WO2020133585A1 - Hard transition metal boride material and preparation method therefor - Google Patents

Hard transition metal boride material and preparation method therefor Download PDF

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WO2020133585A1
WO2020133585A1 PCT/CN2019/071259 CN2019071259W WO2020133585A1 WO 2020133585 A1 WO2020133585 A1 WO 2020133585A1 CN 2019071259 W CN2019071259 W CN 2019071259W WO 2020133585 A1 WO2020133585 A1 WO 2020133585A1
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powder
transition metal
metal boride
sintering
hard material
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PCT/CN2019/071259
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Chinese (zh)
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龙莹
黄路江
车金涛
林华泰
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广东工业大学
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Definitions

  • the invention belongs to the field of transition metal materials, and particularly relates to a transition metal boride hard material and a preparation method thereof.
  • Hardness is an important indicator to measure the performance of materials, mainly expressing the ability of materials to resist elastic deformation and plastic deformation. Generally, we call the material with Vickers hardness greater than 40GPa super hard material. Superhard materials not only have high hardness and wear resistance, but also have high compression resistance, thermal conductivity and chemical stability, so they are very important in the fields of industrial production, medicine, geology, metallurgy, electronics and military defense. Status.
  • Superhard materials can be divided into two categories: traditional superhard materials and new superhard materials.
  • Traditional superhard materials mainly include diamond and cubic boron nitride.
  • Diamond mainly has problems such as poor thermal stability and chemical stability. When heated to 800 °C in air, it is easily oxidized. When processing iron-containing metal workpieces, carbon will Infiltration into the workpiece leads to wear and work hardening of the workpiece, making it unsuitable for processing ferrous workpieces; and cubic boron nitride currently has problems such as very expensive preparation costs.
  • the invention provides a transition metal boride hard material and a preparation method thereof, which solves the technical problems that the existing super hard material is expensive to prepare, the workpiece is easy to wear and the work is hardened.
  • the invention provides a method for preparing a transition metal boride hard material, which is characterized by comprising the following steps:
  • Step 1 Ball milling osmium powder, MT powder and boron powder by mechanochemical method to obtain mixed Os 1-x MT x B 2 powder, where x is 0.01-0.5, MT is rhenium element, tungsten element or iridium element;
  • Step 2 Add an appropriate amount of magnesium oxide to the Os 1-x MT x B 2 powder obtained in Step 1, and use a grinding bowl to fully grind the mixed powder of Os 1-x MT x B 2 after adding magnesium oxide until the mixture is uniform , And then sieved to obtain uniformly mixed MgO-Os 1-x MT x B 2 powder;
  • Step 3 Sinter the MgO-Os 1-x MT x B 2 powder obtained in Step 2 to obtain a transition metal boride hard material.
  • the mixture of the osmium powder and the MT powder in step 1 is osmium-MT powder, and the molar ratio of the original powder of the osmium-MT powder and the boron powder is 1: (2-5).
  • the molar ratio of the original powder of osmium-MT powder to the boron powder is 1: (2.25-2.5).
  • the molar ratio of the original powder of osmium powder, rhenium powder and boron powder is 0.9:0.1:(2.25-5), further preferably 0.9:0.1:(2.25-2.5);
  • the equipment used in the mechanochemical method is one or more of a high-energy ball mill, a vibration ball mill, a planetary ball mill, and a field assisted ball mill.
  • the field assisted ball mill includes a plasma assisted high energy ball mill.
  • the mass fraction of the magnesium oxide powder is 1wt.%-12wt.%.
  • step 2 after the step 2 and before the step 3, it further includes sufficient grinding and sieving.
  • the milling time is 20-30 min, and the diameter of the sieve is 100-200 mesh.
  • the sintering is pressureless sintering, hot press sintering or spark plasma sintering.
  • the sintering temperature is 1400°C-1800°C.
  • the sintering temperature is 1600°C-1750°C.
  • the temperature increase rate of the pressureless sintering is 3-15°C/min and the holding time is 1-2h; the temperature increase rate of the hot press sintering is 5-15°C/min and the sintering pressure is 20MPa-70MPa, heat preservation The pressure holding time is 1-2h; the temperature rise rate of the spark plasma sintering is 100-200°C/min, the sintering pressure is 20MPa-70MPa, and the heat preservation pressure holding time is 10-15min.
  • the invention also provides a transition metal boride hard material, which is prepared by the method for preparing the transition metal boride hard material.
  • the preparation method of the transition metal boride hard material provided by the invention obtains the bulk material with high density and excellent comprehensive performance by adding magnesium oxide; and by controlling the sintering parameters, the highest possible material density is obtained, and the sintering process and The interrelationship between the amount of MgO added-the microstructure of the bulk material and the mechanical properties of the density-bulk material is used to guide the adjustment of the process parameters and the amount of MgO added to optimize the performance of the material.
  • the transition metal boride hard material prepared by adding magnesium oxide in the embodiment of the present invention can have a density value of about 99.59% and a Vickers hardness value of about 33.24 GPa or even higher.
  • Fig. 2 shows the bulk of Os 0.9 Re 0.1 B 2 powder in Examples 1-4 of the present invention after adding 0, 3, 6 , and 9 wt.% MgO to 1600°C discharge plasma sintering, and Os 0.9 Re in Examples 5-6 XRD pattern of the block after 0.1 B 2 powder was added with 0, 3wt.% MgO and sintered at 1750°C by hot pressing;
  • FIG. 3 is a cross-sectional SEM image and point energy spectrum of Os 0.9 Re 0.1 B 2 powder after 1600° C. discharge plasma sintering in Example 1 of the present invention
  • FIG. 4 is a cross-sectional sweep energy spectrum of the bulk of Os 0.9 Re 0.1 B 2 powder after discharge plasma sintering at 1600°C in Example 1 of the present invention
  • FIG. 5 is a cross-sectional SEM image and a point energy spectrum of the block after the Os 0.9 Re 0.1 B 2 powder is added with 3wt.% MgO and sintered at 1600°C in Example 2 of the present invention;
  • FIG. 6 is a cross-sectional scanning energy spectrum of the block after the Os 0.9 Re 0.1 B 2 powder is added with 3wt.% MgO in the second embodiment of the present invention and sintered by 1600°C discharge plasma;
  • Example 7 is a cross-sectional SEM image and point energy spectrum of the block after the Os 0.9 Re 0.1 B 2 powder in Example 3 of the present invention is added with 6wt.% MgO and sintered by 1600°C discharge plasma;
  • FIG. 8 is a cross-sectional scanning energy spectrum of the block after the Os 0.9 Re 0.1 B 2 powder is added with 6 wt.% MgO and sintered at 1600°C in Example 3 of the present invention
  • FIG. 9 is a cross-sectional SEM image and point energy spectrum of the block after the Os 0.9 Re 0.1 B 2 powder is added with 9wt.% MgO at 1600°C by spark plasma sintering in Example 4 of the present invention
  • FIG. 10 is a cross-sectional scanning energy spectrum of a block after the Os 0.9 Re 0.1 B 2 powder is added with 9 wt.% MgO and sintered at 1600° C. in Example 4 of the present invention;
  • Example 11 is a cross-sectional SEM image and point energy spectrum of the bulk of the Os 0.9 Re 0.1 B 2 powder after being hot-pressed at 1750°C in Example 5 of the present invention
  • Example 12 is a cross-sectional SEM image and a point energy spectrum of the block after the Os 0.9 Re 0.1 B 2 powder is added with 3wt.% MgO and sintered at 1750°C in Example 6 of the present invention;
  • Example 13 is a backscattering diagram of the polished surface of the bulk of Os 0.9 Re 0.1 B 2 powder after being hot-pressed at 1750°C in Example 5 of the present invention:
  • FIG. 14 is a backscattering diagram of the polished surface of the block after the Os 0.9 Re 0.1 B 2 powder is added with 3wt.% MgO and sintered at 1750°C in Example 6 of the present invention:
  • the embodiment of the present invention provides a transition metal boride hard material and a preparation method thereof, which solves the technical problems that the existing super hard material is expensive to prepare, the workpiece is easy to wear, and the work is hardened.
  • Os 0.9 Re 0.1 B 2 is used as an example, and Os 0.9 Re 0.1 B 2 powder is synthesized by using a high-energy ball mill model 8000M of SPEX Company of the United States, and then the synthesized powder is densified and sintered at a high temperature.
