Hostname: page-component-cd9895bd7-hc48f Total loading time: 0 Render date: 2024-12-29T07:10:55.094Z Has data issue: false hasContentIssue false

Laser Light Scattering Observations of Liquid–Liquid Phase Separation in a Polymer-Induced Liquid-Precursor (PILP) Mineralization Process

Published online by Cambridge University Press:  01 February 2011

Elaine DiMasi*
Affiliation:
Brookhaven National Laboratory, Upton NY 11973
Tianbo Liu
Affiliation:
Brookhaven National Laboratory, Upton NY 11973
Matthew J. Olszta
Affiliation:
University of Florida, Gainesville FL 32611
Laurie B. Gower*
Affiliation:
University of Florida, Gainesville FL 32611
*
*Email address for correspondence: dimasi@bnl.gov
Email address for correspondence: lgowe@mse.ufl.edu
Get access

Abstract

A Polymer-Induced Liquid-Precursor (PILP) process for mineralization of calcium carbonate has been studied in-situ by laser light scattering. Static and dynamic light scattering data were obtained from CaCl2 solutions containing poly(aspartic acid). Under these conditions calcium carbonate mineralizes through a liquid droplet precursor phase when the solution is exposed to the decomposition products of ammonium carbonate. Our measurements probe the integrated scatterer mass and the apparent hydrodynamic radius Rh,app of the droplets as they nucleate and coalesce. The data reveal three stages in the formation of the PILP phase: an early stage of droplet growth to Rh,app ≈ 250 nm; a mid-time stage of fluctuations and polydispersity in particle size; and a final growth period where Rh,app increases from 350 nm to the micron scale. Aggregation of precursor droplets, rather than atom-by-atom growth, is the dominant mechanism of mineral formation under these conditions. With respect to biomineralization, this first observation of 100-nm-scale droplets is significant, implying a possibility to mineralize from the liquid phase within the nanoscale compartments in which many biominerals form.

Type
Research Article
Copyright
Copyright © Materials Research Society 2005

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

Footnotes

1

Penn State University, State College PA 16802

2

Present Address: Lehigh University, Bethlehem PA 18015

References

1 Dan, N., TIBTECH 18 (2000).Google Scholar
2 Buijnsters, P. J. J. A. et al, Langmuir 17, 3623 (2001).Google Scholar
3 Han, Y.-J. and Aizenberg, J., Angew. Chemie 42, 3668 (2003).Google Scholar
4 Lochhead, M. J., Letellier, S. R., and Vogel, V., J. Phys. Chem. B 101, 10821 (1997).Google Scholar
5 Pach, L., Hrabe, Z., Komarneni, S., and Roy, R., J. Mater. Res. 5, 2928 (1990).Google Scholar
6 Agarwal, P. and Bergland, K. A., Cryst. Growth Des. 3, 941 (2003).Google Scholar
7 Kim, I. W., Robertson, R. E., and Zand, R., Cryst. Growth Des. 5, 513 (2005).Google Scholar
8 Lakshminarayanan, R., Kini, R. M., and Valiyaveettil, S., PNAS 99 (2002).Google Scholar
9 Beniash, E. et al, Proc. R. Soc. Lond. B, 461 (1997).Google Scholar
10 Wilt, F., J. Struct. Biol. 126, 216 (1999).Google Scholar
11 Brooks, R. et al, Proc. Royal Soc. London 243A, 145 (1950).Google Scholar
12 DiMasi, E., Patel, V. M., Sivakumar, M., Olszta, M. J., Yang, Y. P., and Gower, L. B., Langmuir 18, 8902 (2002).Google Scholar
13 Bolze, J., Peng, B., Dingenouts, N., Panine, P., Narayanan, T., and Ballauff, M., Langmuir 18, 8364 (2002).Google Scholar
14 Pontoni, D. et al, J. Phys. Chem. B 107, 5123 (2003).Google Scholar
15 Gower, L. B. and Odom, D. J., J. Crystal Growth 210, 719 (2000).Google Scholar
16 Olszta, M. J., Douglas, E. P., and Gower, L. B., in Materials Inspired by Biology, MRS Proceedings Volume 774, page 127, Warrendale PA (2003).Google Scholar
17 Kim, Y. and Gower, L. B., in Materials Inspired by Biology, MRS Proceedings Volume 774, page 141, Warrendale PA (2003).Google Scholar
18 Liu, T., Rulkens, R., Wegner, G., and Chu, B., Macromolecules 31, 6119 (1998).Google Scholar