WO2020103235A1 - 一种过渡金属硼化物硬质陶瓷材料及其制备方法和应用 - Google Patents

一种过渡金属硼化物硬质陶瓷材料及其制备方法和应用

Info

Publication number
WO2020103235A1
WO2020103235A1 PCT/CN2018/121024 CN2018121024W WO2020103235A1 WO 2020103235 A1 WO2020103235 A1 WO 2020103235A1 CN 2018121024 W CN2018121024 W CN 2018121024W WO 2020103235 A1 WO2020103235 A1 WO 2020103235A1
Authority
WO
WIPO (PCT)
Prior art keywords
transition metal
powder
ceramic material
metal boride
hard ceramic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2018/121024
Other languages
English (en)
French (fr)
Inventor
龙莹
黄路江
车金涛
林华泰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong University of Technology
Original Assignee
Guangdong University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangdong University of Technology filed Critical Guangdong University of Technology
Publication of WO2020103235A1 publication Critical patent/WO2020103235A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/5805—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/5805—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
    • C04B35/58064—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/404—Refractory metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/666—Applying a current during sintering, e.g. plasma sintering [SPS], electrical resistance heating or pulse electric current sintering [PECS]
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/668—Pressureless sintering
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Definitions

  • superhard materials are widely used in many fields such as precision manufacturing, aerospace, machinery and medical treatment, and are known as industrial "teeth".
  • the main superhard materials are diamond and cubic boron nitride, but the thermal stability and chemical inertness of diamond are relatively poor, and the cutting of iron-containing workpieces is easy to graphitize, and its use range is limited to a certain extent; cubic boron nitride is currently The second hardest material, although it can replace diamond on the cutting iron-containing workpieces, but the synthesis of cubic boron nitride requires high temperature and high pressure, and the cost is relatively high. Therefore, there is an urgent need to find a new type of super-hard material.
  • the research of new superhard materials mainly includes B-C-N-O series and transition metals (Re, Os, Ru, Ir) and light elements (B, N, C) series.
  • transition metals Re, Os, Ru, Ir
  • B, N, C light elements
  • ReB 2 type hexagonal structure OsB 2 for the first time by mechanochemical methods, but they found that part of the ReB 2 type hexagonal structure OsB 2 was transformed into orthogonal in the subsequent spark plasma sintering process. Structure, the occurrence of phase change will cause the performance of the material to decrease.
  • the researches of Chinese Patent CN107043260A and Chinese Patent CN107188565A found that ReB 2 type hexagonal structure OsB 2 undergoes a phase transition to an orthogonal structure at above 600 °C.
  • Re rhenium
  • Ir iridium
  • W tungsten
  • Os 1-x MT x B 2 (MT Re, W, Ir, etc.) transition metal boride hard material without sintering aid, through SPS sintering, hot pressing sintering and pressureless sintering block
  • the density of the material is not high, and the corresponding mechanical properties are also very low.
  • the present invention provides a transition metal boride hard material.
  • the material has the advantages of high density and excellent mechanical properties.
  • Another object of the present invention is to provide the application of the above transition metal boride hard material.