  • Os high-purity osmium powder
  • Re rhenium powder
  • B boron
  • Os 0.9 Re 0.1 B 2 powder after sieving was sintered with discharge plasma at 1600°C, 40 MPa, and holding pressure for 15 minutes to obtain Os 0.9 Re 0.1 B 2 bulk material.
  • Os 0.9 Re 0.1 B 2 was used as an example, and Os 0.9 Re 0.1 B 2 powder was synthesized using a high-energy ball mill model 8000M of the United States SPEX company, and then the synthesized powder was added at high temperature by adding magnesium oxide as a sintering aid. The densification sintering is carried out.
  • high-purity osmium powder (Os), rhenium powder (Re) in which the molar ratio of osmium powder to rhenium powder is 9:1
  • boron (B) powder are stoichiometric ratio 1:3 ingredients.
  • the grinding balls used are made of tungsten carbide, the number is 6, the diameter is 11.20mm, and the ball-to-material ratio is 4:1.
  • Os 0.9 Re 0.1 B 2 powder added with 3 wt.% MgO was sintered with discharge plasma at 1600° C., 40 MPa, and holding pressure for 15 minutes to obtain Os 0.9 Re 0.1 B 2 bulk material with 3 wt.% MgO added.
  • Os 0.9 Re 0.1 B 2 was used as an example, and Os 0.9 Re 0.1 B 2 powder was synthesized using a high-energy ball mill model 8000M of the United States SPEX company, and then the synthesized powder was added at high temperature by adding magnesium oxide as a sintering aid. The densification sintering is carried out.
  • high-purity osmium powder (Os), rhenium powder (Re) in which the molar ratio of osmium powder to rhenium powder is 9:1
  • boron (B) powder are stoichiometric ratio 1:3 ingredients.
  • the grinding balls used are made of tungsten carbide, the number is 6, the diameter is 11.20mm, and the ball-to-material ratio is 4:1.
  • Os 0.9 Re 0.1 B 2 powder added with 6 wt.% MgO was sintered with discharge plasma at 1600° C., 40 MPa, and holding pressure for 15 minutes to obtain Os 0.9 Re 0.1 B 2 bulk material with 6 wt.% MgO added.
  • Os 0.9 Re 0.1 B 2 was used as an example, and Os 0.9 Re 0.1 B 2 powder was synthesized using a high-energy ball mill model 8000M of the United States SPEX company, and then the synthesized powder was added at high temperature by adding magnesium oxide as a sintering aid. The densification sintering is carried out.
  • high-purity osmium powder (Os), rhenium powder (Re) in which the molar ratio of osmium powder to rhenium powder is 9:1
  • boron (B) powder are stoichiometric ratio 1:3 ingredients.
  • the grinding balls used are made of tungsten carbide, the number is 6, the diameter is 11.20mm, and the ball-to-material ratio is 4:1.
  • Os 0.9 Re 0.1 B 2 powder added with 9 wt.% MgO was sintered with discharge plasma at 1600° C., 40 MPa, and holding pressure for 15 minutes to obtain a bulk material of Os 0.9 Re 0.1 B 2 added with 9 wt.% MgO.
  • Os 0.9 Re 0.1 B 2 is used as an example, and Os 0.9 Re 0.1 B 2 powder is synthesized by using a high-energy ball mill model 8000M of SPEX Company of the United States, and then the synthesized powder is densified and sintered at a high temperature.
  • Os high-purity osmium powder
  • Re rhenium powder
  • B boron
  • Os 0.9 Re 0.1 B 2 powder after sieving treatment was sintered in a hot press furnace at 1750°C, 30 MPa, and holding pressure for 1 hour to obtain Os 0.9 Re 0.1 B 2 bulk material.
  • Os 0.9 Re 0.1 B 2 was used as an example, and Os 0.9 Re 0.1 B 2 powder was synthesized using a high-energy ball mill model 8000M of the United States SPEX company, and then the synthesized powder was added at high temperature by adding magnesium oxide as a sintering aid. The densification sintering is carried out.
  • high-purity osmium powder (Os), rhenium powder (Re) in which the molar ratio of osmium powder to rhenium powder is 9:1
  • boron (B) powder are stoichiometric ratio 1:3 ingredients.
  • the grinding balls used are made of tungsten carbide, the number is 6, the diameter is 11.20mm, and the ball-to-material ratio is 4:1.
  • Os 0.9 Re 0.1 B 2 powder added with 3 wt.% MgO was sintered in a hot-press furnace at 1750° C., 30 MPa, and holding pressure for 1 h to obtain a bulk material of Os 0.9 Re 0.1 B 2 added with 3 wt.% MgO.
  • Fig. 2 is the block and implementation of Os 0.9 Re 0.1 B 2 powder after 0. 3, 6 , 9 wt.% magnesium oxide sintering aid after 1400°C discharge plasma sintering in Example 1-4 of the invention after 40 hours of ball milling
  • Fig. 3, Fig. 5, Fig. 7 and Fig. 9 are the blocks after adding 0, 3, 6, and 9wt.% magnesium oxide sintering aid to the Os 0.9 Re 0.1 B 2 powder after being ball milled for 40h after 1600°C discharge plasma sintering SEM image and point energy spectrum of the cross-section
  • Figure 4, Figure 6, Figure 8 and Figure 10 are the Os 0.9 Re 0.1 B 2 powder added to 0, 3, 6, 9wt.% magnesium oxide sintering aid after 40h of ball milling, respectively After 1600°Cdischarge plasma sintering, the cross-section energy spectrum of the block is measured. It is known from Fig.
  • the sample added with 0wt.% magnesium oxide has small grains but many pores, its density is only 78.9%, and the hardness value is 30.2 ⁇ 4.347GPa.
  • the black area is mainly It is the enriched area of boron and oxygen, combined with its surface scanning energy spectrum.
  • Figure 4 shows that there are elements such as Os, Re, B, w, C, and O, where the peak of B is relatively high, indicating that there is more excess boron
  • Figure 7 shows that the sample with 6wt.% magnesia added has a more uniform cross-sectional grain size, and the grains are in the shape of long rods.
  • the aspect ratio is slightly larger than the sample with 0, 3, and 9wt.% magnesia added.
  • the form is mostly transgranular fracture, with a density of 94.63% and a hardness value of 33.2 ⁇ 4.51GPa.
  • Both the point energy spectrum in Figure 7 and the surface scanning energy spectrum in Figure 8 detect the presence of Mg element; 5 and Figure 9 shows that the sample with 3 and 9wt.% magnesium oxide has a non-uniform grain distribution in the cross section.
  • the sample with 3wt.% magnesium oxide has a black area with excess boron enrichment.
  • the sample with 9wt.% magnesium oxide has a main cross section. There are two sizes of grains, of which the “darker” regions are mainly the enriched regions of Mg and O elements.
  • the density of the sample with the addition of 9wt.% can reach 99.59%, indicating that the magnesium oxide
  • the addition contributes to the densification and sintering of the MgO-Os 0.9 Re 0.1 B 2 block, and within a certain range, the more the amount of addition, the higher the density, but from the hardness value, the sample with 6wt.% magnesium oxide
  • the highest hardness value indicates that the addition of magnesium oxide contributes to the densification of the MgO-Os 0.9 Re 0.1 B 2 block, and the addition of magnesium oxide at about 6wt.% has better performance.
  • Fig. 11 and Fig. 12 are the SEM photograph and point energy spectrum of the block cross section of Os 0.9 Re 0.1 B 2 powder after adding 0 and 3wt.% magnesium oxide and sintering at 1750°C and hot pressing, respectively. It can be seen from Fig. 11 and Fig. 12 that the sintered samples without addition and addition of 3wt.% magnesium oxide have similar microstructures, and the fracture forms are all transgranular fractures. There are pores in the order, and the density is not high, but the density of the block with 3wt.% magnesium oxide is increased to a certain extent compared with that without the addition. The density values are 79% and 89.2%, respectively. Combining with the energy spectrum of the corresponding point, only excess B exists between the grain boundaries in FIG. 11 and no other second phases exist; and Mg and O elements still exist at the grain boundaries in FIG. 12.
  • Fig. 13 and Fig. 14 are the back scattering diagrams of the polished surface of the block after Os 0.9 Re 0.1 B 2 powder is added with 0 and 3wt.% magnesia sintering aid after 1750°C hot pressing sintering: the two groups of samples can be seen from the figure The grain size is larger and there are some black areas, which may be the accumulation of excess boron powder to generate black areas. It is also possible that the gas generated by the volatilization of boron powder during the sintering process is too late to be discharged to form pores.
