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Title: Structure and transport properties of dense polycrystalline clathrate-II (K,Ba) 16(Ga,Sn) 136 synthesized by a new approach employing SPS

Abstract

Tin clathrate-II framework-substituted compositions are of current interest as potential thermoelectric materials for medium-temperature applications. A review of the literature reveals different compositions reported with varying physical properties, which depend strongly on the exact composition as well as the processing conditions. We therefore initiated an approach whereby single crystals of two different (K,Ba) 16(Ga,Sn) 136 compositions were first obtained, followed by grinding of the crystals into fine powder for low temperature spark plasma sintering consolidation into dense polycrystalline solids and subsequent high temperature transport measurements. Powder X-ray refinement results indicate that the hexakaidecahedra are empty, K and Ba occupying only the decahedra. Their electrical properties depend on composition and have very low thermal conductivities. As a result, the structural and transport properties of these materials are compared to that of other Sn clathrate-II compositions.

Authors:
 [1];  [2];  [2];  [1]; ORCiD logo [1];  [1]
  1. Univ. of South Florida, Tampa, FL (United States)
  2. Clemson Univ., Clemson, SC (United States)
Publication Date:
Research Org.:
Univ. of South Florida, Tampa, FL (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1361383
Grant/Contract Number:  
FG02-04ER46145
Resource Type:
Accepted Manuscript
Journal Name:
Materials
Additional Journal Information:
Journal Volume: 9; Journal Issue: 9; Journal ID: ISSN 1996-1944
Publisher:
MDPI
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; clathrate; SPS processing; thermoelectrics

Citation Formats

Wei, Kaya, Zeng, Xiaoyu, Tritt, Terry M., Khabibullin, Artem R., Woods, Lilia M., and Nolas, George S. Structure and transport properties of dense polycrystalline clathrate-II (K,Ba)16(Ga,Sn)136 synthesized by a new approach employing SPS. United States: N. p., 2016. Web. doi:10.3390/ma9090732.
Wei, Kaya, Zeng, Xiaoyu, Tritt, Terry M., Khabibullin, Artem R., Woods, Lilia M., & Nolas, George S. Structure and transport properties of dense polycrystalline clathrate-II (K,Ba)16(Ga,Sn)136 synthesized by a new approach employing SPS. United States. doi:10.3390/ma9090732.
Wei, Kaya, Zeng, Xiaoyu, Tritt, Terry M., Khabibullin, Artem R., Woods, Lilia M., and Nolas, George S. Fri . "Structure and transport properties of dense polycrystalline clathrate-II (K,Ba)16(Ga,Sn)136 synthesized by a new approach employing SPS". United States. doi:10.3390/ma9090732. https://www.osti.gov/servlets/purl/1361383.
@article{osti_1361383,
title = {Structure and transport properties of dense polycrystalline clathrate-II (K,Ba)16(Ga,Sn)136 synthesized by a new approach employing SPS},
author = {Wei, Kaya and Zeng, Xiaoyu and Tritt, Terry M. and Khabibullin, Artem R. and Woods, Lilia M. and Nolas, George S.},
abstractNote = {Tin clathrate-II framework-substituted compositions are of current interest as potential thermoelectric materials for medium-temperature applications. A review of the literature reveals different compositions reported with varying physical properties, which depend strongly on the exact composition as well as the processing conditions. We therefore initiated an approach whereby single crystals of two different (K,Ba)16(Ga,Sn)136 compositions were first obtained, followed by grinding of the crystals into fine powder for low temperature spark plasma sintering consolidation into dense polycrystalline solids and subsequent high temperature transport measurements. Powder X-ray refinement results indicate that the hexakaidecahedra are empty, K and Ba occupying only the decahedra. Their electrical properties depend on composition and have very low thermal conductivities. As a result, the structural and transport properties of these materials are compared to that of other Sn clathrate-II compositions.},
doi = {10.3390/ma9090732},
journal = {Materials},
number = 9,
volume = 9,
place = {United States},
year = {2016},
month = {8}
}