  • a transition metal boride hard ceramic material is Os 1-x MT x B 2 , where MT is Re, W or Ir; x is 0.01 to 0.5;
  • the transition metal boride hard ceramic material is made of Os, MT and B powder under argon gas by mechanochemical method to make Os 1-x MT x B 2 powder, wherein Os : MT: B mole in the mixed powder The ratio is (0.5 ⁇ 0.99) :( 0.01 ⁇ 0.5) :( 2.25 ⁇ 5); Add the sintering aid Ni to Os 1-x MT x B 2 powder, grind and sieve to treat Os 1 containing Ni -x MT x B 2 powder is obtained by sintering at 1400 ⁇ 1800 °C.
  • the addition amount of the sintering aid Ni is 1-12 wt.% Of the Os 1-x MT x B 2 powder; the B powder is amorphous, and the molar ratio of Os, MT and B is 0.9: 0.1: (2.25 ⁇ 5).
  • the density of the transition metal boride hard ceramic material is 85-99%, and the Vickers hardness value of the transition metal boride hard ceramic material is 1700-4000 Hv.
  • the main phase of the transition metal boride hard ceramic material has a hexagonal structure and Os 1-x MT x B 2 is ReB 2 type.
  • the preparation method of the transition metal boride hard ceramic material includes the following specific steps:
  • Ni - containing Os 1-x MT x B 2 powder obtained in step S2 is obtained by sintering at 1400-1800 ° C.
  • the equipment used in the mechanochemical method in step S1 is a high-energy ball mill, a vibrating ball mill, a planetary ball mill, or a plasma assisted high-energy ball mill.
  • the milling time in step S2 is 20-30 min, and the hole diameter of the sieve is 100-200 mesh.
  • the sintering method in step S3 is pressureless sintering, hot press sintering or spark plasma sintering.
  • the temperature increase rate in the pressureless sintering is 3-15 ° C / min, and the holding time is 1-2h; the temperature increase rate in the hot pressure sintering is 5-15 ° C / min, and the sintering pressure is 20-70MPa ,
  • the sintering pressure should be as large as possible in the interval of 20MPa-70MPa, and the holding time for heat preservation should be 1 ⁇ 2h;
  • the heating rate of the discharge plasma sintering is 100 ⁇ 200 °C / min, the sintering pressure is 20 ⁇ 70MPa, heat preservation
  • the pressure holding time is 10 ⁇ 15min.
  • transition metal boride hard ceramic material in the field of cutting tools or grinding industry.
  • the cutting tool is a dry cutting tool containing ferrous metal.
  • the present invention has the following beneficial effects:
  • the present invention intends to use the solid-liquid sintering principle to promote the compaction of the bulk during the sintering process by establishing the relationship between the sintering process and the amount of Ni added-the bulk material microstructure and the density-bulk material mechanical properties.
  • the method of chemical sintering is used to guide the adjustment of process parameters and the amount of Ni added to optimize the main phase, crystal structure, density and hardness of the material.
  • FIG. 1 is an XRD pattern of Os-Re-B mixed powder high-energy ball milling in Example 1 and Comparative Example 1 after 40 hours.
  • FIG 2 is a Os 0.9 Re 0.1 B 2 powder of Comparative Example 1 after 40h ball milling in Example 1 and Os 0.9 Re 0.1 B 2 powder added 3wt.% Ni sintering aid was 1750 °C, after hot pressing sintering 30MPa Block XRD pattern.
  • FIG 3 is a powder of Comparative Example 2 Os powder 0.9 Re 0.1 B 1 and Example 1 Os 0.9 Re 0.1 B added 3wt.% Ni sintering aid was 1750 °C, SEM cross-section of the block after sintering, and hot pressing 30MPa EDS photos.
