Aluminum-induced dreierketten chain cross-links increase the mechanical properties of nanocrystalline calcium aluminosilicate hydrate
Abstract
The incorporation of Al and increased curing temperature promotes the crystallization and cross-linking of calcium (alumino)silicate hydrate (C-(A-)S-H), which is the primary binding phase in most contemporary concrete materials. However, the influence of Al-induced structural changes on the mechanical properties at atomistic scale is not well understood. Herein, synchrotron radiation-based high-pressure X-ray diffraction is used to quantify the influence of dreierketten chain cross-linking on the anisotropic mechanical behavior of C-(A-)S-H. We show that the ab-planar stiffness is independent of dreierketten chain defects, e.g. vacancies in bridging tetrahedra sites and Al for Si substitution. The c-axis of non-cross-linked C-(A-)S-H is more deformable due to the softer interlayer opening but stiffens with decreased spacing and/or increased zeolitic water and Ca2+ of the interlayer. Dreierketten chain cross-links act as ‘columns’ to resist compression, thus increasing the bulk modulus of C-(A-)S-H. We provide the first experimental evidence on the influence of the Al-induced atomistic configurational change on the mechanical properties of C-(A-)S-H. Our work advances the fundamental knowledge of C-(A-)S-H on the lowest level of its hierarchical structure, and thus can impact the way that innovative C-(A-)S-H-based cementitious materials are developed using a ‘bottom-up’ approach.
- Authors:
-
- Univ. of California, Berkeley, CA (United States). Dept. of Civil and Environmental Engineering
- Univ. of California, Berkeley, CA (United States). Dept. of Civil and Environmental Engineering; Yale Univ., New Haven, CT (United States). School of Forestry & Environmental Studies
- Univ. of California, Berkeley, CA (United States). Dept. of Chemical & Biomolecular Engineering
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source
- Univ. of California, Berkeley, CA (United States). Dept. of Civil and Environmental Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); National Research Foundation (Singapore); Chinese Scholarship Council
- OSTI Identifier:
- 1408423
- Grant/Contract Number:
- AC02-05CH11231; DMR-1410557; 201206090127
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Scientific Reports
- Additional Journal Information:
- Journal Volume: 7; Journal ID: ISSN 2045-2322
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; civil engineering; mechanical properties; mineralogy
Citation Formats
Geng, Guoqing, Myers, Rupert J., Li, Jiaqi, Maboudian, Roya, Carraro, Carlo, Shapiro, David A., and Monteiro, Paulo J. M. Aluminum-induced dreierketten chain cross-links increase the mechanical properties of nanocrystalline calcium aluminosilicate hydrate. United States: N. p., 2017.
Web. doi:10.1038/srep44032.
Geng, Guoqing, Myers, Rupert J., Li, Jiaqi, Maboudian, Roya, Carraro, Carlo, Shapiro, David A., & Monteiro, Paulo J. M. Aluminum-induced dreierketten chain cross-links increase the mechanical properties of nanocrystalline calcium aluminosilicate hydrate. United States. https://doi.org/10.1038/srep44032
Geng, Guoqing, Myers, Rupert J., Li, Jiaqi, Maboudian, Roya, Carraro, Carlo, Shapiro, David A., and Monteiro, Paulo J. M. Fri .
"Aluminum-induced dreierketten chain cross-links increase the mechanical properties of nanocrystalline calcium aluminosilicate hydrate". United States. https://doi.org/10.1038/srep44032. https://www.osti.gov/servlets/purl/1408423.