  • Re rhenium
  • Ir iridium
  • W tungsten

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Abstract

The present invention belongs to the field of transition metal materials, and in particular relates to a hard transition metal boride material and a preparation method therefor. Provided is a method for preparing the hard transition metal boride material, comprising the following steps: step 1: ball-milling an osmium powder, an MT powder and a boron powder by means of a mechanochemical method to obtain a mixed Os1-xMTxB2 powder; step 2: adding an appropriate amount of magnesium oxide into the Os1-xMTxB2 powder, fully milling the Os1-xMTxB2 mixed powder with the magnesium oxide added using a mortar until uniformly mixing same, and then subjecting same to a sieving treatment, so as to obtain a uniformly mixed MgO-Os1-xMTxB2 powder; and step 3: sintering the MgO-Os1-xMTxB2 powder to obtain the hard transition metal boride material. Also provided is the hard transition metal boride material prepared by the method. The hard transition metal boride material and the preparation method therefor provided solve the technical problems of the expensive preparation cost of existing superhard materials, ease of wear of a workpiece, work hardening, etc.

Description

一种过渡金属硼化物硬质材料及其制备方法Transition metal boride hard material and preparation method thereof 技术领域Technical field
本发明属于过渡金属材料领域，尤其涉及一种过渡金属硼化物硬质材料及其制备方法。The invention belongs to the field of transition metal materials, and particularly relates to a transition metal boride hard material and a preparation method thereof.
背景技术Background technique
硬度是衡量材料性能的一项重要指标，主要表述材料抵抗弹性变形、塑性变形的能力。通常我们把维氏硬度大于40GPa的材料称为超硬材料。超硬材料不仅具有高硬度和耐磨性，而且还具有高的抗压缩性、热导率和化学稳定性，因此在工业生产、医学、地质、冶金、电子及军事国防等领域都占有相当重要的地位。Hardness is an important indicator to measure the performance of materials, mainly expressing the ability of materials to resist elastic deformation and plastic deformation. Generally, we call the material with Vickers hardness greater than 40GPa super hard material. Superhard materials not only have high hardness and wear resistance, but also have high compression resistance, thermal conductivity and chemical stability, so they are very important in the fields of industrial production, medicine, geology, metallurgy, electronics and military defense. Status.
超硬材料可以分为传统超硬材料和新型超硬材料两大类。传统超硬材料主要包括金刚石和立方氮化硼，金刚石主要存在热稳定性和化学稳定性较差等问题，在空气中加热到800℃易被氧化且在加工含铁类金属工件时，碳会渗入到工件中导致工件磨损和加工硬化，使之不适合加工含铁的工件；而立方氮化硼目前存在制备成本非常昂贵等问题。Superhard materials can be divided into two categories: traditional superhard materials and new superhard materials. Traditional superhard materials mainly include diamond and cubic boron nitride. Diamond mainly has problems such as poor thermal stability and chemical stability. When heated to 800 ℃ in air, it is easily oxidized. When processing iron-containing metal workpieces, carbon will Infiltration into the workpiece leads to wear and work hardening of the workpiece, making it unsuitable for processing ferrous workpieces; and cubic boron nitride currently has problems such as very expensive preparation costs.
因此，现有的超硬材料制备成本昂贵、工件易磨损且加工硬化成为了本领域技术人员亟待解决的技术问题。Therefore, the existing super-hard materials are expensive to prepare, work pieces are prone to wear, and work hardening has become a technical problem to be urgently solved by those skilled in the art.
发明内容Summary of the invention
本发明提供了一种过渡金属硼化物硬质材料及其制备方法，解决了现有的超硬材料制备成本昂贵、工件易磨损且加工硬化的技术问题。The invention provides a transition metal boride hard material and a preparation method thereof, which solves the technical problems that the existing super hard material is expensive to prepare, the workpiece is easy to wear and the work is hardened.
本发明提供了一种过渡金属硼化物硬质材料的制备方法，其特征在于，包括以下步骤：The invention provides a method for preparing a transition metal boride hard material, which is characterized by comprising the following steps:
步骤1：采用机械化学法将锇粉、MT粉和硼粉球磨得到混合Os 1-xMT xB 2粉末，其中x为0.01-0.5，MT为铼元素、钨元素或铱元素； Step 1: Ball milling osmium powder, MT powder and boron powder by mechanochemical method to obtain mixed Os 1-x MT x B 2 powder, where x is 0.01-0.5, MT is rhenium element, tungsten element or iridium element;
步骤2：在步骤1中得到的Os 1-xMT xB 2粉末中添加适量氧化镁，利用碾钵对添加氧化镁后的Os 1-xMT xB 2混合粉末进行充分碾磨至混合均匀，再进行过筛处理，得到混合均匀的MgO-Os 1-xMT xB 2粉末； Step 2: Add an appropriate amount of magnesium oxide to the Os 1-x MT x B 2 powder obtained in Step 1, and use a grinding bowl to fully grind the mixed powder of Os 1-x MT x B 2 after adding magnesium oxide until the mixture is uniform , And then sieved to obtain uniformly mixed MgO-Os 1-x MT x B 2 powder;
步骤3：将步骤2得到的MgO-Os 1-xMT xB 2粉末进行烧结得到过渡金属硼化物硬质材料。 Step 3: Sinter the MgO-Os 1-x MT x B 2 powder obtained in Step 2 to obtain a transition metal boride hard material.
优选的，步骤1中所述锇粉与所述MT粉的混合物为锇-MT粉，所述锇-MT粉与所述硼粉的原粉摩尔比例为1∶(2-5)。Preferably, the mixture of the osmium powder and the MT powder in step 1 is osmium-MT powder, and the molar ratio of the original powder of the osmium-MT powder and the boron powder is 1: (2-5).
更优选的，所述锇-MT粉与所述硼粉的原粉摩尔比例为1∶(2.25-2.5)。More preferably, the molar ratio of the original powder of osmium-MT powder to the boron powder is 1: (2.25-2.5).
更优选的，所述锇粉、铼粉和硼粉的原粉摩尔比例为0.9∶0.1∶(2.25-5)，进一步优选为0.9∶0.1∶(2.25-2.5)；More preferably, the molar ratio of the original powder of osmium powder, rhenium powder and boron powder is 0.9:0.1:(2.25-5), further preferably 0.9:0.1:(2.25-2.5);
优选的，所述机械化学法采用的设备为高能球磨机、振动球磨机、行星式球磨机和场辅助球磨机中的一种或多种。Preferably, the equipment used in the mechanochemical method is one or more of a high-energy ball mill, a vibration ball mill, a planetary ball mill, and a field assisted ball mill.
具体的，所述场辅助球磨机包括等离子体辅助高能球磨机。Specifically, the field assisted ball mill includes a plasma assisted high energy ball mill.
优选的，所述氧化镁粉的质量分数为1wt.％-12wt.％。Preferably, the mass fraction of the magnesium oxide powder is 1wt.%-12wt.%.
优选的，在所述步骤2之后，所述步骤3之前还包括充分碾磨和过筛。Preferably, after the step 2 and before the step 3, it further includes sufficient grinding and sieving.
优选的，所述碾磨的时间为20-30min，所述过筛的筛孔直径为100-200目。Preferably, the milling time is 20-30 min, and the diameter of the sieve is 100-200 mesh.
优选的，所述烧结为无压烧结、热压烧结或放电等离子烧结。Preferably, the sintering is pressureless sintering, hot press sintering or spark plasma sintering.
优选的，所述烧结温度为1400℃-1800℃。Preferably, the sintering temperature is 1400°C-1800°C.
更优选的，所述烧结温度为1600℃-1750℃。More preferably, the sintering temperature is 1600°C-1750°C.
优选的，所述无压烧结的升温速率为3-15℃/min，保温时间为1-2h；所述热压烧结的升温速率为5-15℃/min，烧结压力为20MPa-70MPa，保温保压时间为1-2h；所述放电等离子烧结的升温速率为100-200℃/min，烧结压力为20MPa-70MPa，保温保压时间为10-15min。Preferably, the temperature increase rate of the pressureless sintering is 3-15°C/min and the holding time is 1-2h; the temperature increase rate of the hot press sintering is 5-15°C/min and the sintering pressure is 20MPa-70MPa, heat preservation The pressure holding time is 1-2h; the temperature rise rate of the spark plasma sintering is 100-200°C/min, the sintering pressure is 20MPa-70MPa, and the heat preservation pressure holding time is 10-15min.