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Works referenced in this record:

Clathrate Structure of Silicon Na8Si46 and NaxSi136 (x < 11)
journal, December 1965


Simple Approach for Selective Crystal Growth of Intermetallic Clathrates
journal, March 2011

  • Stefanoski, Stevce; Beekman, Matt; Wong-Ng, Winnie
  • Chemistry of Materials, Vol. 23, Issue 6
  • DOI: 10.1021/cm103135k

Synthesis and Structural Characterization of Single-Crystal K 7.5 Si 46 and K 17.8 Si 136 Clathrates
journal, October 2011

  • Stefanoski, Stevce; Nolas, George S.
  • Crystal Growth & Design, Vol. 11, Issue 10
  • DOI: 10.1021/cg200756r

Preparation and Crystal Growth of Na 24 Si 136
journal, July 2009

  • Beekman, Matt; Baitinger, Michael; Borrmann, Horst
  • Journal of the American Chemical Society, Vol. 131, Issue 28
  • DOI: 10.1021/ja903362b

Pressure Effects on the Size of Type-I and Type-II Si-Clathrates Synthesized by Spark Plasma Sintering
journal, December 2012

  • Stefanoski, S.; Blosser, M. C.; Nolas, G. S.
  • Crystal Growth & Design, Vol. 13, Issue 1
  • DOI: 10.1021/cg3013443

Efficient route to phase selective synthesis of type II silicon clathrates with low sodium occupancy
journal, January 2014

  • Krishna, Lakshmi; Baranowski, Lauryn L.; Martinez, Aaron D.
  • CrystEngComm, Vol. 16, Issue 19
  • DOI: 10.1039/C3CE42626B

Rapid crystal growth of type-II clathrates A 8 Na 16 Si 136 (A = K, Rb, Cs) by spark plasma sintering
journal, January 2015

  • Dong, Yongkwan; Nolas, George S.
  • CrystEngComm, Vol. 17, Issue 11
  • DOI: 10.1039/C4CE02221A

Precursor routes to quaternary intermetallics: Synthesis, crystal structure, and physical properties of clathrate-II Cs8Na16Al24Si112
journal, May 2016


Thermoelectric Clathrates
journal, January 2001


Inorganic clathrate-II materials of group 14: synthetic routes and physical properties
journal, January 2008

  • Beekman, M.; Nolas, G. S.
  • J. Mater. Chem., Vol. 18, Issue 8
  • DOI: 10.1039/B706808E

Semiconducting clathrates: synthesis, structure and properties
journal, September 2004


Better thermoelectrics through glass-like crystals
journal, November 2015

  • Beekman, Matt; Morelli, Donald T.; Nolas, George S.
  • Nature Materials, Vol. 14, Issue 12
  • DOI: 10.1038/nmat4461

Off-center rattling and thermoelectric properties of type-II clathrate (K, Ba) 24 (Ga, Sn, ) 136 single crystals
journal, December 2011


Thermoelectric and transport properties of sintered n -type K 8 Ba 16 Ga 40 Sn 96 with type-II clathrate structure
journal, July 2014

  • Koda, Shota; Kishimoto, Kengo; Akai, Koji
  • Journal of Applied Physics, Vol. 116, Issue 2
  • DOI: 10.1063/1.4889822

Thermoelectric properties of sintered type-II clathrates (K, Ba) 24 (Ga, Sn) 136 with various carrier concentrations
journal, September 2015

  • Kishimoto, Kengo; Koda, Shota; Akai, Koji
  • Journal of Applied Physics, Vol. 118, Issue 12
  • DOI: 10.1063/1.4931433

Tin Clathrates with the Type II Structure
journal, January 2013

  • Schäfer, Marion C.; Bobev, Svilen
  • Journal of the American Chemical Society, Vol. 135, Issue 5
  • DOI: 10.1021/ja3112934

K and Ba distribution in the structures of the clathrate compounds K x Ba 16− x (Ga,Sn) 136 ( x = 0.8, 4.4, and 12.9) and K x Ba 8− x (Ga,Sn) 46 ( x = 0.3)
journal, March 2013