@article{osti_1408423,
title = {Aluminum-induced dreierketten chain cross-links increase the mechanical properties of nanocrystalline calcium aluminosilicate hydrate},
author = {Geng, Guoqing and Myers, Rupert J. and Li, Jiaqi and Maboudian, Roya and Carraro, Carlo and Shapiro, David A. and Monteiro, Paulo J. M.},
abstractNote = {The incorporation of Al and increased curing temperature promotes the crystallization and cross-linking of calcium (alumino)silicate hydrate (C-(A-)S-H), which is the primary binding phase in most contemporary concrete materials. However, the influence of Al-induced structural changes on the mechanical properties at atomistic scale is not well understood. Herein, synchrotron radiation-based high-pressure X-ray diffraction is used to quantify the influence of dreierketten chain cross-linking on the anisotropic mechanical behavior of C-(A-)S-H. We show that the ab-planar stiffness is independent of dreierketten chain defects, e.g. vacancies in bridging tetrahedra sites and Al for Si substitution. The c-axis of non-cross-linked C-(A-)S-H is more deformable due to the softer interlayer opening but stiffens with decreased spacing and/or increased zeolitic water and Ca2+ of the interlayer. Dreierketten chain cross-links act as ‘columns’ to resist compression, thus increasing the bulk modulus of C-(A-)S-H. We provide the first experimental evidence on the influence of the Al-induced atomistic configurational change on the mechanical properties of C-(A-)S-H. Our work advances the fundamental knowledge of C-(A-)S-H on the lowest level of its hierarchical structure, and thus can impact the way that innovative C-(A-)S-H-based cementitious materials are developed using a ‘bottom-up’ approach.},
doi = {10.1038/srep44032},
journal = {Scientific Reports},
number = ,
volume = 7,
place = {United States},
year = {Fri Mar 10 00:00:00 EST 2017},
month = {Fri Mar 10 00:00:00 EST 2017}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 116 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
The Role of Al in Cross-Linking of Alkali-Activated Slag Cements
journal, November 2014
- Myers, Rupert J.; Bernal, Susan A.; Gehman, John D.
- Journal of the American Ceramic Society, Vol. 98, Issue 3
Does the Al substitution in C–S–H(I) change its mechanical property?
journal, January 2011
- Oh, Jae Eun; Clark, Simon M.; Monteiro, Paulo J. M.
- Cement and Concrete Research, Vol. 41, Issue 1
Unlocking the secrets of Al-tobermorite in Roman seawater concrete
journal, October 2013
- Jackson, M. D.; Chae, S. R.; Mulcahy, S. R.
- American Mineralogist, Vol. 98, Issue 10
The real structures of clinotobermorite and tobermorite 9 Å: OD character, polytypes, and structural relationships [The real structures of clinotobermorite and tobermorite 9 Å: OD character, polytypes, and structural relationships]
journal, March 2000
- Merlino, Stefano; Bonaccorsi, Elena; Armbruster, Thomas
- European Journal of Mineralogy, Vol. 12, Issue 2
Mechanism of aluminium incorporation into C–S–H from ab initio calculations
journal, January 2014
- Pegado, Luís; Labbez, Christophe; Churakov, Sergey V.
- J. Mater. Chem. A, Vol. 2, Issue 10
Least-Squares Fitting of a Straight line
journal, May 1966
- York, Derek
- Canadian Journal of Physics, Vol. 44, Issue 5
Alkali-activated fly ashes
journal, August 1999
- Palomo, A.; Grutzeck, M. W.; Blanco, M. T.
- Cement and Concrete Research, Vol. 29, Issue 8
The real structure of tobermorite 11A: normal and anomalous forms, OD character and polytypic modifications [The real structure of tobermorite 11A: normal and anomalous forms, OD character and polytypic modifications]
journal, May 2001
- Merlino, Stefano; Bonaccorsi, Elena; Armbruster, Thomas
- European Journal of Mineralogy, Vol. 13, Issue 3
Quantum Mechanical Metric for Internal Cohesion in Cement Crystals
journal, December 2014
- Dharmawardhana, C. C.; Misra, A.; Ching, Wai-Yim
- Scientific Reports, Vol. 4, Issue 1
The Crystal Structure of Tobermorite 14 A (Plombierite), a C-S-H Phase
journal, March 2005
- Bonaccorsi, Elena; Merlino, Stefano; Kampf, Anthony R.