本发明还提供了一种过渡金属硼化物硬质材料，由上述的过渡金属硼化物硬质材料的制备方法制得。The invention also provides a transition metal boride hard material, which is prepared by the method for preparing the transition metal boride hard material.
本发明提供的过渡金属硼化物硬质材料制备方法，通过添加氧化镁获得致密度高综合性能优异的块体材料；且通过控制烧结参数，获得尽可能高的材料致密度，建立了烧结工艺及MgO添加量-块体材料微观结构和致密度-块体材料力学性能之间的相互关系，用于指导工艺参数和MgO添加量的调控，实现对材料性能的优化。本发明添加氧化镁实施例制备的过渡金属硼化物硬质材料，其致密度值可以达到99.59％左右、维氏硬度值可以达到33.24GPa左右甚至更高。The preparation method of the transition metal boride hard material provided by the invention obtains the bulk material with high density and excellent comprehensive performance by adding magnesium oxide; and by controlling the sintering parameters, the highest possible material density is obtained, and the sintering process and The interrelationship between the amount of MgO added-the microstructure of the bulk material and the mechanical properties of the density-bulk material is used to guide the adjustment of the process parameters and the amount of MgO added to optimize the performance of the material. The transition metal boride hard material prepared by adding magnesium oxide in the embodiment of the present invention can have a density value of about 99.59% and a Vickers hardness value of about 33.24 GPa or even higher.
附图说明BRIEF DESCRIPTION
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其它的附图。In order to more clearly explain the embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings required in the embodiments or the description of the prior art. Obviously, the drawings in the following description are only These are some embodiments of the present invention. For those of ordinary skill in the art, without paying any creative labor, other drawings can be obtained based on these drawings.
图1为本发明实施例1-6中Os-Re-B混合粉末高能球磨40h后的XRD图谱；1 is the XRD pattern of the Os-Re-B mixed powder high-energy ball milling in Examples 1-6 of the present invention after 40 hours;
图2为本发明实施例1-4中Os 0.9Re 0.1B 2粉末分别添加0、3、6、9wt.％MgO经1600℃放电等离子烧结后的块体和实施例5-6中Os 0.9Re 0.1B 2粉末分别添加0、3wt.％MgO经1750℃热压烧结后的块体XRD图谱； Fig. 2 shows the bulk of Os 0.9 Re 0.1 B 2 powder in Examples 1-4 of the present invention after adding 0, 3, 6 , and 9 wt.% MgO to 1600°C discharge plasma sintering, and Os 0.9 Re in Examples 5-6 XRD pattern of the block after 0.1 B 2 powder was added with 0, 3wt.% MgO and sintered at 1750℃ by hot pressing;
图3为本发明实施例1中Os 0.9Re 0.1B 2粉末经1600℃放电等离子烧结后块体的断面SEM图和点能谱图； FIG. 3 is a cross-sectional SEM image and point energy spectrum of Os 0.9 Re 0.1 B 2 powder after 1600° C. discharge plasma sintering in Example 1 of the present invention;
图4为本发明实施例1中Os 0.9Re 0.1B 2粉末经1600℃放电等离子烧结后块体的断面面扫能谱图； FIG. 4 is a cross-sectional sweep energy spectrum of the bulk of Os 0.9 Re 0.1 B 2 powder after discharge plasma sintering at 1600°C in Example 1 of the present invention;
图5为本发明实施例2中Os 0.9Re 0.1B 2粉末添加3wt.％MgO经1600℃放电等离子烧结后块体的断面SEM图和点能谱图； FIG. 5 is a cross-sectional SEM image and a point energy spectrum of the block after the Os 0.9 Re 0.1 B 2 powder is added with 3wt.% MgO and sintered at 1600°C in Example 2 of the present invention;
图6为本发明实施例2中Os 0.9Re 0.1B 2粉末添加3wt.％MgO经1600℃放电等离子烧结后块体的断面面扫能谱图； FIG. 6 is a cross-sectional scanning energy spectrum of the block after the Os 0.9 Re 0.1 B 2 powder is added with 3wt.% MgO in the second embodiment of the present invention and sintered by 1600°C discharge plasma;
图7为本发明实施例3中Os 0.9Re 0.1B 2粉末添加6wt.％MgO经1600℃放电等离子烧结后块体的断面SEM图和点能谱图； 7 is a cross-sectional SEM image and point energy spectrum of the block after the Os 0.9 Re 0.1 B 2 powder in Example 3 of the present invention is added with 6wt.% MgO and sintered by 1600°C discharge plasma;
图8为本发明实施例3中Os 0.9Re 0.1B 2粉末添加6wt.％MgO经1600℃放电等离子烧结后块体的断面面扫能谱图； FIG. 8 is a cross-sectional scanning energy spectrum of the block after the Os 0.9 Re 0.1 B 2 powder is added with 6 wt.% MgO and sintered at 1600°C in Example 3 of the present invention;
图9为本发明实施例4中Os 0.9Re 0.1B 2粉末添加9wt.％MgO经1600℃放电等离子烧结后块体的断面SEM图和点能谱图； FIG. 9 is a cross-sectional SEM image and point energy spectrum of the block after the Os 0.9 Re 0.1 B 2 powder is added with 9wt.% MgO at 1600°C by spark plasma sintering in Example 4 of the present invention;
图10为本发明实施例4中Os 0.9Re 0.1B 2粉末添加9wt.％MgO经1600℃放电等离子烧结后块体的断面面扫能谱图； FIG. 10 is a cross-sectional scanning energy spectrum of a block after the Os 0.9 Re 0.1 B 2 powder is added with 9 wt.% MgO and sintered at 1600° C. in Example 4 of the present invention;
图11为本发明实施例5中Os 0.9Re 0.1B 2粉末经1750℃热压烧结后块体的断面SEM图和点能谱图； 11 is a cross-sectional SEM image and point energy spectrum of the bulk of the Os 0.9 Re 0.1 B 2 powder after being hot-pressed at 1750°C in Example 5 of the present invention;
图12为本发明实施例6中Os 0.9Re 0.1B 2粉末添加3wt.％MgO经1750℃热压烧结后块体的断面SEM图和点能谱图； 12 is a cross-sectional SEM image and a point energy spectrum of the block after the Os 0.9 Re 0.1 B 2 powder is added with 3wt.% MgO and sintered at 1750°C in Example 6 of the present invention;
图13为本发明实施例5中Os 0.9Re 0.1B 2粉末经1750℃热压烧结后的块体抛光面背散射图： 13 is a backscattering diagram of the polished surface of the bulk of Os 0.9 Re 0.1 B 2 powder after being hot-pressed at 1750°C in Example 5 of the present invention:
图14为本发明实施例6中Os 0.9Re 0.1B 2粉末添加3wt.％MgO经1750℃热压烧结后的块体抛光面背散射图： FIG. 14 is a backscattering diagram of the polished surface of the block after the Os 0.9 Re 0.1 B 2 powder is added with 3wt.% MgO and sintered at 1750°C in Example 6 of the present invention:
具体实施方式detailed description
本发明实施例提供了一种过渡金属硼化物硬质材料及其制备方法，解决了现有的超硬材料制备成本昂贵、工件易磨损且加工硬化的技术问题。The embodiment of the present invention provides a transition metal boride hard material and a preparation method thereof, which solves the technical problems that the existing super hard material is expensive to prepare, the workpiece is easy to wear, and the work is hardened.
为使得本发明的发明目的、特征、优点能够更加的明显和易懂，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，下面所描述的实施例仅仅是本发明一部分实施例，而非全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。In order to make the purpose, features, and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be described clearly and completely in conjunction with the drawings in the embodiments of the present invention. Obviously, the following The described embodiments are only a part of the embodiments of the present invention, but not all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by a person of ordinary skill in the art without making creative efforts fall within the protection scope of the present invention.
