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Crystal structures and constitution of the binary system iridium-boron

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Abstract

The constitution of the binary system Ir-B has been established between 10 and 70 at.% boron for temperatures above 700°C based on differential scanning calorimetry, electron probe microanalysis, and isothermal low temperature annealing experiments (≤1000°C). Four binary phases have been found, namely Ir4B5+x , Ir5B4+x and the high and low temperature modification of Ir4B3-x . X-ray structure analyses were performed on single crystals of Ir4B5+x (x = 0, Ir4B5 type; space group C2/m; a = 1.05200(2), b = 0.289564(6) and c = 0.60958(1) nm, β = 91.156(2)°), Ir5B4+x (x=0, Ir5B4 type; space group I41/a; a = 0.62777(1) and b = 1.02599(2) nm) and on the low temperature modification of Ir4B3-x (x=0, IrB0.9 type; space group Cmc21; a = 0.27728(1), b = 0.75742(2) and c = 0.73152(2) nm). The high temperature modification of Ir4B3-x (WC type; space group \(P\overline 6 m2\); a = 0.28137(5) and c = 0.2828(1) nm) has been confirmed by X-ray powder diffraction. By means of the first-principle calculations, in combination with the evolutionary structural search algorithm, the compositions, structures and enthalpies of the Ir-B system have been investigated theoretically. Confirming the experimental observations on Ir4B5, Ir5B4 and Ir4B3, we have investigated several metastable phases at other stoichiometries, such as IrB, IrB2 and Ir3B2. We also proposed three thermodynamically and dynamically stable new structures of oF28-Ir4B3, oC8-IrB and mC10-Ir3B2, which may be synthesized under certain conditions.

中文摘要

本文通过 差示扫描量热法、电子探针以及等温低温退火处理, 系统地研究了铱硼二元体系在元素含量10%~70%;范围内 化 合物的结构及组成, 并成功的合成及表征了四种化合物: Ir4B5+x , Ir5B4+x ;以及Ir4B3;−129:832x 的高温和低温相. 运用单晶衍射法确定了Ir4B5+x (x = 0, Ir4B5;型; 空间群C2/m a = 1.05200(2), b = 0.289564(6), c = 0.60958(1) nm, β = 91.156(2)°), Ir5B4+x (x = 0, Ir5B4型; 空间群I 41/a a = 0.62777(1), b = 1.02599(2) nm);以及Ir4B3−x 低温相 (x = 0, IrB0.9型; 空间群Cmc 21 a = 0.27728(1), b = 0.75742(2), c = 0.73152(2) nm)的晶格常数及结构. 运用粉末衍射法确定了Ir4B3−x 高温相(WC;型; 空间群\(P\overline 6 m2\) a = 0.28137(5), c = 0.2828(1) nm)的晶格常数及结构. 通过 第一性原理计算结合结构演化搜索方法, 从理论上研究了该体系的组成, 结构以及相稳定性. 除了验证实验合成的Ir4B5, Ir5B4;以及Ir4B3;, 本文还预测了三个可能在一定条件下合成的新稳定结构: oF28-Ir4B3, oC8-IrB;以及mC10-Ir3B2.

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References

  1. Ivanovskii AL. The search for novel superhard and incompressible materials on the basis of higher borides of s, p, d metals. J Superhard Mater, 2011, 33: 7387

    Article  Google Scholar 

  2. Gu Q, Krauss G, Steurer W. Transition metal borides: superhard versus ultra incompressible. Adv Mater, 2008, 20: 3620–3626

    Article  Google Scholar 

  3. Chung HY, Yang JM, Weinberger MB, et al. Synthesis of ultra-incompressible superhard rhenium diboride at ambient pressure. Science, 2007, 316: 436–439

    Article  Google Scholar 

  4. Zeiringer I, Rogl P, Polt J, et al. Crystal structure of W1-x B3 and phase equilibria in the boron-rich part of the systems Mo-Rh-B and W-{Ru,Os,Rh,Ir,Ni,Pd,Pt}-B. J Phase Equilib and Diff, 2014, 35: 384–395

