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Title: Structural Evolution in Hollandite Solid Solutions Across the A-Site Compositional Range from Ba 1.33 Ga 2.66 Ti 5.34 O 16 to Cs 1.33 Ga 1.33 Ti 6.67 O 16

Authors:
 [1];  [2];  [2];  [3];  [1];
  1. Department of Materials Science and Engineering, Clemson University, Clemson South Carolina 29634
  2. Chemical and Engineering Materials Division, Oak Ridge National Laboratory, Oak Ridge Tennessee 37831
  3. Department of Environmental Engineering and Earth Science, Clemson University, Clemson South Carolina 29634
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1401004
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of the American Ceramic Society
Additional Journal Information:
Journal Volume: 99; Journal Issue: 12; Related Information: CHORUS Timestamp: 2017-10-20 16:14:36; Journal ID: ISSN 0002-7820
Publisher:
Wiley-Blackwell
Country of Publication:
United States
Language:
English

Citation Formats

Xu, Yun, Feygenson, Mikhail, Page, Katharine, Nickles, Lindsay Shuller, Brinkman, Kyle S., and Vanderah, ed., T. Structural Evolution in Hollandite Solid Solutions Across the A-Site Compositional Range from Ba 1.33 Ga 2.66 Ti 5.34 O 16 to Cs 1.33 Ga 1.33 Ti 6.67 O 16. United States: N. p., 2016. Web. doi:10.1111/jace.14443.
Xu, Yun, Feygenson, Mikhail, Page, Katharine, Nickles, Lindsay Shuller, Brinkman, Kyle S., & Vanderah, ed., T. Structural Evolution in Hollandite Solid Solutions Across the A-Site Compositional Range from Ba 1.33 Ga 2.66 Ti 5.34 O 16 to Cs 1.33 Ga 1.33 Ti 6.67 O 16. United States. doi:10.1111/jace.14443.
Xu, Yun, Feygenson, Mikhail, Page, Katharine, Nickles, Lindsay Shuller, Brinkman, Kyle S., and Vanderah, ed., T. 2016. "Structural Evolution in Hollandite Solid Solutions Across the A-Site Compositional Range from Ba 1.33 Ga 2.66 Ti 5.34 O 16 to Cs 1.33 Ga 1.33 Ti 6.67 O 16". United States. doi:10.1111/jace.14443.
@article{osti_1401004,
title = {Structural Evolution in Hollandite Solid Solutions Across the A-Site Compositional Range from Ba 1.33 Ga 2.66 Ti 5.34 O 16 to Cs 1.33 Ga 1.33 Ti 6.67 O 16},
author = {Xu, Yun and Feygenson, Mikhail and Page, Katharine and Nickles, Lindsay Shuller and Brinkman, Kyle S. and Vanderah, ed., T.},
abstractNote = {},
doi = {10.1111/jace.14443},
journal = {Journal of the American Ceramic Society},
number = 12,
volume = 99,
place = {United States},
year = 2016,
month = 8
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1111/jace.14443