  • Schäfer, Marion C.; Bobev, Svilen
  • Acta Crystallographica Section C Crystal Structure Communications, Vol. 69, Issue 4
  • DOI: 10.1107/S0108270113006203

Preparation, Transport Properties, and Structure Analysis by Resonant X-ray Scattering of the Type I Clathrate Cs 8 Cd 4 Sn 42
journal, March 2002

  • Wilkinson, A. P.; Lind, C.; Young, R. A.
  • Chemistry of Materials, Vol. 14, Issue 3
  • DOI: 10.1021/cm0107880

Structural characterization and low-temperature physical properties of p-type single-crystal K8Ga8.5Sn37.5 grown by self-flux method
journal, August 2013


Simultaneous structure and carrier tuning of dimorphic clathrate Ba 8 Ga 16 Sn 30
journal, June 2008


Interplay between thermoelectric and structural properties of type-I clathrate K 8 Ga 8 Sn 38 single crystals
journal, April 2010


Structural, Chemical, and Transport Properties of a New Clathrate Compound:  Cs 8 Zn 4 Sn 42
journal, September 1999

  • Nolas, G. S.; Weakley, T. J. R.; Cohn, J. L.
  • Chemistry of Materials, Vol. 11, Issue 9
  • DOI: 10.1021/cm990164i

Ba8Ga16Sn30 with type-I clathrate structure: Drastic suppression of heat conduction
journal, January 2008

  • Avila, M. A.; Suekuni, K.; Umeo, K.
  • Applied Physics Letters, Vol. 92, Issue 4
  • DOI: 10.1063/1.2831926

Preparation and thermoelectric properties of sintered n -type K 8 M 8 Sn 38 ( M = Al, Ga and In) with the type-I clathrate structure
journal, October 2012


Structural Characterization and Thermal Conductivity of Type-I Tin Clathrates
journal, July 2000

  • Nolas, G. S.; Chakoumakos, B. C.; Mahieu, B.
  • Chemistry of Materials, Vol. 12, Issue 7
  • DOI: 10.1021/cm990686y

Structural analysis of Sr8Ga16Ge30 clathrate compound
journal, February 2000

  • Schujman, S. B.; Nolas, G. S.; Young, R. A.
  • Journal of Applied Physics, Vol. 87, Issue 3
  • DOI: 10.1063/1.372044

EXPGUI , a graphical user interface for GSAS
journal, April 2001


Transport Properties of Bulk Thermoelectrics: An International Round-Robin Study, Part II: Thermal Diffusivity, Specific Heat, and Thermal Conductivity
journal, March 2013

  • Wang, Hsin; Porter, Wallace D.; Böttner, Harald
  • Journal of Electronic Materials, Vol. 42, Issue 6
  • DOI: 10.1007/s11664-013-2516-0

Effective ionic radii in oxides and fluorides
journal, May 1969

  • Shannon, R. D.; Prewitt, C. T.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 25, Issue 5
  • DOI: 10.1107/S0567740869003220

Chemical trends of the rattling phonon modes in alloyed germanium clathrates
journal, June 2000

  • Dong, Jianjun; Sankey, Otto F.; Ramachandran, Ganesh K.
  • Journal of Applied Physics, Vol. 87, Issue 11
  • DOI: 10.1063/1.373447

Semiconducting Ge clathrates: Promising candidates for thermoelectric applications
journal, July 1998

  • Nolas, G. S.; Cohn, J. L.; Slack, G. A.
  • Applied Physics Letters, Vol. 73, Issue 2
  • DOI: 10.1063/1.121747

The maximum possible conversion efficiency of silicon‐germanium thermoelectric generators
journal, September 1991

  • Slack, Glen A.; Hussain, Moayyed A.
  • Journal of Applied Physics, Vol. 70, Issue 5
  • DOI: 10.1063/1.349385

Estimation of the thermal band gap of a semiconductor from seebeck measurements
journal, July 1999


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