  • FIG. 4 is a cross-sectional scanning photograph of a block of Os 0.9 Re 0.1 B 2 with 3 wt.% Ni sintering aid added to the Os 0.9 Re 0.1 B 2 powder in Example 1.
  • FIG. 4 is a cross-sectional scanning photograph of a block of Os 0.9 Re 0.1 B 2 with 3 wt.% Ni sintering aid added to the Os 0.9 Re 0.1 B 2 powder in Example 1.
  • FIG 5 is a Comparative Example 1 was added in 3 wt Os 0.9 Re 0.1 B 2 powder in Example 1 Os 0.9 Re 0.1 B 2 powder.% Ni sintering aid was 1750 °C, block polished surface after hot press sintering 30MPa Backscatter.
  • Os 0.9 Re 0.1 B 2 powder was synthesized using a high-energy ball mill with a model of 8000M from the US SPEX company, and then an appropriate amount of Ni powder was added as a sintering aid for densification and sintering.
  • high-purity osmium powder (Os), rhenium powder (Re) (where 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.
  • Os 0.9 Re 0.1 B 2 powder added with 3wt.% Ni was sintered in a hot-press furnace at 1750 ° C, 30MPa, and kept under heat and pressure for 1h to obtain a bulk material of Os 0.9 Re 0.1 B 2 added with 3wt.% Ni.
  • Os 0.9 Re 0.1 B 2 powder was synthesized using a high-energy ball mill model 8000M of the American SPEX company, and then densified and sintered.
  • Os high-purity osmium powder
  • Re rhenium powder
  • B boron powder
  • 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 obtained after high-energy ball milling for 40 h was sintered in a hot-press furnace at 1750 ° C. and 30 MPa, and kept under heat and pressure for 1 h to obtain Os 0.9 Re 0.1 B 2 bulk material.
  • Fig. 2 is the block of the Os 0.9 Re 0.1 B 2 powder after being ball milled for 40 hours in Comparative Example 1 and the Os 0.9 Re 0.1 B 2 powder in Example 1 after adding 3wt.% Ni sintering aid and sintered by hot pressing at 1750 °C and 30MPa XRD pattern. It can be seen from (a) in FIG. 2 that the Os 0.9 Re 0.1 B 2 powder and the Os 0.9 Re 0.1 B 2 powder after 40 h of ball milling are added with 3wt.% Ni for hot-press sintering at 1750 ° C and 30 MPa.
  • FIG 3 is a powder of Comparative Example 2 Os powder 0.9 Re 0.1 B 1 and Example 1 Os 0.9 Re 0.1 B added 3wt.% Ni sintering aid was 1750 °C, SEM cross-section of the block after sintering, and hot pressing 30MPa EDS photos. Among them, (a) and (b) are without added Ni, and (c) and (d) are added with 3wt.% Ni.
  • Fig. 4 is a scanning photograph of the cross-section of the Os 0.9 Re 0.1 B 2 block with 3 wt.% Ni sintering aid added to the Os 0.9 Re 0.1 B 2 powder in Example 1, and it can be seen from Fig. 4 that Os and Re are present in the sintered sample , B, O and Ni elements, and the distribution of each element is uneven, in which Ni element is mainly distributed at the grain boundary.
  • Comparative Example 5 is added 1 Os 0.9 Re 0.1 B 2 powder in Example 1 Os 0.9 Re 0.1 B 2 powder 3wt.% Ni sintering aid was 1750 °C, block polished surface after hot press sintering back 30MPa scattering.
  • Example 2 The difference from Example 1 is that 6wt.% Ni is added as a sintering aid.
  • Example 2 The difference from Example 1 is that 9wt.% Ni is added as a sintering aid.
  • Example 2 The difference from Example 1 is that 12 wt.% Ni is added as a sintering aid.
  • Example 2 The difference from Example 1 is that Os 0.9 Re 0.1 B 2 powder added with 3wt.% Ni is sintered with SPS at 1600 ° C, 40MPa, and holding pressure for 10 minutes.
  • Example 2 The difference from Example 1 is that Os 0.9 Re 0.1 B 2 powder added with 3wt.% Ni is sintered in a pressure-free furnace at 1700 ° C and a heat preservation pressure for 90 minutes.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Products (AREA)

