https://orcid.org/0000-0001-5746-2298
Abstract
Magnesium sulfate (MgSO4) is a salt that has the potential to damage portland cement-based materials. This paper argues that the mechanism of damage is dependent on the concentration of MgSO4 and reports the results of the change in the micromechanical properties of calcium-silicate-hydrate (C-S-H) when exposed to different MgSO4 concentrations . Different concentrations were selected starting from the concentration found in seawater and increasing up to 20 g/l, which is the concentration considered for accelerated tests. The micromechanical properties of C-S-H were probed using nanoindentation; X-ray diffraction measurements were also performed on C-S-H specimens. A Mori-Tanaka homogenization scheme was employed to upscale these results, yielding two homogenization levels. At low MgSO4 concentrations (2.2 and 4 g/l) the formation of brucite and gypsum crystals in the pore solution contributes to the overall magnitude of the elastic modulus of the specimen, while at higher concentrations of MgSO4 (10 and 20 g/l), decalcification of C-S-H is observed, which results in the degradation of C-S-H micromechanical properties.
Issue Section:
Technical Papers
References
1.
Ma
X.
, Çopuroglu
O.
, Schlangen
E.
, Han
N.
, and King
F.
, “Experimental and Numerical Study on Cement Paste Degradation under External Sulfate Attack
,” in Proceedings of the Ninth International Conference on Fracture Mechanics of Concrete and Concrete Structures
(Paris
: International Union of Laboratories and Experts in Construction Materials, Systems and Structures
, 2016
), 1
–9
, https://doi.org/10.21012/FC9.0882.
Kunther
W.
, Lothenbach
B.
, and Scrivener
K. L.
, “Deterioration of Mortar Bars Immersed in Magnesium Containing Sulfate Solutions
,” Materials and Structures
46
(February 2013
): 2003
–2011
, https://doi.org/10.1617/s11527-013-0032-63.
Bonen
D.
and Cohen
M. D.
, “Magnesium Sulfate Attack on Portland Cement Paste-I. Microstructural Analysis
,” Cement and Concrete Research
22
, no. 1
(January 1992
): 169
–180
, https://doi.org/10.1016/0008-8846(92)90147-N4.
Ragab
A. M.
, Elgammal
M. A.
, Hodhod
O. A. G.
, and Ahmed
T. E.
, “Evaluation of Field Concrete Deterioration under Real Conditions of Seawater Attack
,” Construction and Building Materials
119
(August 2016
): 130
–144
, https://doi.org/10.1016/j.conbuildmat.2016.05.0145.
Jakobsen
U. H.
, De Weerdt
K.
, and Geiker
M. R.
, “Elemental Zonation in Marine Concrete
,” Cement and Concrete Research
85
(July 2016
): 12
–27
, https://doi.org/10.1016/j.cemconres.2016.02.0066.
Jakobsen
U. H.
, “Microstructural Surface Deterioration of Concrete Exposed to Seawater; Results after 2 Years Exposure
,” in 14th Euroseminar on Microscopy Applied to Building Materials
(Copenhagen, Denmark
: Danish Technological Institute
, 2013
), 10
–14
.7.
Neville
A. M.
, “Behaviour of Concrete in Saturated and Weak Solutions of Magnesium Sulphate or Calcium Chloride
,” Journal of Materials Science
4
(1969
): 781
–816
.8.
Dramé
H.
, Beaudoin
J. J.
, and Raki
L.
, “A Comparative Study of the Volume Stability of C-S-H (I) and Portland Cement Paste in Aqueous Salt Solutions
,” Journal of Materials Science
42
(August 2007
): 6837
–6846
, https://doi.org/10.1007/s10853-006-1328-59.
Ulm
F.-J.
, Constantinides
G.
, and Keukamp
F. H.
, “Is Concrete a Poromechanics Materials?—A Multiscale Investigation of Poroelastic Properties
,” Materials and Structures
37
(January 2004
): 43
–58
, https://doi.org/10.1007/BF0248162610.