实施例1Example 1
(1)本实施例以Os 0.9Re 0.1B 2为例，采用美国SPEX公司型号为8000M的高能球磨机合成Os 0.9Re 0.1B 2粉末，然后对合成的粉末在高温下进行致密化烧结。首先，在充满氩气的手套箱中将高纯的锇粉(Os)，铼粉(Re)(其中锇粉与铼粉的摩尔比例为9∶1)与硼(B)粉按化学计量比1∶3进行配料。使用的磨球为碳化钨材质，数量为6个，直径尺寸为11.20mm，球料比为4∶1。 (1) In this embodiment, Os 0.9 Re 0.1 B 2 is used as an example, and Os 0.9 Re 0.1 B 2 powder is synthesized by using a high-energy ball mill model 8000M of SPEX Company of the United States, and then the synthesized powder is densified and sintered at a high temperature. First, in a glove box filled with argon, high-purity osmium powder (Os), rhenium powder (Re) (in which the molar ratio of osmium powder to rhenium powder is 9:1) and boron (B) powder are stoichiometric ratio 1:3 ingredients. The grinding balls used are made of tungsten carbide, the number is 6, the diameter is 11.20mm, and the ball-to-material ratio is 4:1.
(2)将装好粉体和磨球的球磨罐固定在高能球磨机的夹具上，对其进行球磨40h，为防止电动机过热，设定每球磨1h停机20min。(2) Fix the ball mill jar with the powder and balls installed on the fixture of the high-energy ball mill, and perform ball milling for 40 hours. To prevent the motor from overheating, set the machine to stop for 20 minutes every 1 hour.
(3)取一定量高能球磨40h后的Os-Re-B混合粉末，对粉末进行过筛处理，筛孔规格为200目。(3) Take a certain amount of Os-Re-B mixed powder after 40 hours of high-energy ball milling, sieve the powder, and the mesh size is 200 mesh.
(4)将过筛后的Os 0.9Re 0.1B 2粉末采用放电等离子进行1600℃、40MPa、保温保压15min烧结，得到Os 0.9Re 0.1B 2块体材料。 (4) Os 0.9 Re 0.1 B 2 powder after sieving was sintered with discharge plasma at 1600°C, 40 MPa, and holding pressure for 15 minutes to obtain Os 0.9 Re 0.1 B 2 bulk material.
实施例2Example 2
(1)本实施例以Os 0.9Re 0.1B 2为例，采用美国SPEX公司型号为8000M的高能球磨机合成Os 0.9Re 0.1B 2粉末，然后通过添加氧化镁作为烧结助剂对合 成的粉末在高温下进行致密化烧结。首先，在充满氩气的手套箱中将高纯的锇粉(Os)，铼粉(Re)(其中锇粉与铼粉的摩尔比例为9∶1)与硼(B)粉按化学计量比1∶3进行配料。使用的磨球为碳化钨材质，数量为6个，直径尺寸为11.20mm，球料比为4∶1。 (1) In this example, Os 0.9 Re 0.1 B 2 was used as an example, and Os 0.9 Re 0.1 B 2 powder was synthesized using a high-energy ball mill model 8000M of the United States SPEX company, and then the synthesized powder was added at high temperature by adding magnesium oxide as a sintering aid. The densification sintering is carried out. First, in a glove box filled with argon, high-purity osmium powder (Os), rhenium powder (Re) (in which the molar ratio of osmium powder to rhenium powder is 9:1) and boron (B) powder are stoichiometric ratio 1:3 ingredients. The grinding balls used are made of tungsten carbide, the number is 6, the diameter is 11.20mm, and the ball-to-material ratio is 4:1.
(2)将装好粉体和磨球的球磨罐固定在高能球磨机的夹具上，对其进行球磨40h，为防止电动机过热，设定每球磨1h停机20min。(2) Fix the ball mill jar with the powder and balls installed on the fixture of the high-energy ball mill, and perform ball milling for 40 hours. To prevent the motor from overheating, set the machine to stop for 20 minutes every 1 hour.
(3)取一定量高能球磨40h后的Os-Re-B混合粉末，加入质量分数为3％的MgO粉末，利用碾钵碾磨混合均匀，再对混合均匀的粉末过筛处理，筛孔规格为200目。(3) Take a certain amount of Os-Re-B mixed powder after 40 hours of high-energy ball milling, add MgO powder with a mass fraction of 3%, use a bowl to grind and mix evenly, then sieve the mixed powder, and screen size 200 mesh.
(4)将添加3wt.％MgO的Os 0.9Re 0.1B 2粉末采用放电等离子进行1600℃、40MPa、保温保压15min烧结，得到添加3wt.％MgO的Os 0.9Re 0.1B 2块体材料。 (4) Os 0.9 Re 0.1 B 2 powder added with 3 wt.% MgO was sintered with discharge plasma at 1600° C., 40 MPa, and holding pressure for 15 minutes to obtain Os 0.9 Re 0.1 B 2 bulk material with 3 wt.% MgO added.
实施例3Example 3
(1)本实施例以Os 0.9Re 0.1B 2为例，采用美国SPEX公司型号为8000M的高能球磨机合成Os 0.9Re 0.1B 2粉末，然后通过添加氧化镁作为烧结助剂对合成的粉末在高温下进行致密化烧结。首先，在充满氩气的手套箱中将高纯的锇粉(Os)，铼粉(Re)(其中锇粉与铼粉的摩尔比例为9∶1)与硼(B)粉按化学计量比1∶3进行配料。使用的磨球为碳化钨材质，数量为6个，直径尺寸为11.20mm，球料比为4∶1。 (1) In this example, Os 0.9 Re 0.1 B 2 was used as an example, and Os 0.9 Re 0.1 B 2 powder was synthesized using a high-energy ball mill model 8000M of the United States SPEX company, and then the synthesized powder was added at high temperature by adding magnesium oxide as a sintering aid. The densification sintering is carried out. First, in a glove box filled with argon, high-purity osmium powder (Os), rhenium powder (Re) (in which the molar ratio of osmium powder to rhenium powder is 9:1) and boron (B) powder are stoichiometric ratio 1:3 ingredients. The grinding balls used are made of tungsten carbide, the number is 6, the diameter is 11.20mm, and the ball-to-material ratio is 4:1.
(2)将装好粉体和磨球的球磨罐固定在高能球磨机的夹具上，对其进行球磨40h，为防止电动机过热，设定每球磨1h停机20min。(2) Fix the ball mill jar with the powder and balls installed on the fixture of the high-energy ball mill, and perform ball milling for 40 hours. To prevent the motor from overheating, set the machine to stop for 20 minutes every 1 hour.
(3)取一定量高能球磨40h后的Os-Re-B混合粉末，加入质量分数为6％的MgO粉末，利用碾钵碾磨混合均匀，再对混合均匀的粉末过筛处理，筛孔规格为200目。(3) Take a certain amount of Os-Re-B mixed powder after 40 hours of high-energy ball milling, add MgO powder with a mass fraction of 6%, use a grinding bowl to grind and mix evenly, then sieve the mixed powder, and screen size 200 mesh.
(4)将添加6wt.％MgO的Os 0.9Re 0.1B 2粉末采用放电等离子进行1600℃、40MPa、保温保压15min烧结，得到添加6wt.％MgO的Os 0.9Re 0.1B 2块体材料。 (4) Os 0.9 Re 0.1 B 2 powder added with 6 wt.% MgO was sintered with discharge plasma at 1600° C., 40 MPa, and holding pressure for 15 minutes to obtain Os 0.9 Re 0.1 B 2 bulk material with 6 wt.% MgO added.
实施例4Example 4
(1)本实施例以Os 0.9Re 0.1B 2为例，采用美国SPEX公司型号为8000M的高能球磨机合成Os 0.9Re 0.1B 2粉末，然后通过添加氧化镁作为烧结助剂对合成的粉末在高温下进行致密化烧结。首先，在充满氩气的手套箱中将高纯的 锇粉(Os)，铼粉(Re)(其中锇粉与铼粉的摩尔比例为9∶1)与硼(B)粉按化学计量比1∶3进行配料。使用的磨球为碳化钨材质，数量为6个，直径尺寸为11.20mm，球料比为4∶1。 (1) In this example, Os 0.9 Re 0.1 B 2 was used as an example, and Os 0.9 Re 0.1 B 2 powder was synthesized using a high-energy ball mill model 8000M of the United States SPEX company, and then the synthesized powder was added at high temperature by adding magnesium oxide as a sintering aid. The densification sintering is carried out. First, in a glove box filled with argon, high-purity osmium powder (Os), rhenium powder (Re) (in which the molar ratio of osmium powder to rhenium powder is 9:1) and boron (B) powder are stoichiometric ratio 1:3 ingredients. The grinding balls used are made of tungsten carbide, the number is 6, the diameter is 11.20mm, and the ball-to-material ratio is 4:1.