    Article  Google Scholar 

  5. Rau JV, Latini A. New hard and superhard materials: RhB1.1 and IrB1.35. Chem Mater, 2009, 21: 1407–1409

    Article  Google Scholar 

  6. Latini A, Rau JV, Teghil R, Generosi A, Albertini VR. Superhard properties of rhodium and iridium boride films. J Appl Mater Interfaces, 2010, 2: 581–587

    Article  Google Scholar 

  7. Buddery JH, Welch AJE. Borides and silicides of the platinum metals. Nature, 1951, 167: 362

    Article  Google Scholar 

  8. Samsonov GV, Kosenko VA, Rud’ BM, Sidorova VG. Preparation and properties of the compound IrB1.1. Inorg Mater, 1972, 8: 671–672

    Google Scholar 

  9. Brukl CE, Rudy E. Ternary Phase Equilibria in the Transition-Metal-Boron-Carbon-Silicon System. Air Force Materials Laboratory Technical Report (AFML-TR-65-2), 1967, 14: 31–42

    Google Scholar 

  10. Reinacher G. Hot-stage microscope determination of the solidus temperatures of iridium alloys with about 1 wt.% boron, phosphorus or silicon. Metall, 1965, 19: 707–711

    Google Scholar 

  11. Kosenko VA, Zhidkova TG. Synthesis and some chemical properties of iridium boride IrB1.1. Ukr Khim Zh, 1974, 40: 18–20

    Google Scholar 

  12. Aronsson B, Stenberg E, Åselius J. Borides of rhenium and the platinum metals. The crystal structure of Re7B3, ReB3, Rh7B3, RhB1.1 (ap-proximate composition), IrB1.1 (approximate composition) and PtB. Acta Chem Scand, 1960, 14: 733–741

    Google Scholar 

  13. Aronsson B. The crystal structure of RuB2, OsB2 and IrB1.35 and some general comments on the crystal chemistry of borides in the composition range MeB-MeB3. Acta Chem Scand, 1963, 17: 2036–2050

    Article  Google Scholar 

  14. Lundström T, Tergenius LE. Refinement of the crystal structure of the non-stoichiometric moride IrB1.35 (approximate composition). Acta Chem Scand, 1973, 27: 3705–3711

    Article  Google Scholar 

  15. Haschke H. Structural Chemical Investigations on Complex Borides and Carbides, as well as on Silicides and Germanides of Rare Earth Metals. Dissertation for Doctoral Degree. University of Vienna, 1966.

    Google Scholar 

  16. Rogl P, Nowotny H, Benesovsky F. Ein Beitrag zur Strukturchemie der Iridiumboride. Monatshefte für Chemie, 1971, 102: 678–686 (in Germany)

    Article  Google Scholar 

  17. Vandenberg JH, Matthias BT, Corenzwit E, Barz H. Superconductivity of some binary and ternary transition metal borides. Mat Res Bull, 1975, 10: 889–894

    Article  Google Scholar 

  18. Zhao WJ, Wang JX. Structural, mechanical, and electronic properties of TaB2, TaB, IrB2, and IrB: first-principle calculations. J Solid State Chem, 2009, 182: 1280–1286

    Google Scholar 

  19. Wang DY, Wang B, Wang XY. New crystal structures of IrB and IrB2: first-principles calculations. J Phys Chem C, 2012, 116: 21961–21966

    Article  Google Scholar 

  20. Hao X, Wu Z, Xu Y, et al. Trends in elasticity and electronic structure of 5d transition metal diborides: first-principles calculations. J Phys Condens Matter, 2007, 19: 196212

    Article  Google Scholar 

  21. Wang Y, Chen W, Chen X, et al. Crystal structures, stability, electronic and elastic properties of 4d and 5d transition metal monoborides: first-principles calculations. J Alloys Compd, 2012, 538: 115–124