- Journal of the American Ceramic Society, Vol. 88, Issue 3
Aluminum Incorporation to Dreierketten Silicate Chains
journal, March 2009
- Manzano, H.; Dolado, J. S.; Ayuela, A.
- The Journal of Physical Chemistry B, Vol. 113, Issue 9
First-Principles Study of Elastic Constants and Interlayer Interactions of Complex Hydrated Oxides: Case Study of Tobermorite and Jennite
journal, October 2009
- Shahsavari, Rouzbeh; Buehler, Markus J.; Pellenq, Roland J. -M.
- Journal of the American Ceramic Society, Vol. 92, Issue 10
Experimental determination of bulk modulus of 14Å tobermorite using high pressure synchrotron X-ray diffraction
journal, February 2012
- Oh, Jae Eun; Clark, Simon M.; Wenk, Hans-Rudolf
- Cement and Concrete Research, Vol. 42, Issue 2
Model structures for C-(A)-S-H(I)
journal, November 2014
- Richardson, Ian G.
- Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 70, Issue 6, p. 903-923
Tobermorites; their real structure and order-disorder (OD) character
journal, October 1999
- Merlino, Stefano; Bonaccorsi, Elena; Armbruster, Thomas
- American Mineralogist, Vol. 84, Issue 10
Location of Aluminum in Substituted Calcium Silicate Hydrate (C-S-H) Gels as Determined by 29Si and 27Al NMR and EELS
journal, September 1993
- Richardson, Ian G.; Brough, Adrian R.; Brydson, Rik
- Journal of the American Ceramic Society, Vol. 76, Issue 9
Rietveld refinement of the structures of 1.0 C-S-H and 1.5 C-S-H
journal, November 2012
- Battocchio, Francesco; Monteiro, Paulo J. M.; Wenk, Hans-Rudolf
- Cement and Concrete Research, Vol. 42, Issue 11
Influence of aluminium on the conversion of calcium silicate hydrate gels into 11 Å tobermorite at 90°C and 120°C
journal, May 1975
- Mitsuda, T.; Taylor, H. F. W.
- Cement and Concrete Research, Vol. 5, Issue 3
Structural characterization of C–S–H and C–A–S–H samples—Part I: Long-range order investigated by Rietveld analyses
journal, December 2009
- Renaudin, Guillaume; Russias, Julie; Leroux, Fabrice
- Journal of Solid State Chemistry, Vol. 182, Issue 12
Composition–solubility–structure relationships in calcium (alkali) aluminosilicate hydrate (C-(N,K-)A-S-H)
journal, January 2015
- Myers, Rupert J.; L'Hôpital, Emilie; Provis, John L.
- Dalton Transactions, Vol. 44, Issue 30
Effect of temperature and aluminium on calcium (alumino)silicate hydrate chemistry under equilibrium conditions
journal, February 2015
- Myers, Rupert J.; L'Hôpital, Emilie; Provis, John L.
- Cement and Concrete Research, Vol. 68
A molecular dynamics study of the aluminosilicate chains structure in Al-rich calcium silicate hydrated (C-S-H) gels
journal, June 2008
- Manzano, H.; Dolado, J. S.; Griebel, M.
- physica status solidi (a), Vol. 205, Issue 6
The use of nitrogen adsorption to assess the microstructure of cement paste
journal, May 2001
- Garci Juenger, Maria C.; Jennings, Hamlin M.
- Cement and Concrete Research, Vol. 31, Issue 6
Structural characterization of C–S–H and C–A–S–H samples—Part II: Local environment investigated by spectroscopic analyses
journal, December 2009
- Renaudin, Guillaume; Russias, Julie; Leroux, Fabrice
- Journal of Solid State Chemistry, Vol. 182, Issue 12
Atomic and nano-scale characterization of a 50-year-old hydrated C3S paste
journal, November 2015
- Geng, Guoqing; Taylor, Rae; Bae, Sungchul
- Cement and Concrete Research, Vol. 77
Engineering the bonding scheme in C–S–H: The iono-covalent framework
journal, February 2008
- Pellenq, R. J. -M.; Lequeux, N.; van Damme, H.