(2)将装好粉体和磨球的球磨罐固定在高能球磨机的夹具上，对其进行球磨40h，为防止电动机过热，设定每球磨1h停机20min。(2) Fix the ball mill jar with the powder and balls installed on the fixture of the high-energy ball mill, and perform ball milling for 40 hours. To prevent the motor from overheating, set the machine to stop for 20 minutes every 1 hour.
(3)取一定量高能球磨40h后的Os-Re-B混合粉末，加入质量分数为9％的MgO粉末，利用碾钵碾磨混合均匀，再对混合均匀的粉末过筛处理，筛孔规格为200目。(3) Take a certain amount of Os-Re-B mixed powder after 40 hours of high-energy ball milling, add MgO powder with a mass fraction of 9%, use a mortar to grind and mix evenly, then sieve the mixed powder, and screen size 200 mesh.
(4)将添加9wt.％MgO的Os 0.9Re 0.1B 2粉末采用放电等离子进行1600℃、40MPa、保温保压15min烧结，得到添加9wt.％MgO的Os 0.9Re 0.1B 2块体材料。 (4) Os 0.9 Re 0.1 B 2 powder added with 9 wt.% MgO was sintered with discharge plasma at 1600° C., 40 MPa, and holding pressure for 15 minutes to obtain a bulk material of Os 0.9 Re 0.1 B 2 added with 9 wt.% MgO.
实施例5Example 5
(1)本实施例以Os 0.9Re 0.1B 2为例，采用美国SPEX公司型号为8000M的高能球磨机合成Os 0.9Re 0.1B 2粉末，然后对合成的粉末在高温下进行致密化烧结。首先，在充满氩气的手套箱中将高纯的锇粉(Os)，铼粉(Re)(其中锇粉与铼粉的摩尔比例为9∶1)与硼(B)粉按化学计量比1∶3进行配料。使用的磨球为碳化钨材质，数量为6个，直径尺寸为11.20mm，球料比为4∶1。 (1) In this embodiment, Os 0.9 Re 0.1 B 2 is used as an example, and Os 0.9 Re 0.1 B 2 powder is synthesized by using a high-energy ball mill model 8000M of SPEX Company of the United States, and then the synthesized powder is densified and sintered at a high temperature. First, in a glove box filled with argon, high-purity osmium powder (Os), rhenium powder (Re) (in which the molar ratio of osmium powder to rhenium powder is 9:1) and boron (B) powder are stoichiometric ratio 1:3 ingredients. The grinding balls used are made of tungsten carbide, the number is 6, the diameter is 11.20mm, and the ball-to-material ratio is 4:1.
(2)将装好粉体和磨球的球磨罐固定在高能球磨机的夹具上，对其进行球磨40h，为防止电动机过热，设定每球磨1h停机20min。(2) Fix the ball mill jar with the powder and balls installed on the fixture of the high-energy ball mill, and perform ball milling for 40 hours. To prevent the motor from overheating, set the machine to stop for 20 minutes every 1 hour.
(3)取一定量高能球磨40h后的Os-Re-B混合粉末，对粉末进行过筛处理，筛孔规格为200目。(3) Take a certain amount of Os-Re-B mixed powder after 40 hours of high-energy ball milling, sieve the powder, and the mesh size is 200 mesh.
(4)将过筛处理后的Os 0.9Re 0.1B 2粉末采用热压炉进行1750℃、30MPa、保温保压1h烧结，得到Os 0.9Re 0.1B 2块体材料。 (4) Os 0.9 Re 0.1 B 2 powder after sieving treatment was sintered in a hot press furnace at 1750°C, 30 MPa, and holding pressure for 1 hour to obtain Os 0.9 Re 0.1 B 2 bulk material.
实施例6Example 6
(1)本实施例以Os 0.9Re 0.1B 2为例，采用美国SPEX公司型号为8000M的高能球磨机合成Os 0.9Re 0.1B 2粉末，然后通过添加氧化镁作为烧结助剂对合成的粉末在高温下进行致密化烧结。首先，在充满氩气的手套箱中将高纯的锇粉(Os)，铼粉(Re)(其中锇粉与铼粉的摩尔比例为9∶1)与硼(B)粉按化学计量比1∶3进行配料。使用的磨球为碳化钨材质，数量为6个，直径尺寸为11.20mm，球料比为4∶1。 (1) In this example, Os 0.9 Re 0.1 B 2 was used as an example, and Os 0.9 Re 0.1 B 2 powder was synthesized using a high-energy ball mill model 8000M of the United States SPEX company, and then the synthesized powder was added at high temperature by adding magnesium oxide as a sintering aid. The densification sintering is carried out. First, in a glove box filled with argon, high-purity osmium powder (Os), rhenium powder (Re) (in which the molar ratio of osmium powder to rhenium powder is 9:1) and boron (B) powder are stoichiometric ratio 1:3 ingredients. The grinding balls used are made of tungsten carbide, the number is 6, the diameter is 11.20mm, and the ball-to-material ratio is 4:1.
(2)将装好粉体和磨球的球磨罐固定在高能球磨机的夹具上，对其进行球磨40h，为防止电动机过热，设定每球磨1h停机20min。(2) Fix the ball mill jar with the powder and balls installed on the fixture of the high-energy ball mill, and perform ball milling for 40 hours. To prevent the motor from overheating, set the machine to stop for 20 minutes every 1 hour.
(3)取一定量高能球磨40h后的Os-Re-B混合粉末，加入质量分数为3％的MgO粉末，利用碾钵碾磨混合均匀，再对混合均匀的粉末过筛处理，筛孔规格为200目。(3) Take a certain amount of Os-Re-B mixed powder after 40 hours of high-energy ball milling, add MgO powder with a mass fraction of 3%, use a bowl to grind and mix evenly, then sieve the mixed powder, and screen size 200 mesh.
(4)将添加3wt.％MgO的Os 0.9Re 0.1B 2粉末采用热压炉进行1750℃、30MPa、保温保压1h烧结，得到添加3wt.％MgO的Os 0.9Re 0.1B 2块体材料。 (4) Os 0.9 Re 0.1 B 2 powder added with 3 wt.% MgO was sintered in a hot-press furnace at 1750° C., 30 MPa, and holding pressure for 1 h to obtain a bulk material of Os 0.9 Re 0.1 B 2 added with 3 wt.% MgO.
图1为本发明实施例1-6中Os-Re-B混合粉末高能球磨40h后的XRD图谱，其中(Os，Re＝9∶1)∶B＝1∶3。由图可知，混合粉在化学计量比Os-Re-B为0.9∶0.1∶3的条件下，高能球磨40h后，其所得到的产物主相为具有六方结构的ReB 2型Os 0.9Re 0.1B 2粉体。此外，合成的粉体中还存在少量的WC，可能来自于球磨罐和磨球的污染。 FIG. 1 is an XRD pattern of the Os-Re-B mixed powder high-energy ball milling in Examples 1-6 of the present invention after 40 hours, wherein (Os, Re=9:1): B=1:3. It can be seen from the figure that the mixed powder under the stoichiometric ratio of Os-Re-B is 0.9: 0.1: 3 , after high-energy ball milling for 40h, the main phase of the product obtained is ReB 2 type Os 0.9 Re 0.1 B with hexagonal structure 2 powder. In addition, there is a small amount of WC in the synthesized powder, which may come from the pollution of the ball mill jar and the ball.
