0.5。
  3. 根据权利要求2所述的制备方法，其特征在于，所述钨粉、硼粉和铼粉的摩尔比为0.9∶0.1∶5。
  4. 根据权利要求1所述的制备方法，其特征在于，所述保护气氛为氩气。
  5. 根据权利要求1所述的制备方法，其特征在于，所述高能球磨的仪器选自高能球磨机、振动球磨机、行星式球磨机、场辅助球磨机或离子体辅助高能球磨机；所述球磨的时间为1～40h。
  6. 根据权利要求5所述的制备方法，其特征在于，所述高能球磨的球料比为3∶1～6∶1。
  7. 根据权利要求6所述的制备方法，其特征在于，所述高能球磨的球料比为4∶1～5∶1。
  8. 根据权利要求6所述的制备方法，其特征在于，所述高能球磨使用的磨球的直径为11～12mm。
  9. 根据权利要求1所述的制备方法，其特征在于，所述烧结方法包括热压烧结、无压烧结，放电等离子烧结、微波烧结或场辅助烧结。
  10. 根据权利要求9所述的制备方法，其特征在于，所述烧结温度为1200℃～1600℃，保温时间为1h～2h。
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