- Cement and Concrete Research, Vol. 38, Issue 2
Chemical composition mapping with nanometre resolution by soft X-ray microscopy
journal, September 2014
- Shapiro, David A.; Yu, Young-Sang; Tyliszczak, Tolek
- Nature Photonics, Vol. 8, Issue 10
Generalized Structural Description of Calcium–Sodium Aluminosilicate Hydrate Gels: The Cross-Linked Substituted Tobermorite Model
journal, April 2013
- Myers, Rupert J.; Bernal, Susan A.; San Nicolas, Rackel
- Langmuir, Vol. 29, Issue 17
Mechanical properties of crystalline calcium-silicate-hydrates: comparison with cementitious C-S-H gels
journal, June 2007
- Manzano, H.; Dolado, J. S.; Guerrero, A.
- physica status solidi (a), Vol. 204, Issue 6
DIOPTAS : a program for reduction of two-dimensional X-ray diffraction data and data exploration
journal, May 2015
- Prescher, Clemens; Prakapenka, Vitali B.
- High Pressure Research, Vol. 35, Issue 3
Advances in alternative cementitious binders
journal, December 2011
- Juenger, M. C. G.; Winnefeld, F.; Provis, J. L.
- Cement and Concrete Research, Vol. 41, Issue 12
A model for the C-A-S-H gel formed in alkali-activated slag cements
journal, October 2011
- Puertas, F.; Palacios, M.; Manzano, H.
- Journal of the European Ceramic Society, Vol. 31, Issue 12
Calibration of the pressure dependence of the R 1 ruby fluorescence line to 195 kbar
journal, June 1975
- Piermarini, G. J.; Block, S.; Barnett, J. D.
- Journal of Applied Physics, Vol. 46, Issue 6
Incorporation of aluminium in calcium-silicate-hydrates
journal, September 2015
- L’Hôpital, E.; Lothenbach, B.; Le Saout, G.
- Cement and Concrete Research, Vol. 75
Rietveld texture analysis from TOF neutron diffraction data
journal, September 2010
- Wenk, H. -R.; Lutterotti, L.; Vogel, S. C.
- Powder Diffraction, Vol. 25, Issue 3
Role of interatomic bonding in the mechanical anisotropy and interlayer cohesion of CSH crystals
journal, October 2013
- Dharmawardhana, C. C.; Misra, A.; Aryal, S.
- Cement and Concrete Research, Vol. 52
The effect of two types of C-S-H on the elasticity of cement-based materials: Results from nanoindentation and micromechanical modeling
journal, January 2004
- Constantinides, Georgios; Ulm, Franz-Josef
- Cement and Concrete Research, Vol. 34, Issue 1
X-ray diffraction: a powerful tool to probe and understand the structure of nanocrystalline calcium silicate hydrates
journal, September 2013
- Grangeon, Sylvain; Claret, Francis; Linard, Yannick
- Acta Crystallographica Section B Structural Science Crystal Engineering and Materials, Vol. 69, Issue 5, p. 465-473
Material and Elastic Properties of Al-Tobermorite in Ancient Roman Seawater Concrete
journal, May 2013
- Jackson, Marie D.; Moon, Juhyuk; Gotti, Emanuele
- Journal of the American Ceramic Society, Vol. 96, Issue 8
Combinatorial molecular optimization of cement hydrates
journal, September 2014
- Abdolhosseini Qomi, M. J.; Krakowiak, K. J.; Bauchy, M.
- Nature Communications, Vol. 5, Issue 1
Elasticity and constitution of the Earth's interior
journal, June 1952
- Birch, Francis
- Journal of Geophysical Research, Vol. 57, Issue 2
A molecular dynamics study of the aluminosilicate chains structure in Al-rich calcium silicate hydrated (C-S-H) gels
journal, June 2008
- Manzano, H.; Dolado, J. S.; Griebel, M.
