B6O/TiB2复合材料的高温高压反应烧结

张瑜 贺端威 王永坤 刘银娟 胡艺 王江华

张瑜, 贺端威, 王永坤, 刘银娟, 胡艺, 王江华. B6O/TiB2复合材料的高温高压反应烧结[J]. 高压物理学报, 2015, 29(3): 178-184. doi: 10.11858/gywlxb.2015.03.003
引用本文: 张瑜, 贺端威, 王永坤, 刘银娟, 胡艺, 王江华. B6O/TiB2复合材料的高温高压反应烧结[J]. 高压物理学报, 2015, 29(3): 178-184. doi: 10.11858/gywlxb.2015.03.003
ZHANG Yu, HE Duan-Wei, WANG Yong-Kun, LIU Yin-Juan, HU Yi, WANG Jiang-Hua. Reactive Sintering of B6O/TiB2 Composites at High Temperature and High Pressure[J]. Chinese Journal of High Pressure Physics, 2015, 29(3): 178-184. doi: 10.11858/gywlxb.2015.03.003
Citation: ZHANG Yu, HE Duan-Wei, WANG Yong-Kun, LIU Yin-Juan, HU Yi, WANG Jiang-Hua. Reactive Sintering of B6O/TiB2 Composites at High Temperature and High Pressure[J]. Chinese Journal of High Pressure Physics, 2015, 29(3): 178-184. doi: 10.11858/gywlxb.2015.03.003

B6O/TiB2复合材料的高温高压反应烧结

doi: 10.11858/gywlxb.2015.03.003
基金项目: 国家自然基金(51472171,11427810)
详细信息
    作者简介:

    张瑜(1988-), 女, 硕士研究生, 主要从事超硬及复合材料的高压合成与应用研究.E-mail:815616997@qq.com

    通讯作者:

    贺端威(1969—), 男,教授,博士生导师,主要从事高压科学与技术、超硬材料及纳米材料的研究.E-mail:duanweihe@scu.edu.cn

  • 中图分类号: O521.21

Reactive Sintering of B6O/TiB2 Composites at High Temperature and High Pressure

  • 摘要: 以B和TiO2为初始原料,依据压力可抑制原子长程扩散的动力学效应,通过高温高压(4~5 GPa,1 200~1 500 ℃)一步反应烧结法制备B6O/TiB2复合材料。当B和TiO2物质的量之比为14.0:0.8时,在5 GPa、1 200 ℃、保温30 min条件下得到的烧结样品性能较好,非晶硼(纯度93%~94%)过量混合粉末样品的硬度最高约为29 GPa,高纯晶体硼(纯度99.99%)过量混合粉末样品的硬度最高约为32 GPa,相对密度可高达99%。实验结果表明:高压抑制晶粒过度长大,同时又有利于B6O的合成,使其合成温度比常压下有所降低;在高压反应烧结过程中,合成的第二相TiB2晶粒和样品中的非晶相有效地消耗了残余应力,起到了增韧作用。

     

  • 图  高压高温反应烧结实验样品组装图

    Figure  1.  Sample assembly schematic of reactive sintering experiment for producing B6O/TiB2 materials at high pressure and high temperature

    图  真空热处理和高温高压烧结30 min后, 非晶硼完全混合粉末样品的XRD图谱

    Figure  2.  Comparison of XRD patterns showing phase compositions of a reactive sintered mixture consisting of amorphous B and TiO2 (molar ratio:14:1) after 30 minutes' treatment of vacuum heating and high-pressure high-temperature sintering

    图  过量晶体硼块体烧结(5 GPa,1 200 ℃,60 min)样品的SEM图(深灰色:TiB2晶粒,亮灰色:B6O晶粒)

    Figure  3.  SEM image showing distributed TiB2 grains (dark grey) and B6O grains (bright grey) of a reactive sintered mixture consisting of crystalline B and TiO2 (molar ratio: 14.0:0.8) by high-pressure high-temperature (5 GPa, 1 200 ℃, 60 min) sintering

    图  不同条件下的维式硬度值

    Figure  4.  Vicker's hardness values under different conditions

    图  过量晶体硼块体烧结(5 GPa,1 200 ℃,60 min)样品抛光面裂纹偏转和弯曲的SEM图

    Figure  5.  SEM micrographs of the polished surfaces with deflecting and curving crack around TiB2 grains of a reactive sintered mixture consisting of crystalline B and TiO2 (molar ratio:14.0:0.8) under high-pressure high-temperature condition (5 GPa, 1 200 ℃, 60 min)