Jennings
H. M.
, Thomas
J. J.
, Gevrenov
J. S.
, Constantinides
G.
, and Ulm
F.-J.
, “A Multi-technique Investigation of the Nanoporosity of Cement Paste
,” Cement and Concrete Research
37
, no. 3
(March 2007
): 329
–336
, https://doi.org/10.1016/j.cemconres.2006.03.02111.
Benveniste
Y.
, “A New Approach to the Application of Mori-Tanaka’s Theory in Composite Materials
,” Mechanics of Materials
6
(1987
): 147
–157
.12.
Wesselsky
A.
and Jensen
O. M.
, “Synthesis of Pure Portland Cement Phases
,” Cement and Concrete Research
39
, no. 11
(November 2009
): 973
–980
, https://doi.org/10.1016/j.cemconres.2009.07.01313.
Taylor
H. F. W.
, “Reactions during Cooling, Grinding or Storage,” in Cement Chemistry
, 2nd ed. (London
: Thomas Telford Publishing
, 1997
), 77
–84
.14.
Snellings
R.
, Bazzoni
A.
, and Scrivener
K.
, “The Existence of Amorphous Phase in Portland Cements: Physical Factors Affecting Rietveld Quantitative Phase Analysis
,” Cement and Concret Reseraach
59
(May 2014
): 139
–146
, https://doi.org/10.1016/j.cemconres.2014.03.00215.
Taylor
H. F. W.
, Cement Chemistry
(London
: Academic Press
, 1990
).16.
Collepardi
M.
and Massidda
L.
, “Hydration of Tricalcium Silicate
,” Journal of the American Ceramic Society
54
, no. 9
(1971
): 419
–422
, https://doi.org/10.1111/j.1151-2916.1971.tb12378.x17.
Baoping He
B.
, Two‐Dimensional X‐Ray Diffraction,
2nd ed. (Hoboken, NJ
: John Wiley & Sons, Inc.
, 2018
), https://doi.org/10.1002/978111935608018.
De la Torre
A. G.
and Arranda
M. A. G.
, “Accuracy in Rietveld Quantitative Phase Analysis of Portland Cements Research Papers
,” Journal of Applied Crystallography
36
(2003
): 1169
–1176
, https://doi.org/10.1107/S002188980301375X19.
León-Reina
L.
, De la Torre
A. G.
, Porras-Vázquez
J. M.
, Cruz
M.
, Ordonez
L. M.
, Alcobé
X.
, Gispert-Guirado
F.
, et al., “Round Robin on Rietveld Quantitative Phase Analysis of Portland Cements
,” Journal of Applied Crystallography
42
(2009
): 906
–916
, https://doi.org/10.1107/S002188980902837420.
Powers
T. C.
and Brownyard
T. L.
, “Studies of the Physical Properties of Hardened Portland Cement Paste
,” Journal of American Concrete Institute
18
(1947
): 845
–880
.21.
Jennings
H. M.
and Tennis
P. D.
, “Model for the Developing Microstructure in Portland Cement Pastes
,” Journal of the American Ceramic Society
77
, no. 12
(December 1994
): 3161
–3172
, https://doi.org/10.1111/j.1151-2916.1994.tb04565.x22.
Ulm
F.-J.
, Lemarchand
E.
, and Heukamp
F. H.
, “Elements of Chemomechanics of Calcium Leaching of Cement-Based Materials at Different Scales
,” Engineering Fracture Mechanics
70
, nos. 7–8
(May 2003
): 871
–889
, https://doi.org/10.1016/S0013-7944(02)00155-823.
Collier
N. C.
, “Transition and Decomposition Temperatures of Cement Phases - a Collection of Thermal Analysis Data
,” Ceramics-Silikáty
60
, no. 4
(2016
): 338
–343
, https://doi.org/10.13168/cs.2016.005024.
Viczian
I.
, “Foldvari, Maria: Handbook of the Thermogravimetric System of Minerals and Its Use in Geological Practice
,” Central European Geology
56
, no. 4
(December 2013
): 397.25.