Abstract

一种过渡金属硼化物硬质陶瓷材料及其制备方法和应用。所述过渡金属硼化物硬质陶瓷材料为Os l-xMT xB 2，其中，MT为Re，W或Ir；x为0.01～0.5；是在惰性气体下，利用机械化学法将Os、MT和B粉末混合制成Os l-xMT xB 2粉末；在Os l-xMT xB粉末中添加烧结助剂Ni，碾磨后过筛处理，将含Ni的Os l-xMT xB 2粉末经1400～1800℃烧结制得。通过添加Ni作为烧结助剂，降低块体的烧结温度、得到致密度较高的块体材料，改善了块体材料的力学性能。该陶瓷材料可以用于切削刀具和研磨等工业领域。

Description

一种过渡金属硼化物硬质陶瓷材料及其制备方法和应用 技术领域
本发明属于无机非金属材料技术领域，更具体地，涉及一种过渡金属硼化物硬质陶瓷材料Os 1-xMT xB 2(MT＝Re，W，Ir)及其制备方法和应用。
背景技术
随着工业化的快速发展，对高性能材料的需求越来越大。超硬材料广泛应用于精密制造、航空航天、机械和医疗等众多领域，被称为工业上的“牙齿”。目前主要的超硬材料是金刚石和立方氮化硼，但金刚石的热稳定性和化学惰性比较差，且切削含铁类工件容易石墨化，其使用范围受到一定的限制；立方氮化硼是目前第二硬的材料，虽在切屑含铁类工件上可替代金刚石，但立方氮化硼的合成需要在高温高压下，成本比较高。因此，迫切需要寻找一种新型的超硬材料。
新型超硬材料的研究主要有B-C-N-O系列和过渡金属(Re、Os、Ru、Ir)与轻元素(B、N、C)系列。在B-C-N-O系列化合物的研究中虽取得了很大的进展，但其合成的条件苛刻，制造成本过高，所以为了寻求物美价廉的超硬材料，很多研究者们投身于过渡金属与轻元素的研究。
在过渡金属元素与轻元素的研究中，锇因其具有最高的价电子密度而受到关注。研究人员通过第一性原理计算预测OsB 2具有三种类型的结构：(1)RuB 2型正交结构(2)ReB 2型六方结构(3)AlB 2型六方结构，并且计算结果表明六方结构的硬度要高于正交结构。但由于ReB 2型六方结构OsB 2为亚稳相，一直以来，实验研究制备的OsB 2均为RuB 2型正交结构。如美国专利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，但他们在随后的放电等离子烧结过程中，发现部分ReB 2型六方结构OsB 2转变为正交结构，相变的发生会导致材料性能降低。中国专利CN107043260A和中国专利CN107188565A的研究发现ReB 2型六方结构的OsB 2在600℃以上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。目前，Os 1-xMT xB 2(MT＝Re，W，Ir等)过渡金属硼化物硬质材料在未添加烧结助剂情况下，通过SPS烧结、热压烧结和无压烧结后块体材料的致密度都不高，相应的力学性能表征也很低。
发明内容
为了解决上述现有技术存在的不足和缺点，本发明提供了一种过渡金属硼化物硬质材料。该材料具有致密度高、力学性能优异等优点。
本发明的另一目的在于提供一种上述过渡金属硼化物硬质材料的制备方法。该方法通过添加烧结助剂Ni提高Os 1-xMT xB 2(MT＝Re，W，Ir)过渡金属硼化物硬质材料致密度和力学性能。
本发明的再一目的在于提供上述过渡金属硼化物硬质材料的应用。
本发明的目的通过下述技术方案来实现：
一种过渡金属硼化物硬质陶瓷材料，所述过渡金属硼化物硬质陶瓷材料为Os 1-xMT xB 2，其中，MT为Re，W或Ir；x为0.01～0.5；
所述过渡金属硼化物硬质陶瓷材料是在氩气下，利用机械化学法将Os、MT和B粉末混合制成Os 1-xMT xB 2粉末，其中混合粉末中Os∶MT∶B摩尔比为(0.5～0.99)∶(0.01～0.5)∶(2.25～5)；在Os 1-xMT xB 2粉末中添加烧结助剂Ni，碾磨后过筛处理，将含Ni的Os 1-xMT xB 2粉末经1400～1800℃烧结制得。
优选地，所述烧结助剂Ni的添加量为Os 1-xMT xB 2粉末的1～12wt.％；所述的B粉为非晶态，所述Os、MT和B的摩尔比为0.9∶0.1∶(2.25～5)。
优选地，所述过渡金属硼化物硬质陶瓷材料的致密度为85～99％，所述过渡金属硼化物硬质陶瓷材料的维氏硬度值为1700～4000Hv。