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  • Ba{sub 1.33}Sb{sub 2.66}Al{sub 5.33}O{sub 16} is a triple Hollandite, which crystallizes in a tetragonal cell (I4/m no. 87) with a=b=9.86090(5) A and c=8.77612(6) A. Its crystal structure was characterized using electron diffraction and X-ray powder diffraction; it is isotypic to K{sub 1.33}Mg{sub 3.11}Sb{sub 4.89}O{sub 16}, K{sub 1.76}Mg{sub 3.25}Sb{sub 4.75}O{sub 16} and to K{sub 1.8}Li{sub 2.45}Sb{sub 5.55}O{sub 16}. In the rutile chains of Ba{sub 1.33}Sb{sub 2.66}Al{sub 5.33}O{sub 16}, the ordering of Al and Sb atoms into unmixed sites induces the tripling of the c parameter compared to a 'single' Hollandite structure. The Ba{sup 2+} cations are dispersed along c, in themore » largest tunnels on non-split and fully occupied sites. They lie into Ba-Ba pairs separated by vacancies. Their regular arrangement has been confirmed by high resolution electron microscopy. Electrochemical experiments have also been performed in Li-ion cell but no Li insertion was detected. - Graphical Abstract: The new Ba{sub 1.33}Sb{sub 2.66}Al{sub 5.33}O{sub 16} triple Hollandite has been synthesized and characterized by X-ray diffraction, electron microscopy, and cyclic voltammetry. Highlights: > Synthesis of a new barium antimonium aluminium oxide with a Hollandite structure. > X-ray diffraction, electron microscopy and cyclic voltammetry studies. > Presence of cationic vacancies but no Li insertion activity.« less
  • A wide range of barium titanate hollandites of the form Ba{sub x}{sup 2+}M{sub x}{sup 2+}Ti{sub 8-x}{sup 4+}O{sub 16} (M=Zn, Co, Mg, Fe and Mn) and Ba{sub x}{sup 2+}M{sub 2x}{sup 3+}Ti{sub 8-2x}{sup 4+}O{sub 16} (M=Fe) with nominal x ranging from 1.0 to 1.4 have been synthesized and examined to investigate the solid solution range and the nature of the ordering of the Ba ions. Electron diffraction studies confirm that the barium titanate hollandites are composite modulated single phase solid solutions made up of mutually incommensurable (along b) framework and Ba ion sub-structures. The overall superspace group symmetry was found to bemore » I'2/m(0,x2,0)1. The symbol I' here refers to the superspace centering operation {l_brace}x{sub 1}+12,x{sub 2}+12,x{sub 3}+12,x{sub 4}+12{r_brace} (see below). Both the framework and the Ba sub-structures have the same I2/m average structure space group symmetry. The solid solution ranges for the hollandites were calculated from the positions of well-defined superlattice peaks in X-ray diffraction patterns. The effect of cooling rate on Ba ion ordering is also examined.« less
  • Crystal structures of solid solutions of BiMn{sub 1-x}Sc{sub x}O{sub 3} with x=0.05, 0.1, 0.2, 0.3, 0.4, 0.5, and 0.7 were studied with synchrotron X-ray powder diffraction. The strong Jahn-Teller distortion, observed in BiMnO{sub 3} at 300 K and associated with orbital order, disappeared already in BiMn{sub 0.95}Sc{sub 0.05}O{sub 3}. The orbital-ordered phase did not appear in BiMn{sub 0.95}Sc{sub 0.05}O{sub 3} down to 90 K. Almost the same octahedral distortions were observed in BiMn{sub 1-x}Sc{sub x}O{sub 3} with 0.05<=x<=0.7 at room temperature and in BiMnO{sub 3} at 550 K above the orbital ordering temperature T{sub OO}=473 K. These results allowed usmore » to conclude that the remaining octahedral distortions observed in BiMnO{sub 3} above T{sub OO} are the structural feature originated from the highly distorted monoclinic structure. - Graphical Abstract: Compositional dependence of octahedral distortion parameters DELTA(M1O{sub 6}) and DELTA(M2O{sub 6}) in solid solutions BiMn{sub 1-x}Sc{sub x}O{sub 3} at 300 K.« less
  • The BaIr{sub 1-x}Mn{sub x}O{sub 3} (0.0<=x<=1.0) solid solutions were synthesized by using the solid-state chemical method and high pressure sintering in the pressure range 0-5 GPa. According to the pressure-composition 'phase diagram' at 1000 deg. C, the 9M BaIr{sub 1-x}Mn{sub x}O{sub 3} transforms to the 6M form at 5 GPa and x<=1/6. In the x range 0.5-1.0, it transforms to the 9R form in a large pressure range. For the 9M BaIrO{sub 3}, the Mn ions substitution for Ir ions enhances the semiconducting property, and reduces the weak ferromagnetism. When x is larger than 1/3, the 9M/9R BaIr{sub 1-x}Mn{sub x}O{submore » 3} behave spin-glass-like state at low temperature, with the glass transition temperature T{sub g} about 60 K. For the 6M BaIrO{sub 3}, the Mn ions doping results in that it transforms to insulator and spin-glass-like magnetism from the initial paramagnetic metal. - Graphical abstract: The BaRu{sub 1-x}Mn{sub x}O{sub 3} solid solutions were synthesized by using the solid-state chemical method and high-pressure sintering, and the pressure-composition 'phase diagram' at 1000 deg. C was obtained.« less