Bellmann
F.
, Möser
B.
, and Stark
J.
, “Influence of Sulfate Solution Concentration on the Formation of Gypsum in Sulfate Resistance Test Specimen
,” Cement and Concrete Research
36
, no. 2
(February 2006
): 358
–363
, https://doi.org/10.1016/j.cemconres.2005.04.00626.
Beaudoin
J. J.
, Catinaud
S.
, and Marchand
J.
, “Volume Stability of Calcium Hydroxide in Aggressive Solutions
,” Cement and Concrete Research
31
, no. 1
(January 2001
): 149
–151
, https://doi.org/10.1016/S0008-8846(00)00433-627.
Al-Dulaijan
S. U.
, “Sulfate Resistance of Plain and Blended Cements Exposed to Magnesium Sulfate Solutions
,” Construction and Building Materials
21
, no. 8
(August 2007
): 1792
–1802
, https://doi.org/10.1016/j.conbuildmat.2006.05.01728.
Constantinides
G.
, “Invariant Mechanical Properties of C-S-H in Cement-Based Materials: Instrumented Nanoindentation and Microporomechanical Modeling
” (PhD diss., Massachusetts Institute of Technology
, 2006
).29.
Scrivener
K.
, Snellings
R.
, and Lothenbach
B.
, eds., A Practical Guide to Microstructural Analysis of Cementitious Materials (Boca Raton, FL: CRC Press
, 2016
), https://doi.org/10.1201/b1907430.
Mondal
P.
, “Nanomechanical Properties of Cementitious Materials
” (PhD diss., Northwestern University
, 2008
).31.
Constantinides
G.
, Ulm
F.-J.
, and Van Vliet
K.
, “On the Use of Nanoindentation for Cementitious Materials
,” Materials and Structures
36
(April 2003
): 191
–196
, https://doi.org/10.1007/BF0247955732.
Hu
C.
and Li
Z.
, “A Review on the Mechanical Properties of Cement-Based Materials Measured by Nanoindentation
,” Construction and Building Materials
90
(August 2015
): 80
–90
, https://doi.org/10.1016/j.conbuildmat.2015.05.00833.
Oliver
W. C.
and Pharr
G. M.
, “An Improved Technique for Determining Hardness and Elastic Modulus Using Load and Displacement Sensing Indentation Experiments
,” Journal of Materials Reserach
7
, no. 6
(June 1992
): 1564
–1583
, https://doi.org/10.1557/JMR.1992.156434.
McLachlan
G.
and Peel
D.
, “The EMMIX Algorithm for the Fitting of Normal and t-Components
,” Journal of Statistcal Software
4
, no. 2
(July 1999
): 1
–14
, https://doi.org/10.18637/jss.v004.i0235.
Dempster
A. P.
, Laird
N. M.
, and Rubin
D. B.
, “Maximum Likelihood from Incomplete Data via the EM Algorithm
,” Journal of the Royal Statistical Society
39
, no. 1
(1977
): 1
–38
.36.
Constantinides
G.
and Ulm
F.-J.
, “The Effect of Two Types of C-S-H on the Elasticity of Cement-Based Materials: Results from Nanoindentation and Micromechanical Modeling
,” Cement and Concrete Reserach
34
, no. 1
(January 2004
): 67
–80
, https://doi.org/10.1016/S0008-8846(03)00230-837.
Malvern Panalytical “
HighScore Plus
,” Malvern Panalytical, 2020
, https://web.archive.org/web/20211020190141/https://www.malvernpanalytical.com/en/products/category/software/x-ray-diffraction-software/highscore-with-plus-option38.
Kunther
W.
, Lothenbach
B.
, and Skibsted
J.
, “Influence of the Ca/Si Ratio of the C-S-H Phase on the Interaction with Sulfate Ions and Its Impact on the Ettringite Crystallization Pressure
,” Cement and Concrete Research
69
(March 2015
): 37
–49
, https://doi.org/10.1016/j.cemconres.2014.12.00239.