优选地，所述过渡金属硼化物硬质陶瓷材料的主相具有六方结构的Os 1-xMT xB 2为ReB 2型。
所述的过渡金属硼化物硬质陶瓷材料的制备方法，包括以下具体步骤：
S1.在惰性气体下，利用机械化学法将Os、MT和B粉混合制成Os 1-xMT xB 2粉末；
S2.在Os 1-xMT xB 2粉末中添加烧结助剂Ni，碾磨后过筛处理；
S3.将步骤S2得到的含Ni的Os 1-xMT xB 2粉末，在1400～1800℃经烧结制得。
优选地，步骤S1中所述机械化学法采用的设备为高能球磨机、振动球磨机、行星式球磨机或等离子体辅助高能球磨机。
优选地，步骤S2中所述碾磨的时间为20～30min，所述筛的孔直径为100～200目。
优选地，步骤S3中所述烧结的方法为无压烧结、热压烧结或放电等离子烧 结。
更为优选地，所述无压烧结中升温速率为3～15℃/min，保温时间为1～2h；所述热压烧结中升温速率为5～15℃/min，烧结压力为20～70MPa，烧结压力在区间20MPa-70MPa中尽可能选择较大的压力，保温保压时间为1～2h；所述放电等离子烧结中升温速率为100～200℃/min，烧结压力为20～70MPa，保温保压时间为10～15min。
所述的过渡金属硼化物硬质陶瓷材料在切削刀具或研磨工业领域中的应用。
优选地，所述切削刀具为含铁类金属的干切削刀具。
与现有技术相比，本发明具有以下有益效果：
1.本发明选择合适的Ni添加量，获得致密度高，硬度高、块体主相可控的过渡金属硼化物硬质陶瓷材料Os 1-xMT xB 2(MT＝Re，W，Ir)，其主相具有六方结构的Os 1-xMT xB 2为ReB 2型。
2.本发明通过控制烧结参数，获得较高的块体材料致密度，致密度在85～99％之间。
3.本发明拟通过建立烧结工艺及Ni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，在烧结过程中利用固液相烧结原理来促进块体的致密化烧结的方法，用于指导工艺参数和Ni添加量的调控，实现对材料主相、晶体结构、致密度和硬度的优化。
4.本发明制备的过渡金属硼化物硬质陶瓷材料Os 1-xMT xB 2(MT＝Re，W，Ir)可以有效用于切削刀具，特别是含铁类金属的高速干切削。
附图说明
图1是实施例1和对比例1中Os-Re-B混合粉末高能球磨40h后的XRD图。
图2是对比例1中经球磨40h后的Os 0.9Re 0.1B 2粉末和实施例1中Os 0.9Re 0.1B 2粉末中添加3wt.％Ni烧结助剂经1750℃、30MPa热压烧结后的块体XRD图。
图3是对比例1中Os 0.9Re 0.1B 2粉末和实施例1中Os 0.9Re 0.1B 2粉末中添加3wt.％Ni烧结助剂经1750℃、30MPa热压烧结后的块体断面SEM和EDS照片。
图4是实施例1中Os 0.9Re 0.1B 2粉末中添加3wt.％Ni烧结助剂的Os 0.9Re 0.1B 2块体断面面扫照片。
图5是对比例1中Os 0.9Re 0.1B 2粉末和实施例1中Os 0.9Re 0.1B 2粉末中添加3 wt.％Ni烧结助剂经1750℃、30MPa热压烧结后的块体抛光面背散射。
具体实施方式
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。
实施例1
(1)以Os 0.9Re 0.1B 2粉末为例，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粉体，然后添加适量的Ni粉末作为烧结助剂进行致密化烧结。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。
(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。
(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Ni粉末，利用碾钵碾磨混合均匀，再对混合均匀后的粉末过筛处理，筛孔规格为200目。
(4)将添加3wt.％Ni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.％Ni的Os 0.9Re 0.1B 2块体材料。