    表  1  B6O/TiB2样品在不同条件下测量的密度和相对密度

    Table  1.   Measured density and relative density of B6O/TiB2 samples at different experiment conditions

    Initial reactive
    materials
    Molar
    ratio
    Sintering conditions ρactual/
    (g/cm3)
    κ/
    (%)
    Pressure/(GPa) Temperature/(℃) Dwelling time/(min)
    Ba+TiO2 14.0:1.0 4.0 1 200 30 2.62 90.2
    Ba+TiO2 14.0:1.0 4.5 1 200 30 2.67 91.9
    Ba+TiO2 14.0:1.0 5.0 1 200 30 2.76 95.0
    Ba+TiO2 14.0:0.8 5.0 1 200 30 2.68 95.3
    Bc+TiO2 14.0:0.8 5.0 1 200 30 2.80 99.4
    Note:Superscript ‘a’ means amorphous while ‘c’ means crystalline.
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  • [1] Petrak D R, Ruh R, Atkins G R. Mechanical properties of hot-pressed boron suboxide and boron[J]. Am Ceram Soc Bull, 1974, 53: 569-573. http://ci.nii.ac.jp/naid/80012972638
    [2] He D W, Shieh S R, Duffy T S. Strength and equation of state of boron suboxide from radial X-ray diffraction in a diamond cell under nonhydrostatic compression[J]. Phys Rev B, 2004, 70(18): 184121. doi: 10.1103/PhysRevB.70.184121
    [3] He D W, Akaishi M, Scott B L, et al. Growth of boron suboxide crystals in the B-B2O3 system at high pressure and high temperature[J]. J Mater Res, 2002, 17(2): 284-290. doi: 10.1557/JMR.2002.0041
    [4] Hubert H, Devouard B, Garvie L A J, et al. Icosahedral packing of B12 icosahedra in boron suboxide(B6O)[J]. Nature, 1998, 391(6665): 376-378. doi: 10.1038/34885
    [5] He D W, Zhao Y S, Daemen L, et al. Boron suboxide: As hard as cubic boron nitride[J]. Appl Phys Lett, 2002, 81(4): 643-645. doi: 10.1063/1.1494860
    [6] Rizzo H F, Simmons W C, Bielstein H O. The existence and formation of the solid B6O[J]. J Electrochem Soc, 1962, 109(11): 1079-1082. doi: 10.1149/1.2425241
    [7] Lee S, Kim S W, Bylander D M, et al. Crystal structure, formation enthalpy, and energy bands of B6O[J]. Phys Rev B, 1991, 44(8): 3550. doi: 10.1103/PhysRevB.44.3550
    [8] Badzian A R. Superhard material comparable in hardness to diamond[J]. Appl Phys Lett, 1988, 53(25): 2495-2497. doi: 10.1063/1.100528
    [9] Kobayashi M, Higashi I, Brodhag C, et al. Structure of B6O boron-suboxide by Rietveld refinement[J]. J Mater Sci, 1993, 28(8): 2129-2134. doi: 10.1007/BF00367573
    [10] Andreev Y G. Superhard boron-rich borides and studies of the BCN system[J]. Mater Sci Eng A, 1996, 209(1): 16-22. http://www.sciencedirect.com/science/article/pii/0921509395100954
    [11] Liu X Y, Zhao X D, Hou W M, et al. A new route for the synthesis of boron suboxide B7O[J]. J Alloy Compd, 1995, 223(1): L7-L9. doi: 10.1016/0925-8388(95)01558-2
    [12] Olofsson M, Lundström T. Synthesis and structure of non-stoichiometric B6O[J]. J Alloy Compd, 1997, 257(1): 91-95. http://www.sciencedirect.com/science/article/pii/S092583889700008X
    [13] Hubert H, Garvie L A J, Devouard B, et al. High-pressure, high-temperature synthesis and characterization of boron suboxide(B6O)[J]. Chem Mater, 1998, 10(6): 1530-1537. doi: 10.1021/cm970433+
    [14] Yu S W, Wang G H, Yin S Y, et al. Nanostructured films of Boron suboxide by pulsed laser deposition[J]. Phys Lett A, 2000, 268(4): 442-447. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=1675d64bb4fd1ec150de42e33a9d74c6