    Article  Google Scholar 

  22. Spear KE. Correlations and Predictions of Metal-Boron Phase Equilibria. In Proceedings of a Workshop held in Gaithersburg 1977. US Dep Commerce, Natl Bur Stand, Spec Publ SP-496/2, 1978, 744–762

    Google Scholar 

  23. Ipser H, Rogl P. Constitution diagrams of the binary systems Pd-B and Ir-B. J Less-Common Metals, 1981, 82: 362

    Article  Google Scholar 

  24. Rogl P, Effenberg G (eds.). Phase Diagrams of Ternary Metal-Boron-Carbon Systems. Ohio: ASM International, 1988, 150–153

    Google Scholar 

  25. Zivkovic D, Stuparevic L. Calculations of the thermodynamic properties in the Ir-B system based on the known phase diagram. RMZMaterials and Geoenvironmen, 2005, 52: 463–468

    Google Scholar 

  26. Meschel SV, Kleppa OJ. Enthalpies of formation of refractory borides of 5d elements by high temperature direct synthesis calorimetry: IrB1.35 and OsB2.5. J Alloys Compd, 1991, 177: 159–166

    Article  Google Scholar 

  27. Van der Auwera-Mahieu A, Peeters R, McIntyre NS, Drowart J. Mass spectrometric determination of dissociation energies of the borides and silicides of some transition metals. Trans Faraday Soc, 1970, 66: 809–816

    Article  Google Scholar 

  28. Rodriguez-Carvajal J. Recent developments of the program FULLPROF. Physica B, 1993, 55: 192

    Google Scholar 

  29. Sheldrick GM. SHELXS-97. Acta Cryst, 1990, A46: 467–473

    Article  Google Scholar 

  30. Sheldrick GM. Program SHELX-97 for Crystal Structure Determination. University of Goettingen, 1997.

    Google Scholar 

  31. Farrugia LJ. WINGX suite for small-molecule single-crystal crystallography. J Appl Cryst, 1999, 32: 837–838

    Article  Google Scholar 

  32. Gelato LM, Parthé E. STRUCTURE TIDY — a computer program to standardize crystal structure data. J Appl Cryst, 1987, 20: 139–143

    Article  Google Scholar 

  33. Hohenberg P, Kohn W. Inhomogeneous electron gas. Phys Rev B, 1964, 136: 864

    Article  Google Scholar 

  34. Kohn W, Sham LJ. Self-consistent equations including exchange and correlation effects. Phys Rev A, 1965, 140: 1133

    Article  Google Scholar 

  35. Kresse G, Hafner J. Ab initio molecular dynamics for liquid metals. Phys Rev B, 1993, 47: 558–561

    Article  Google Scholar 

  36. Kresse G, Furthmüller J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput Mat Sci, 1996, 6: 15–50

    Article  Google Scholar 

  37. Blöchl PE, Jepsen O, Andersen OK. Improved tetrahedron method for Brillouin-zone integrations. Phys Rev B, 1994, 23: 16223

    Article  Google Scholar 

  38. Perdew JP, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Phys Rev Lett, 1996, 77: 3865

    Article  Google Scholar 

  39. Togo A, Oba F, Tanaka I. First-principles calculations of the ferroelastic transition between rutile-type and CaCl2-type SiO2 at high pressures. Phys Rev B, 2008. 78: 134106.