对比例1
(1)以Os 0.9Re 0.1B 2粉末为例，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粉体，然后进行致密化烧结。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。
(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。
(3)取一定量高能球磨40h后的Os-Re-B混合粉末，对其进行过筛处理，筛孔规格为200目。
(4)将高能球磨40h后得到的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。
图1为实施例1和对比例1中Os-Re-B混合粉末高能球磨40h后的XRD图，其中(Os，Re＝9∶1)∶B＝1∶3。由图1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。
图2为对比例1中球磨40h后的Os 0.9Re 0.1B 2粉末和实施例1中Os 0.9Re 0.1B 2粉末中添加3wt.％Ni烧结助剂经1750℃、30MPa热压烧结后的块体XRD图。由图2中(a)可知，在球磨40h后的Os 0.9Re 0.1B 2粉末和Os 0.9Re 0.1B 2粉末中添加3wt.％Ni进行1750℃、30MPa热压烧结，二者烧结后的XRD图谱中均只存在六方结构的Os 0.9Re 0.1B 2衍射峰，说明烧结助剂Ni的添加没有影响其主相的变化。再结合图2中(b)，可以看出添加3wt.％Ni烧结助剂的块体XRD衍射峰存在一定量的偏移，其原因可能是添加的烧结助剂Ni固溶到Os 0.9Re 0.1B 2晶体中，引起晶格畸变，从而出现峰位偏移。
图3为对比例1中Os 0.9Re 0.1B 2粉末和实施例1中Os 0.9Re 0.1B 2粉末中添加3wt.％Ni烧结助剂经1750℃、30MPa热压烧结后的块体断面SEM和EDS照片。其中，(a)和(b)为无添加Ni，(c)和(d)添加3wt.％Ni。由图3(a)和(c)可知，无添加Ni、添加3wt.％Ni烧结助剂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，从图3中可以看出，均有气孔存在，致密度不高但添加3wt.％Ni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85.3％。(b)和(d)分别是(a)和(b)的局部放大图，由图可知，图3(b)中各晶粒烧结在一起，结合相应的EDS可知，其晶界之间仅存在多余B，不存在其他的第二相；而在添加烧结助剂Ni的图3(d)中晶界处，结合其相对应的EDS图可知，其晶界处除了存在多余的B外，还存在有Ni元素。
图4是实施例1中Os 0.9Re 0.1B 2粉末中添加3wt.％Ni烧结助剂的Os 0.9Re 0.1B 2块体断面面扫照片，由图4可知烧结后的样品中存在Os、Re、B、O和Ni元素，且各元素分布不均，其中Ni元素主要分布在晶界处。图5为对比例1中Os 0.9Re 0.1B 2粉末和实施例1中Os 0.9Re 0.1B 2粉末中添加3wt.％Ni烧结助剂经1750℃、30MPa热压烧结后的块体抛光面背散射。其中，(a)无添加Ni和(b)添加 3wt.％Ni。从图5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。
实施例3
与实施例1不同之处在于：添加6wt.％Ni作为烧结助剂。
实施例4
与实施例1不同之处在于：添加9wt.％Ni作为烧结助剂。
实施例5
与实施例1不同之处在于：添加12wt.％Ni作为烧结助剂。
实施例6
与实施例1不同之处在于：将添加3wt.％Ni的Os 0.9Re 0.1B 2粉末采用SPS进行1600℃，40MPa，保温保压10min烧结。
实施例7
与实施例1不同之处在于：将添加3wt.％Ni的Os 0.9Re 0.1B 2粉末采用无压炉进行1700℃，保温保压90min烧结。
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。