    [15] Shabalala T C, McLachlan D S, Sigalas I, et al. Hard and tough boron suboxide based composites[J]. Ceram Int, 2008, 34(7): 1713-1717. doi: 10.1016/j.ceramint.2007.05.010
    [16] Holcombe C E Jr, Horne O J Jr. Method for preparing boron suboxide: US, 3660031[P]. 1972.
    [17] Johnson O T, Sigalas I, Herrmann M. Comparative study of reactive and non-reactive sintering route for producing B6O-TiB2 materials[J]. Ceram Int, 2014, 40(1): 573-579. doi: 10.1016/j.ceramint.2013.05.140
    [18] Grabis J, Rašmane Dz, Krūmia A, et al. Preparation of boron suboxide nanoparticles and their processing[C]//Proceedings of the IOP Conference Series: Materials Science and Engineering. Bristol: IOP Publishing, 2011.
    [19] Sasai R, Fukatsu H, Kojima T, et al. High pressure consolidation of B6O-diamond mixtures[J]. J Mater Sci, 2001, 36(22): 5339-5343. doi: 10.1023/A:1012499214307
    [20] Itoh H, Yamamoto R, Iwahara H. B6O-cBN composites prepared by high-pressure sintering[J]. J Am Ceram Soc, 2000, 83(3): 501-506. doi: 10.1111/j.1151-2916.2000.tb01224.x/full
    [21] Itoh H, Maekawa I, Iwahara H. Microstructure and mechanical properties of B6O-B4C sintered composites prepared under high pressure[J]. J Mater Sci, 2000, 35(3): 693-698. doi: 10.1023/A:1004753116816
    [22] Thiele M, Herrmann M, Michaelis A. B6O materials with Al2O3/Y2O3 additives densified by FAST/SPS and HIP[J]. J Eur Ceram Soc, 2013, 33(13/14): 2375-2390. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=20fa5a4de61b6f10593af1fd83e227c9
    [23] Chen C, He D W, Kou Z L, et al. B6O-based composite to rival polycrystalline cubic boron bitride[J]. Adv Mater, 2007, 19(23): 4288-4291. doi: 10.1002/adma.200700836
    [24] Thiele M, Herrmann M, Räthel J, et al. Preparation and properties of B6O/TiB2-composites[J]. J Eur Ceram Soc, 2012, 32(8): 1821-1835. doi: 10.1016/j.jeurceramsoc.2011.12.034
    [25] Qian J, Zerda T W, He D W, et al. Micron diamond composites with nanocrystalline silicon carbide bonding[J]. J Mater Res, 2003, 18(5): 1173-1178. doi: 10.1557/JMR.2003.0161
    [26] Xu C, He D W, Wang H K, et al. Synthesis of novel superhard materials under ultrahigh pressure[J]. Chinese Sci Bull, 2014: 1-7. http://kns.cnki.net/KCMS/detail/detail.aspx?dbcode=CJFD&filename=JXTW201436014
    [27] He D W, Zhao Q, Wang W H, et al. Pressure-induced crystallization in a bulk amorphous Zr-based alloy[J]. J Non-Cryst Solids, 2002, 297(1): 84-90. doi: 10.1016/S0022-3093(01)00906-1
    [28] Jiang Z P, Rhine W E. Preparation of titanium diboride from titanium alkoxides and boron powder[J]. Chem Mater, 1992, 4(3): 497-500. doi: 10.1021/cm00021a002
    [29] 李良福.新型无钨硬质合金的研制状况[J].硬质合金, 1999, 16(2): 65-70. http://www.cnki.com.cn/Article/CJFDTotal-YZHJ199902000.htm

    Li L F. The study of new-style tungsten-free cemented carbide[J]. Cemented Carbide, 1999, 16(2): 65-70. (in Chinese) http://www.cnki.com.cn/Article/CJFDTotal-YZHJ199902000.htm
    [30] Itoh H, Maekawa I, Iwahara H. High pressure sintering of B6O powder and properties of the sintered compact[J]. J Soc Mater Sci, 1998, 47(10): 1000-1005. doi: 10.2472/jsms.47.1000
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  • 收稿日期:  2015-03-18
  • 修回日期:  2015-03-27

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