图2为本发明实施例1-4中球磨40h后的Os 0.9Re 0.1B 2粉末分别添加0、3、6、9wt.％氧化镁烧结助剂经1600℃放电等离子烧结后的块体和实施例5-6中球磨40h后的Os 0.9Re 0.1B 2粉末分别添加0、3wt.％氧化镁烧结助剂经1750℃热压烧结后的块体XRD图谱。由图2可知：在球磨40h后的Os 0.9Re 0.1B 2粉末中分别添加0、3、6、9wt.％氧化镁烧结助剂经1600℃放电等离子烧结和在球磨40h后的Os 0.9Re 0.1B 2粉末中分别添加0、3wt.％氧化镁烧结助剂经1750℃热压烧结，六者烧结后的XRD图谱中主相均为六方结构的Os 0.9Re 0.1B 2，说明烧结助剂氧化镁的添加对材料的主相没有影响。 Fig. 2 is the block and implementation of Os 0.9 Re 0.1 B 2 powder after 0. 3, 6 , 9 wt.% magnesium oxide sintering aid after 1400°C discharge plasma sintering in Example 1-4 of the invention after 40 hours of ball milling The XRD pattern of the block after sintering the Os 0.9 Re 0.1 B 2 powder in Example 5-6 after 40 hours of ball milling by adding 0, 3wt.% magnesium oxide sintering aids at 1750°C after hot pressing. It can be seen from FIG. 2 that: 0, 3 , 6, 9wt.% magnesium oxide sintering aid was added to Os 0.9 Re 0.1 B 2 powder after 40h of ball milling, and the plasma sintering at 1600°C and Os 0.9 Re 0.1 after 40h of ball milling B 2 powder was added with 0, 3wt.% magnesium oxide sintering aids respectively, and then hot-press sintered at 1750℃. The XRD patterns of the six sintered powders were all Os 0.9 Re 0.1 B 2 with hexagonal structure, indicating that the sintering aids were oxidized. The addition of magnesium has no effect on the main phase of the material.
图3、图5、图7和图9分别为在球磨40h后的Os 0.9Re 0.1B 2粉末中添加0、3、6、9wt.％氧化镁烧结助剂经1600℃放电等离子烧结后块体的断面SEM图和点能谱图，图4、图6、图8和图10分别为在球磨40h后的Os 0.9Re 0.1B 2粉末中添加0、3、6、9wt.％氧化镁烧结助剂经1600℃放电等离子烧结后块体的断面面扫能谱图。由图3知添加0wt.％氧化镁的样品断面晶粒小但气孔较多，其致密度仅为78.9％，硬度值为30.2±4.347GPa，结合图3黑色区域点的能谱知黑色区域主要为硼和氧的富集区，再结合其面扫能谱图图4可知，存在元素有Os、Re、B、w、C、O，其中B的峰比较高，说明存在较多的富余硼；由图7知添加6wt.％氧化镁的样品断面晶粒尺寸较均匀，晶粒呈长棒状，长 径比要略大于添加0、3、9wt.％氧化镁的样品晶粒长径比，断裂形式多为穿晶断裂，其致密度为94.63％，硬度值达33.2±4.51GPa，在图7中点能谱图和图8中面扫能谱图均检测有Mg元素的存在；而由图5和图9知添加3和9wt.％氧化镁的样品断面晶粒分布不均匀，添加3wt.％氧化镁的样品断面存在多余硼富集的黑色区域，添加9wt.％氧化镁的样品断面主要存在两种尺寸的晶粒，其中“较黑”区域主要为Mg、O元素的富集区域，在图5、图9中的点能谱图和相应图6、图10的面扫能谱图均有Mg元素的存在，且添加9wt.％氧化镁的样品断面能谱图显示Mg元素的峰最高，这与添加的量相一致，添加3和9wt.％氧化镁的样品致密度值分别为90.96％和99.59％，硬度值分别为27.6±1.309GPa和29.1±0.721GPa。综合图3-10可知：随着氧化镁添加的含量增加，MgO-Os 0.9Re 0.1B 2块体的致密度不断地提高，添加9wt.％的样品致密度可达到99.59％，说明氧化镁的添加有助于MgO-Os 0.9Re 0.1B 2块体的致密化烧结，且在一定范围内其添加量越多，致密度越高，但从硬度值来看，添加6wt.％氧化镁的样品硬度值最高，说明氧化镁的添加有助于MgO-Os 0.9Re 0.1B 2块体的致密化，且氧化镁的添加量在6wt.％左右性能较好。 Fig. 3, Fig. 5, Fig. 7 and Fig. 9 are the blocks after adding 0, 3, 6, and 9wt.% magnesium oxide sintering aid to the Os 0.9 Re 0.1 B 2 powder after being ball milled for 40h after 1600°C discharge plasma sintering SEM image and point energy spectrum of the cross-section, Figure 4, Figure 6, Figure 8 and Figure 10 are the Os 0.9 Re 0.1 B 2 powder added to 0, 3, 6, 9wt.% magnesium oxide sintering aid after 40h of ball milling, respectively After 1600℃discharge plasma sintering, the cross-section energy spectrum of the block is measured. It is known from Fig. 3 that the sample added with 0wt.% magnesium oxide has small grains but many pores, its density is only 78.9%, and the hardness value is 30.2±4.347GPa. Combining the energy spectrum of the black area in Fig. 3, the black area is mainly It is the enriched area of boron and oxygen, combined with its surface scanning energy spectrum. Figure 4 shows that there are elements such as Os, Re, B, w, C, and O, where the peak of B is relatively high, indicating that there is more excess boron Figure 7 shows that the sample with 6wt.% magnesia added has a more uniform cross-sectional grain size, and the grains are in the shape of long rods. The aspect ratio is slightly larger than the sample with 0, 3, and 9wt.% magnesia added. The form is mostly transgranular fracture, with a density of 94.63% and a hardness value of 33.2±4.51GPa. Both the point energy spectrum in Figure 7 and the surface scanning energy spectrum in Figure 8 detect the presence of Mg element; 5 and Figure 9 shows that the sample with 3 and 9wt.% magnesium oxide has a non-uniform grain distribution in the cross section. The sample with 3wt.% magnesium oxide has a black area with excess boron enrichment. The sample with 9wt.% magnesium oxide has a main cross section. There are two sizes of grains, of which the “darker” regions are mainly the enriched regions of Mg and O elements. The point energy spectra in Figures 5 and 9 and the corresponding surface scanning energy spectra in Figures 6 and 10 There are Mg elements present, and the cross-sectional energy spectrum of the sample with 9wt.% magnesium oxide shows the highest peak of Mg element, which is consistent with the amount added. The density values of the samples with 3 and 9wt.% magnesium oxide are: 90.96% and 99.59%, the hardness values are 27.6±1.309GPa and 29.1±0.721GPa, respectively. It can be seen from Figures 3-10 that as the content of magnesium oxide increases, the density of the MgO-Os 0.9 Re 0.1 B 2 block continues to increase. The density of the sample with the addition of 9wt.% can reach 99.59%, indicating that the magnesium oxide The addition contributes to the densification and sintering of the MgO-Os 0.9 Re 0.1 B 2 block, and within a certain range, the more the amount of addition, the higher the density, but from the hardness value, the sample with 6wt.% magnesium oxide The highest hardness value indicates that the addition of magnesium oxide contributes to the densification of the MgO-Os 0.9 Re 0.1 B 2 block, and the addition of magnesium oxide at about 6wt.% has better performance.
图11和图12分别为Os 0.9Re 0.1B 2粉末添加0和3wt.％氧化镁经1750℃、热压烧结后的块体断面SEM照片和点能谱图。由图11和图12可知，无添加、添加3wt.％氧化镁烧结后的样品具有相似的微观结构，断裂形式均为穿晶断裂，两组样品的晶粒多为棒状晶且晶粒交错无序，均有气孔存在，致密度不高但添加3wt.％氧化镁的块体致密度较无添加的有一定程度的提高，其致密度值分别为79％和89.2％。结合相应点能谱图，图11中的晶界之间仅存在多余B，不存在其他的第二相；而在图12中的晶界处还存在有Mg、O元素。 Fig. 11 and Fig. 12 are the SEM photograph and point energy spectrum of the block cross section of Os 0.9 Re 0.1 B 2 powder after adding 0 and 3wt.% magnesium oxide and sintering at 1750℃ and hot pressing, respectively. It can be seen from Fig. 11 and Fig. 12 that the sintered samples without addition and addition of 3wt.% magnesium oxide have similar microstructures, and the fracture forms are all transgranular fractures. There are pores in the order, and the density is not high, but the density of the block with 3wt.% magnesium oxide is increased to a certain extent compared with that without the addition. The density values are 79% and 89.2%, respectively. Combining with the energy spectrum of the corresponding point, only excess B exists between the grain boundaries in FIG. 11 and no other second phases exist; and Mg and O elements still exist at the grain boundaries in FIG. 12.