Claims (10)

  1. 一种过渡金属硼化物硬质陶瓷材料，其特征在于，所述过渡金属硼化物硬质陶瓷材料为Os 1-xMT xB 2，其中，MT为Re，W或Ir；x为0.01～0.5；
    所述过渡金属硼化物硬质陶瓷材料是在氩气下，利用机械化学法将Os、MT和B粉末混合制成Os 1-xMT xB 2粉末，其中混合粉末中Os∶MT∶B摩尔比为(0.5～0.99)∶(0.01～0.5)∶(2.25～5)；在Os 1-xMT xB 2粉末中添加烧结助剂Ni，碾磨后过筛处理，将含Ni的Os 1-xMT xB 2粉末经1400～1800℃烧结制得。
  2. 根据权利要求1所述的过渡金属硼化物硬质陶瓷材料，其特征在于，所述烧结助剂Ni的添加量为Os 1-xMT xB 2粉末的1～12wt.％；所述的B粉为非晶态，所述Os、MT和B的摩尔比为0.9∶0.1∶(2.25～5)。
  3. 根据权利要求1所述的过渡金属硼化物硬质陶瓷材料，其特征在于，所述过渡金属硼化物硬质陶瓷材料的致密度为85～99％，所述过渡金属硼化物硬质陶瓷材料的维氏硬度值为1700～4000Hv。
  4. 根据权利要求1所述的过渡金属硼化物硬质陶瓷材料，其特征在于，所述过渡金属硼化物硬质陶瓷材料的主相具有六方结构的Os 1-xMT xB 2为ReB 2型。
  5. 根据权利要求1-4任一项所述的过渡金属硼化物硬质陶瓷材料的制备方法，其特征在于，包括以下具体步骤：
    S1.在惰性气体下，利用机械化学法将Os、MT和B粉混合制成Os 1-xMT xB 2粉末；
    S2.在Os 1-xMT xB 2粉末中添加烧结助剂Ni，碾磨后过筛处理；
    S3.将步骤S2得到的含Ni的Os 1-xMT xB 2粉末，在1400～1800℃经烧结得到过渡金属硼化物硬质陶瓷材料。
  6. 根据权利要求5所述的过渡金属硼化物硬质陶瓷材料的制备方法，其特征在于，步骤S1中所述机械化学法采用的设备为高能球磨机、振动球磨机、行星式球磨机或等离子体辅助高能球磨机。
  7. 根据权利要求5所述的过渡金属硼化物硬质陶瓷材料的制备方法，其特征在于，步骤S2中所述碾磨的时间为20～30min，所述筛的孔直径为100～200目。
  8. 根据权利要求5所述的过渡金属硼化物硬质陶瓷材料的制备方法，其特征在于，步骤S3中所述烧结的方法为无压烧结、热压烧结或放电等离子烧结。
  9. 根据权利要求8所述的过渡金属硼化物硬质陶瓷材料的制备方法，其特征在于，所述无压烧结中升温速率为3～15℃/min，保温时间为1～2h；所述热压烧 结中升温速率为5～15℃/min，烧结压力为20～70MPa，保温保压时间为1～2h；所述放电等离子烧结中升温速率为100～200℃/min，烧结压力为20～70MPa，保温保压时间为10～15min。
  10. 权利要求1-4任一项所述的过渡金属硼化物硬质陶瓷材料在切削刀具或研磨工业领域中的应用。
PCT/CN2018/121024 2018-11-19 2018-12-14 一种过渡金属硼化物硬质陶瓷材料及其制备方法和应用 Ceased WO2020103235A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811378289.5A CN109437915A (zh) 2018-11-19 2018-11-19 一种过渡金属硼化物硬质陶瓷材料及其制备方法和应用
CN201811378289.5 2018-11-19

Publications (1)

Publication Number Publication Date
WO2020103235A1 true WO2020103235A1 (zh) 2020-05-28

Family

ID=65553784

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/121024 Ceased WO2020103235A1 (zh) 2018-11-19 2018-12-14 一种过渡金属硼化物硬质陶瓷材料及其制备方法和应用

Country Status (2)

Country Link
CN (1) CN109437915A (zh)
WO (1) WO2020103235A1 (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109851367B (zh) * 2019-03-11 2021-08-10 华南理工大学 一种棒状(Zr,Hf,Ta,Nb)B2高熵纳米粉体及其制备方法
CN110526715B (zh) * 2019-08-01 2022-01-28 广东工业大学 一种三元钨钌硼化物陶瓷材料及其制备方法与应用
CN110655408B (zh) * 2019-11-13 2021-10-08 哈尔滨工业大学 一种单相碳硼化物固溶体陶瓷材料的制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102924086A (zh) * 2012-11-22 2013-02-13 山东轻工业学院 添加六方氮化硼的硼化钛基自润滑陶瓷刀具材料的制备方法
CN103058662A (zh) * 2013-01-31 2013-04-24 山东轻工业学院 二硼化钛基纳米复合自润滑陶瓷刀具材料及其制备方法
US20140219902A1 (en) * 2013-01-16 2014-08-07 University Of Central Florida Research Foundation, Inc. MECHANOCHEMICAL SYNTHESIS OF HEXAGONAL OsB2
CN107043260A (zh) * 2016-12-07 2017-08-15 广东工业大学 一种新型三元锇铼二硼化物(Os1‑xRexB2)硬质材料及其制备方法
CN107140987A (zh) * 2017-03-31 2017-09-08 广东工业大学 一种Os2B3硬质材料及其制备和应用
CN107188565A (zh) * 2017-05-27 2017-09-22 广东工业大学 一种三元系锇钨二硼化物硬质材料及其制备方法和应用