Bonen
D.
and Cohen
M. D.
, “Magnesium Sulfate Attack on Portland Cement Paste-II. Chemical and Mineralogical Analyses
,” Cement and Concrete Research
22
(1992
): 707
–718
.40.
Jiang
F.
, Speziale
S.
, and Duffy
T. S.
, “Single-Crystal Elasticity of Brucite, Mg(OH)2, to 15 GPa by Brillouin Scattering
,” American Mineralogist
91
, nos. 11–12
(November 2006
): 1893
–1900
, https://doi.org/10.2138/am.2006.221541.
Fu
J.
and Lin
W.
, “Elastic Constants and Homogenized Moduli of Gypsum Structure Based on Density Functional Theory
,” in Proceedings of the 2017 Third International Forum on Energy, Enviornment Science and Materials (IFEESM 2017)
(Shenzhen, China
: Atlantis Press
, 2018
), 390
–395
, https://doi.org/10.2991/ifeesm-17.2018.7342.
Tian
B.
and Cohen
M. D.
, “Does Gypsum Formation during Sulfate Attack on Concrete Lead to Expansion?
” Cement and Concrete Research
30
, no. 1
(January 2000
): 117
–123
, https://doi.org/10.1016/S0008-8846(99)00211-243.
Nied
D.
, Enemark-Rasmussen
K.
, L’Hopital
E.
, Skibsted
J.
, and Lothenbach
B.
, “Properties of Magnesium Silicate Hydrates (M-S-H)
,” Cement and Concrete Research
79
(January 2016
): 323
–332
, https://doi.org/10.1016/j.cemconres.2015.10.00344.
Bernard
E.
, Lothenbeach
B.
, Cau-Dit-Coumes
C.
, Chlique
C.
, Dauzères
A.
, and Pochard
I.
, “Magnesium and Calcium Silicate Hydrates, Part I: Investigation of the Possible Magnesium Incorporation in Calcium Silicate Hydrate (C-S-H) and of the Calcium in Magnesium Silicate Hydrate (M-S-H)
,” Applied Geochemistry
89
(February 2018
): 229
–242
, https://doi.org/10.1016/j.apgeochem.2017.12.00545.
Tennis
P. D.
and Jennings
H. M.
, “A Model for Two Types of Calcium Silicate Hydrate in the Microstructure of Portland Cement Pastes
,” Cement and Concrete Research
30
, no. 6
(June 2000
): 855
–863
, https://doi.org/10.1016/S0008-8846(00)00257-X46.
Jennings
H. M.
, “Colloid Model of C-S-H and Implications to the Problem of Creep and Shrinkage
,” Materials and Structures
37
(January 2004
): 59
–70
, https://doi.org/10.1007/BF0248162747.
Moesen
M.
, “MMTensor 1.0
,” MathWorks
, 2011
, https://web.archive.org/web/20211020192542/https://www.mathworks.com/matlabcentral/fileexchange/32891-mmtensor-1-048.
Xia
X.
, Weidner
D. J.
, and Zhao
H.
, “Equation of State of Brucite: Single-Crystal Brillouin Spectroscopy Study and Polycrystalline Pressure-Volume-Temperature Measurement
,” American Mneralogist
83
, nos. 1–2
(February 1998
): 68
–74
, https://doi.org/10.2138/am-1998-1-20749.
Snahuja
J.
, Dormieux
L.
, Meille
S.
, Hellmich
C.
, and Fritsch
A.
, “Micromechanical Explanation of Elasticity and Strength of Gypsum: From Elongated Anisotropic Crystals to Isotropic Porous Polycrystals
,” Journal of Engineering Mechanics
136
, no. 2
(February 2010
): 239
–253
, https://doi.org/10.1061/(ASCE)EM.1943-7889.0000072
This content is only available via PDF.
All rights reserved. This material may not be reproduced or copied, in whole or part, in any printed, mechanical, electronic, film, or other distribution and storage media, without the written consent of ASTM International.
You do not currently have access to this content.
