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Title: Direct observation of mineral–organic composite formation reveals occlusion mechanism

Abstract

Manipulation of inorganic materials with organic macromolecules enables organisms to create biominerals such as bones and seashells, where occlusion of biomacro-molecules within individual crystals generates superior mechanical properties. Current understanding of this process comes from entrapment of micron-size particles in cooling melts. Here, by studying micelle incorporation in calcite with atomic force microscopy and micromechanical simulations, we show that different mechanisms govern nanoscale occlusion. By simultaneously visualizing the micelles and propagating step edges, we demonstrate that the micelles experience significant compression during occlusion, which is accompanied by cavity formation. This generates local lattice strain, leading to enhanced mechanical properties. These results give new insight into the formation of occlusions in natural and synthetic crystals, and will facilitate the synthesis of multifunctional nanocomposite crystals.

Authors:
 [1]; ORCiD logo [2];  [3];  [4];  [5];  [2];  [6];  [6];  [3];  [2];  [7]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  2. Univ. of Leeds, Leeds (United Kingdom)
  3. Univ. of Sheffield, Sheffield (United Kingdom)
  4. Stanford Univ., Stanford, CA (United States)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Zhejiang Univ., Hangzhou (China)
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  7. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1249368
Alternate Identifier(s):
OSTI ID: 1379025; OSTI ID: 1474347; OSTI ID: 1526977
Report Number(s):
PNNL-SA-114998; LLNL-JRNL-673292
Journal ID: ISSN 2041-1723; ncomms10187
Grant/Contract Number:  
AC05-76RL01830; AC02-05CH11231; AC52-07NA27344
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 7; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; physical sciences; bioengineering; materials science; physical chemistry; Materials science, Biological and medical sciences, Chemistry - Inorganic, organic, physical and analytical chemistry

Citation Formats

Cho, Kang Rae, Kim, Yi -Yeoun, Yang, Pengcheng, Cai, Wei, Pan, Haihua, Kulak, Alexander N., Lau, Jolene L., Kulshreshtha, Prashant, Armes, Steven P., Meldrum, Fiona C., and De Yoreo, James J. Direct observation of mineral–organic composite formation reveals occlusion mechanism. United States: N. p., 2016. Web. doi:10.1038/ncomms10187.
Cho, Kang Rae, Kim, Yi -Yeoun, Yang, Pengcheng, Cai, Wei, Pan, Haihua, Kulak, Alexander N., Lau, Jolene L., Kulshreshtha, Prashant, Armes, Steven P., Meldrum, Fiona C., & De Yoreo, James J. Direct observation of mineral–organic composite formation reveals occlusion mechanism. United States. doi:10.1038/ncomms10187.
Cho, Kang Rae, Kim, Yi -Yeoun, Yang, Pengcheng, Cai, Wei, Pan, Haihua, Kulak, Alexander N., Lau, Jolene L., Kulshreshtha, Prashant, Armes, Steven P., Meldrum, Fiona C., and De Yoreo, James J. Wed . "Direct observation of mineral–organic composite formation reveals occlusion mechanism". United States. doi:10.1038/ncomms10187. https://www.osti.gov/servlets/purl/1249368.
@article{osti_1249368,
title = {Direct observation of mineral–organic composite formation reveals occlusion mechanism},
author = {Cho, Kang Rae and Kim, Yi -Yeoun and Yang, Pengcheng and Cai, Wei and Pan, Haihua and Kulak, Alexander N. and Lau, Jolene L. and Kulshreshtha, Prashant and Armes, Steven P. and Meldrum, Fiona C. and De Yoreo, James J.},
abstractNote = {Manipulation of inorganic materials with organic macromolecules enables organisms to create biominerals such as bones and seashells, where occlusion of biomacro-molecules within individual crystals generates superior mechanical properties. Current understanding of this process comes from entrapment of micron-size particles in cooling melts. Here, by studying micelle incorporation in calcite with atomic force microscopy and micromechanical simulations, we show that different mechanisms govern nanoscale occlusion. By simultaneously visualizing the micelles and propagating step edges, we demonstrate that the micelles experience significant compression during occlusion, which is accompanied by cavity formation. This generates local lattice strain, leading to enhanced mechanical properties. These results give new insight into the formation of occlusions in natural and synthetic crystals, and will facilitate the synthesis of multifunctional nanocomposite crystals.},
doi = {10.1038/ncomms10187},
journal = {Nature Communications},
number = ,
volume = 7,
place = {United States},
year = {2016},
month = {1}
}

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