    Article  Google Scholar 

  40. Oganov AR, Glass CW. Crystal structure prediction using ab initio evolutionary techniques: principles and applications. J Chem Phys, 2006, 124: 244704

    Article  Google Scholar 

  41. Oganov AR, Lyakhov AO, Valle M. How evolutionary crystal structure prediction works—and why. Acc Chem Res, 2011, 44: 227–237

    Article  Google Scholar 

  42. Crespo AJ, Terg enius LE, Lundström T. The solid solution of 4d, 5d and some p-elements in ß-rhombohedral boron. J Less Common Metals, 1981, 77: 147–150

    Article  Google Scholar 

  43. Rogl P. Existence and Crystal Chemistry of Borides, in Inorganic Reactions and Methods: Formation of Bonds to Group-I, -II, and -IIIB Elements. Hoboken: John Wiley & Sons Inc, 1991, 13: 85–167

    Google Scholar 

  44. Teatum E, Gschneidner K, Waber J, Pearson WB (eds.). The Crystal Chemistry and Physics of Metals and Alloys. New York: Wiley-Interscience, 1972

    Google Scholar 

  45. Bärnighausen H. Group-subgroup relations between space groups: a useful tool in crystal chemistry. Commun Math Chem, 1980, 9: 139

    Google Scholar 

  46. Rogl P, DeLong L. New ternary transition metal borides containing uranium and rare earth elements. J Less Common Metals, 1983, 91: 97–106

    Article  Google Scholar 

  47. Villars P, Cenzual K. Pearson’s Crystal Data CD-ROM. ASM International, Ohio, Release 2013/14

    Google Scholar 

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Author information

Authors and Affiliations

  1. Institute of Materials Chemistry and Research, University of Vienna, A-1090, Wien, Austria

    Isolde Zeiringer & Peter Franz Rogl

  2. Shenyang National Laboratory for Materials Science (SYNL), Institute of Metal Research (IMR), Chinese Academy of Sciences (CAS), Shenyang, 110016, China

    Xiyue Cheng & Xing-Qiu Chen

  3. Institute of Solid State Physics, Vienna University of Technology, A-1040, Wien, Austria

    Ernest Bauer

  4. Institute of Mineralogy and Crystallography, University of Vienna, A-1090, Wien, Austria

    Gerald Giester

Authors
  1. Isolde Zeiringer
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  2. Xiyue Cheng
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  3. Xing-Qiu Chen
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  4. Ernest Bauer
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  5. Gerald Giester
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  6. Peter Franz Rogl
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Corresponding authors

Correspondence to Xing-Qiu Chen or Peter Franz Rogl.

Additional information

These authors contributed to this work equally.

Isolde Zeiringer received her PhD degree in chemistry based on her thesis “Non-centrosymmetric Superconductors”, which was performed in the Institute of Physical Chemistry at the University of Vienna. Part of her thesis was performed at the research laboratory in Div. Bajas Temperaturas, CAB-CNEA, Bariloche, Argentina. Currently she has published eleven peer-review papers.

Xiyue Cheng was born in Kangding, Sichuan Province, China. She received her BSc degree from Central South University in 2011. Now she is a PhD candidate in the group of computational materials design at the Institute of Metal Research, Chinese Academy of Sciences. Her research interest focuses on high-throughput computational material design in the aspect of high-performance metallic borides. Xing-

Xing-Qiu Chen obtained his PhD degree in computational materials science at the University of Vienna in 2004 and completed the postdoctoral studies at Vienna Center of Computational Materials Science and Oak Ridge National Laboratory from 2005 to 2010. He is currently a professor at Shenyang National Laboratory for Materials Science funded by Hundred Talent Project. His research interests mainly focus on the computational material design on high-performance structural materials and strongly-correlated metallic alloys.

Peter Franz Rogl holds PhD degree in physics from the University of Vienna (1971) and venia docendi in physical chemistry (1980). Since 2004, he is a full professor at the chair of Physical Chemistry of Materials (Univ. Vienna). He won Sandoz research award of Sandoz Research Center in 1985; Felix Kuschenitz Price of Austrian Academy of Sciences for outstanding research in 1992. He has authored/co-authored more than 600 peer-review papers in journals and 22 books or chapters in books.

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Zeiringer, I., Cheng, X., Chen, XQ. et al. Crystal structures and constitution of the binary system iridium-boron. Sci. China Mater. 58, 649–668 (2015). https://doi.org/10.1007/s40843-015-0078-6

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