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Title: Structural Basis for Metastability in Amorphous Calcium Barium Carbonate (ACBC)

Abstract

Metastable amorphous precursors are emerging as valuable intermediates for the synthesis of materials with compositions and structures far from equilibrium. Recently, it was found that amorphous calcium barium carbonate (ACBC) can be converted into highly barium-substituted “balcite,” a metastable high temperature modification of calcite with exceptional hardness. A systematic analysis ACBC (Ca 1-xBa xCO 3·1.2H 2O) in the range from x = 0–0.5 is presented. Combining techniques that independently probe the local environment from the perspective of calcium, barium, and carbonate ions, with total X-ray scattering and a new molecular dynamics/density functional theory simulations approach, provides a holistic picture of ACBC structure as a function of composition. With increasing barium content, ACBC becomes more ordered at short and medium range, and increasingly similar to crystalline balcite, without developing long-range order. This is not accompanied by a change in the water content and does not carry a significant energy penalty, but is associated with differences in cation coordination resulting from changing carbonate anion orientation. Therefore, the local order imprinted in ACBC may increasingly lower the kinetic barrier to subsequent transformations as it becomes more pronounced. This pathway offers clues to the design of metastable materials by tuning coordination numbers in themore » amorphous solid state.« less

Authors:
 [1];  [2];  [1];  [3];  [2];  [1]
  1. Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1476613
Alternate Identifier(s):
OSTI ID: 1410376
Grant/Contract Number:  
AC02-05CH11231; SC0012704; AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Volume: 28; Journal Issue: 2; Journal ID: ISSN 1616-301X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; amorphous calcium–barium carbonate; biomineralization; metastability; polyamorphism

Citation Formats

Whittaker, Michael L., Sun, Wenhao, DeRocher, Karen A., Jayaraman, Saivenkataraman, Ceder, Gerbrand, and Joester, Derk. Structural Basis for Metastability in Amorphous Calcium Barium Carbonate (ACBC). United States: N. p., 2017. Web. doi:10.1002/adfm.201704202.
Whittaker, Michael L., Sun, Wenhao, DeRocher, Karen A., Jayaraman, Saivenkataraman, Ceder, Gerbrand, & Joester, Derk. Structural Basis for Metastability in Amorphous Calcium Barium Carbonate (ACBC). United States. doi:10.1002/adfm.201704202.
Whittaker, Michael L., Sun, Wenhao, DeRocher, Karen A., Jayaraman, Saivenkataraman, Ceder, Gerbrand, and Joester, Derk. Mon . "Structural Basis for Metastability in Amorphous Calcium Barium Carbonate (ACBC)". United States. doi:10.1002/adfm.201704202. https://www.osti.gov/servlets/purl/1476613.
@article{osti_1476613,
title = {Structural Basis for Metastability in Amorphous Calcium Barium Carbonate (ACBC)},
author = {Whittaker, Michael L. and Sun, Wenhao and DeRocher, Karen A. and Jayaraman, Saivenkataraman and Ceder, Gerbrand and Joester, Derk},
abstractNote = {Metastable amorphous precursors are emerging as valuable intermediates for the synthesis of materials with compositions and structures far from equilibrium. Recently, it was found that amorphous calcium barium carbonate (ACBC) can be converted into highly barium-substituted “balcite,” a metastable high temperature modification of calcite with exceptional hardness. A systematic analysis ACBC (Ca1-xBaxCO3·1.2H2O) in the range from x = 0–0.5 is presented. Combining techniques that independently probe the local environment from the perspective of calcium, barium, and carbonate ions, with total X-ray scattering and a new molecular dynamics/density functional theory simulations approach, provides a holistic picture of ACBC structure as a function of composition. With increasing barium content, ACBC becomes more ordered at short and medium range, and increasingly similar to crystalline balcite, without developing long-range order. This is not accompanied by a change in the water content and does not carry a significant energy penalty, but is associated with differences in cation coordination resulting from changing carbonate anion orientation. Therefore, the local order imprinted in ACBC may increasingly lower the kinetic barrier to subsequent transformations as it becomes more pronounced. This pathway offers clues to the design of metastable materials by tuning coordination numbers in the amorphous solid state.},
doi = {10.1002/adfm.201704202},
journal = {Advanced Functional Materials},
issn = {1616-301X},
number = 2,
volume = 28,
place = {United States},
year = {2017},
month = {11}
}

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