- physica status solidi (a), Vol. 205, Issue 6
Incorporation of aluminium in calcium-silicate-hydrates
journal, September 2015
- L’Hôpital, E.; Lothenbach, B.; Le Saout, G.
- Cement and Concrete Research, Vol. 75
Aluminum Incorporation to Dreierketten Silicate Chains
journal, March 2009
- Manzano, H.; Dolado, J. S.; Ayuela, A.
- The Journal of Physical Chemistry B, Vol. 113, Issue 9
Generalized Structural Description of Calcium–Sodium Aluminosilicate Hydrate Gels: The Cross-Linked Substituted Tobermorite Model
journal, April 2013
- Myers, Rupert J.; Bernal, Susan A.; San Nicolas, Rackel
- Langmuir, Vol. 29, Issue 17
Quantum Mechanical Metric for Internal Cohesion in Cement Crystals
journal, December 2014
- Dharmawardhana, C. C.; Misra, A.; Ching, Wai-Yim
- Scientific Reports, Vol. 4, Issue 1
Mechanism of aluminium incorporation into C–S–H from ab initio calculations
journal, January 2014
- Pegado, Luís; Labbez, Christophe; Churakov, Sergey V.
- J. Mater. Chem. A, Vol. 2, Issue 10
DIOPTAS : a program for reduction of two-dimensional X-ray diffraction data and data exploration
journal, May 2015
- Prescher, Clemens; Prakapenka, Vitali B.
- High Pressure Research, Vol. 35, Issue 3
The Crystal Structure of Tobermorite 14 A (Plombierite), a C-S-H Phase
journal, March 2005
- Bonaccorsi, Elena; Merlino, Stefano; Kampf, Anthony R.
- Journal of the American Ceramic Society, Vol. 88, Issue 3
The real structure of tobermorite 11A: normal and anomalous forms, OD character and polytypic modifications [The real structure of tobermorite 11A: normal and anomalous forms, OD character and polytypic modifications]
journal, May 2001
- Merlino, Stefano; Bonaccorsi, Elena; Armbruster, Thomas
- European Journal of Mineralogy, Vol. 13, Issue 3
Works referencing / citing this record:
The synthesis of 1.13 nm tobermorite from carbonated opoka
journal, June 2018
- Smalakys, G.; Siauciunas, R.
- Journal of Thermal Analysis and Calorimetry, Vol. 134, Issue 1
Densification of the interlayer spacing governs the nanomechanical properties of calcium-silicate-hydrate
journal, September 2017
- Geng, Guoqing; Myers, Rupert J.; Qomi, Mohammad Javad Abdolhosseini
- Scientific Reports, Vol. 7, Issue 1
Understanding the deformation mechanism and mechanical characteristics of cementitious mineral analogues from first principles and reactive force field molecular dynamics
journal, January 2018
- Jiang, Jinyang; Yan, Yiru; Hou, Dongshuai
- Physical Chemistry Chemical Physics, Vol. 20, Issue 20
Effects of CO 2 and temperature on the structure and chemistry of C–(A–)S–H investigated by Raman spectroscopy
journal, January 2017
- Ortaboy, Sinem; Li, Jiaqi; Geng, Guoqing
- RSC Adv., Vol. 7, Issue 77
Quantitative disentanglement of nanocrystalline phases in cement pastes by synchrotron ptychographic X-ray tomography
journal, April 2019
- Cuesta, Ana; De la Torre, Ángeles G.; Santacruz, Isabel
- IUCrJ, Vol. 6, Issue 3
Quantitative disentanglement of nanocrystalline phases in cement pastes by synchrotron ptychographic X-ray tomography
text, January 2019
- Cuesta, Ana; De la Torre, Ángeles G.; Santacruz, Isabel
- International Union of Crystallography (IUCr)