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4836943B2 (ja) * 2004-05-11 2011-12-14 ザ リージェンツ オブ ザ ユニバーシティー オブ カリフォルニア 二ホウ化オスミウム化合物、工具、表面コーティング材、研磨材、コーティング方法、研磨方法、及び、切削方法
CN103172380A (zh) * 2013-02-04 2013-06-26 常熟华融太阳能新型材料科技有限公司 非氧化物陶瓷粉体的喷雾造粒方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102924086A (zh) * 2012-11-22 2013-02-13 山东轻工业学院 添加六方氮化硼的硼化钛基自润滑陶瓷刀具材料的制备方法
US20140219902A1 (en) * 2013-01-16 2014-08-07 University Of Central Florida Research Foundation, Inc. MECHANOCHEMICAL SYNTHESIS OF HEXAGONAL OsB2
CN103058662A (zh) * 2013-01-31 2013-04-24 山东轻工业学院 二硼化钛基纳米复合自润滑陶瓷刀具材料及其制备方法
CN107043260A (zh) * 2016-12-07 2017-08-15 广东工业大学 一种新型三元锇铼二硼化物(Os1‑xRexB2)硬质材料及其制备方法
CN107140987A (zh) * 2017-03-31 2017-09-08 广东工业大学 一种Os2B3硬质材料及其制备和应用
CN107188565A (zh) * 2017-05-27 2017-09-22 广东工业大学 一种三元系锇钨二硼化物硬质材料及其制备方法和应用

Also Published As

Publication number Publication date
CN109437915A (zh) 2019-03-08

Similar Documents

Publication Publication Date Title
JP5838289B2 (ja) 超高硬度ナノ双晶窒化ホウ素バルク材料及びその合成方法
US10259751B2 (en) Tungsten carbide-cubic boron nitride composite material and preparation method thereof
CN106132604B (zh) 立方晶氮化硼烧结体切削工具
JP6293669B2 (ja) 焼結された立方晶窒化ホウ素切削工具
CN109851367B (zh) 一种棒状(Zr,Hf,Ta,Nb)B2高熵纳米粉体及其制备方法
AU2009237260A1 (en) Super-hard enhanced hard-metals
Sun et al. Reactive spark plasma sintering of binderless WC ceramics at 1500 C
WO2012023473A9 (ja) ダイヤモンド多結晶体およびその製造方法
CN104755420A (zh) 多晶金刚石、其制造方法和工具
JP5677638B1 (ja) 切削工具
CN106167413B (zh) 一种原位合成莫来石晶须增韧90氧化铝陶瓷及制备方法
CN108557834A (zh) 一种铬掺杂的四硼化钨超硬材料的制备方法
WO2020103235A1 (zh) 一种过渡金属硼化物硬质陶瓷材料及其制备方法和应用
JPWO2020070776A1 (ja) ダイヤモンド多結晶体、ダイヤモンド多結晶体を備える工具及びダイヤモンド多結晶体の製造方法
JP5340028B2 (ja) 切削工具
CN106587088B (zh) 一种新型三元锇钌硼化物硬质材料及其制备方法
CN110436928A (zh) 高性能纳米孪晶碳化硼陶瓷块体材料及其制备方法
CN107140987A (zh) 一种Os2B3硬质材料及其制备和应用
Yu-Ming et al. The effect of Sintering Temperature on the Structure and Properties of Corundum/mullite Ceramics
US9573249B2 (en) Boron nitride composites
JP2010189203A (ja) ＳｉＣ系耐摩耗材料およびその製造方法
CN108726526A (zh) 一种铼掺杂的四硼化钨材料的制备方法
Zhang et al. Effect of Si coating on prevention of diamond degradation in diamond/glass composite
CN103667845B (zh) 一种利用高温超高压制备纳米结构碳化钨复合块材的方法
CN107043260A (zh) 一种新型三元锇铼二硼化物(Os1‑xRexB2)硬质材料及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18941060

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18941060

Country of ref document: EP

Kind code of ref document: A1