二ホウ化ニオブ

二ホウ化ニオブ
識別情報
CAS登録番号 12007-29-3
PubChem 49781553
ChemSpider 21171230
EC番号 234-503-3
特性
化学式 NbB2
モル質量 114.526 g/mol
外観 灰色粉末
密度 6.97 g/cm3
融点

~3050°C

沸点

N/A

への溶解度 不溶
構造
結晶構造 六方晶系, hP3 a = 3.085 Å, c = 3.311 Å and c/a = 1.071 Å
空間群 P6/mmm, No. 191
危険性
主な危険性 未調査
特記なき場合、データは常温 (25 °C)・常圧 (100 kPa) におけるものである。

二ホウ化ニオブ(Niobium diboride)は、共有結合性の高い耐火セラミック材料で、六方晶系結晶構造を持つ。

合成

二ホウ化ニオブは、構成元素であるニオブホウ素化学量論的反応により合成される[1]。この反応により、材料の正確な化学量論的制御が可能となる。金属熱還元による酸化ニオブ(V)または酸化ニオブ(II)の二ホウ化ニオブへの還元も可能である。下記の反応では、高価ではない前駆体物質からの生成が可能である。

Nb2O5 + 2 B2O3 + 11 Mg → 2 NbB2 + 11 MgO

不要な酸化物生成物の酸浸出のために、反応物としてマグネシウムが用いられる。金属熱還元で全ての酸化ニオブを消費するために、しばしば化学量論的に過剰量のマグネシウムとホウ酸が必要となる。

Jhaらにより、ホウ素存在下での固相反応による酸化ニオブ(II)のホウ素熱還元によるナノロッド(40×800 nm2)の合成が提案されている[2]。またRanらにより、溶融塩のホウ素熱反応により、酸化ニオブ(V)とホウ素からのナノ結晶(61 nm)の合成が提案されている[3]

二ホウ化ニオブのナノ結晶は、M:B比が1:4、アルゴン流下、700℃で30分間の水素化ホウ素ナトリウムによる酸化ニオブ(V)の還元で、合成に成功した[4]

Nb2O5 + 13/2 NaBH4 → 2 NbB2 + 4Na(g,l) + 5/2 NaBO2 + 13 H2(g)

性質と利用

二ホウ化ニオブは、融点が3050℃の超高温セラミックである[5]。~6.97 g/cm3という比較的低密度と高温への耐性により、超音速飛行ロケット推進システム等の航空宇宙分野への応用が期待されている。

同形二ホウ化タンタル二ホウ化ジルコニウム二ホウ化ハフニウム二ホウ化タンタル等と同様に、熱伝導度電気伝導度が比較的高い(電気抵抗率:25.7 μΩ・cm、熱膨張率:7.7×10-6-1[6]

二ホウ化ニオブの部品は通常、熱間圧接[7]放電プラズマ焼結[8]され、その後、機械加工で形が作られる。二ホウ化ニオブの焼結は、材料自体の共有結合性と、焼結中の高密度化の前に粒子の粗さを増大させる表面酸化物の存在により、阻害される。

炭化ホウ素炭素等の付加物とともに無加圧焼結も可能である。付加物は表面酸化物と反応して焼結の推進力を増すが、熱間圧接と比べて機械的性質は弱まる。

出典

  1. ^ Çamurlu, H. Erdem & Filippo Maglia. (2009). “Preparation of nano-size ZrB 2 powder by self-propagating high-temperature synthesis”. Journal of the European Ceramic Society 29 (8): 1501–1506. doi:10.1016/j.jeurceramsoc.2008.09.006. 
  2. ^ Jha, Menaka; Ramanujachary, Kandalam V.; Lofland, Samuel E.; Gupta, Govind; Ganguli, Ashok K. (2011-07-26). “Novel borothermal process for the synthesis of nanocrystalline oxides and borides of niobium” (英語). Dalton Transactions 40 (31): 7879–88. doi:10.1039/c1dt10468c. ISSN 1477-9234. PMID 21743887. https://semanticscholar.org/paper/86f2ed693cfba509317c3f19555fe7c543bd0cb9. 
  3. ^ Ran, Songlin; Sun, Huifeng; Wei, Ya'nan; Wang, Dewen; Zhou, Niming; Huang, Qing (2014-11-01). “Low-Temperature Synthesis of Nanocrystalline NbB2Powders by Borothermal Reduction in Molten Salt” (英語). Journal of the American Ceramic Society 97 (11): 3384–3387. doi:10.1111/jace.13298. ISSN 1551-2916. 
  4. ^ Zoli, Luca; Galizia, Pietro; Silvestroni, Laura; Sciti, Diletta (23 January 2018). “Synthesis of group IV and V metal diboride nanocrystals via borothermal reduction with sodium borohydride”. Journal of the American Ceramic Society 101 (6): 2627–2637. doi:10.1111/jace.15401. https://zenodo.org/record/1292491. 
  5. ^ Perry, Dale L. (2011). Handbook of inorganic compounds (2nd ed.). Boca Raton: Taylor & Francis. ISBN 9781439814611. OCLC 587104373 
  6. ^ Kovenskaya, B.; Serebryakova, T. I. (May 1970). “Physical properties of niobium boride phase”. Soviet Powder Metallurgy and Metal Ceramics 9 (5): 415–417. doi:10.1007/BF00796512. https://link.springer.com/article/10.1007/BF00796512. 
  7. ^ IWASA, Mikio、KINOSHITA, Makoto、HAYAMI, Ryozo、YAMAZAKI, Tatsuo「ホウ化ニオブのホットプレス」『Journal of the Ceramic Association, Japan』第87巻第1006号、1979年6月1日、284–290頁、doi:10.2109/jcersj1950.87.1006_284ISSN 0009-0255 
  8. ^ Sairam, K.; Sonber, J.K.; Murthy, T.S.R.Ch.; Subramanian, C.; Fotedar, R.K.; Hubli, R.C. (2014). “Reaction spark plasma sintering of niobium diboride”. International Journal of Refractory Metals and Hard Materials 43: 259–262. doi:10.1016/j.ijrmhm.2013.12.011. 

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