图13和图14分别为Os 0.9Re 0.1B 2粉末添加0和3wt.％氧化镁烧结助剂经1750℃热压烧结后的块体抛光面背散射图：从图中可以看出两组样品的晶粒尺寸较大且存在一些黑色区域，这可能是多余的硼粉富集生成黑色区域。也有可能是在烧结过程中硼粉挥发产生的气体来不及排出而形成的气孔。 Fig. 13 and Fig. 14 are the back scattering diagrams of the polished surface of the block after Os 0.9 Re 0.1 B 2 powder is added with 0 and 3wt.% magnesia sintering aid after 1750℃ hot pressing sintering: the two groups of samples can be seen from the figure The grain size is larger and there are some black areas, which may be the accumulation of excess boron powder to generate black areas. It is also possible that the gas generated by the volatilization of boron powder during the sintering process is too late to be discharged to form pores.
对比例1Comparative Example 1
美国专利US09701542B2所述，2014年xie等人首次通过机械化学法合成ReB 2型六方结构OsB 2，但在随后的放电等离子烧结过程中，部分ReB 2型 六方结构OsB 2转变为正交结构导致材料性能降低。 As described in US Patent US09701542B2, in 2014, Xie et al. synthesized the ReB 2 type hexagonal structure OsB 2 for the first time through mechanochemical methods, but in the subsequent spark plasma sintering process, part of the ReB 2 type hexagonal structure OsB 2 was transformed into an orthogonal structure, resulting in materials Performance is reduced.
对比例2Comparative Example 2
ReB 2型六方结构的OsB 2在600℃以上温度即发生向正交结构的相变，通过在Os、B原料粉末中掺杂一定量的铼(Re)、铱(Ir)或钨(W)元素，可获得稳定的ReB 2型六方结构第三元素掺杂OsB 2，但具有ReB 2型六方结构第三元素掺杂的OsB 2通过放电等离子烧结、热压烧结和无压烧结后的块体材料致密度都不高，相应的块体力学性能表征也很低。 ReB 2 type hexagonal structure OsB2 2 at a temperature of 600 deg.] C above the phase transition occurs i.e. orthorhombic structure by doping Os, B a quantity of raw material powder of rhenium (Re), iridium (Ir) or tungsten (W) Element, stable ReB 2 type hexagonal structure third element doped OsB 2 , but OsB 2 with ReB 2 type hexagonal structure third element doped OsB 2 by spark plasma sintering, hot press sintering and pressureless sintered bulk The material density is not high, and the corresponding block mechanical properties are also very low.
以上所述，以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。As mentioned above, the above embodiments are only used to illustrate the technical solutions of the present invention, not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still The technical solutions described in the embodiments are modified, or some of the technical features are equivalently replaced; and these modifications or replacements do not deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
本领域的技术人员在不脱离权利要求书确定的本发明的精神和范围的条件下，还可以对以上内容进行各种各样的修改。因此本发明的范围并不仅限于以上的说明，而是由权利要求书的范围来确定的。Those skilled in the art can make various modifications to the above without departing from the spirit and scope of the present invention determined by the claims. Therefore, the scope of the present invention is not limited to the above description, but is determined by the scope of the claims.

Claims (10)

  1. 一种过渡金属硼化物硬质材料的制备方法，其特征在于，包括以下步骤：A method for preparing a transition metal boride hard material, characterized in that it includes the following steps:
    步骤1：采用机械化学法将锇粉、MT粉和硼粉球磨得到混合Os 1-xMT xB 2粉末，其中x为0.01-0.5，MT为铼元素、钨元素或铱元素； Step 1: Ball milling osmium powder, MT powder and boron powder by mechanochemical method to obtain mixed Os 1-x MT x B 2 powder, where x is 0.01-0.5, MT is rhenium element, tungsten element or iridium element;
    步骤2：在步骤1中得到的Os 1-xMT xB 2粉末中添加适量氧化镁，利用碾钵对添加氧化镁后的Os 1-xMT xB 2混合粉末进行充分碾磨至混合均匀，再进行过筛处理，得到混合均匀的MgO-Os 1-xMT xB 2粉末； Step 2: Add an appropriate amount of magnesium oxide to the Os 1-x MT x B 2 powder obtained in Step 1, and use a grinding bowl to fully grind the mixed powder of Os 1-x MT x B 2 after adding magnesium oxide until the mixture is uniform , And then sieved to obtain uniformly mixed MgO-Os 1-x MT x B 2 powder;
    步骤3：将步骤2得到的MgO-Os 1-xMT xB 2粉末进行烧结得到过渡金属硼化物硬质材料。 Step 3: Sinter the MgO-Os 1-x MT x B 2 powder obtained in Step 2 to obtain a transition metal boride hard material.
  2. 根据权利要求1所述的一种过渡金属硼化物硬质材料的制备方法，其特征在于，步骤1中所述锇粉与所述MT粉的混合物为锇-MT粉，所述锇-MT粉与所述硼粉的原粉摩尔比例为1∶(2-5)。The method for preparing a transition metal boride hard material according to claim 1, wherein in step 1, the mixture of the osmium powder and the MT powder is osmium-MT powder, and the osmium-MT powder The molar ratio of the original powder to the boron powder is 1: (2-5).
  3. 根据权利要求1所述的一种过渡金属硼化物硬质材料的制备方法，其特征在于，所述机械化学法采用的设备为高能球磨机、振动球磨机、行星式球磨机和场辅助球磨机中的一种或多种。The method for preparing a transition metal boride hard material according to claim 1, characterized in that the equipment used in the mechanochemical method is one of a high-energy ball mill, a vibration ball mill, a planetary ball mill, and a field-assisted ball mill Or more.
  4. 根据权利要求1所述的一种过渡金属硼化物硬质材料的制备方法，其特征在于，所述氧化镁粉的质量分数为1wt.％-12wt.％。The method for preparing a transition metal boride hard material according to claim 1, wherein the mass fraction of the magnesium oxide powder is 1wt.%-12wt.%.
  5. 根据权利要求1所述的一种过渡金属硼化物硬质材料的制备方法，其特征在于，在所述步骤2之后，所述步骤3之前还包括充分碾磨和过筛。The method for preparing a transition metal boride hard material according to claim 1, characterized in that, after the step 2, and before the step 3, it further includes sufficient grinding and sieving.
  6. 根据权利要求5所述的一种过渡金属硼化物硬质材料的制备方法，其特征在于，所述碾磨的时间为20-30min，所述过筛的筛孔直径为100-200目。The method for preparing a transition metal boride hard material according to claim 5, characterized in that the milling time is 20-30min, and the diameter of the sieve mesh is 100-200 mesh.
  7. 根据权利要求1所述的一种过渡金属硼化物硬质材料的制备方法，其特征在于，所述烧结为无压烧结、热压烧结或放电等离子烧结等烧结方法。The method for preparing a transition metal boride hard material according to claim 1, wherein the sintering is a sintering method such as pressureless sintering, hot press sintering or spark plasma sintering.
  8. 根据权利要求1所述的一种过渡金属硼化物硬质材料的制备方法，其特征在于，所述烧结温度为1400℃-1800℃。The method for preparing a transition metal boride hard material according to claim 1, wherein the sintering temperature is 1400°C-1800°C.
  9. 根据权利要求7所述的一种过渡金属硼化物硬质材料的制备方法，其特征在于，所述无压烧结的升温速率为3-15℃/min，保温时间为1-2h；所述热压烧结的升温速率为5-15℃/min，烧结压力为20MPa-70MPa，保温保压时间为1-2h；所述放电等离子烧结的升温速率为100-200℃/min，烧结压力为 20MPa-70MPa，保温保压时间为10-15min。The method for preparing a transition metal boride hard material according to claim 7, characterized in that, the temperature increase rate of the pressureless sintering is 3-15°C/min, the holding time is 1-2h; the heat The heating rate of pressure sintering is 5-15℃/min, the sintering pressure is 20MPa-70MPa, and the holding time is 1-2h; the heating rate of the spark plasma sintering is 100-200℃/min, and the sintering pressure is 20MPa- 70MPa, holding time is 10-15min.
  10. 一种过渡金属硼化物硬质材料，其特征在于，由权利要求1～9任意一项所述的过渡金属硼化物硬质材料的制备方法制得。A transition metal boride hard material, characterized by being prepared by the method for preparing a transition metal boride hard material according to any one of claims 1-9.
PCT/CN2019/071259 2018-12-27 2019-01-11 Hard transition metal boride material and preparation method therefor WO2020133585A1 (en)

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