Title:
Chloride Binding of Cementitious Materials Exposed to Sodium Chloride Using X-Ray Fluorescence
Author(s):
Marisol Tsui-Chang, Chunyu Qiao, Luca Montanari, Prannoy Suraneni, and W. Jason Weiss
Publication:
Materials Journal
Volume:
116
Issue:
5
Appears on pages(s):
173-179
Keywords:
chloride binding; sodium chloride; titration; X-ray fluorescence
DOI:
10.14359/51716996
Date:
9/1/2019
Abstract:
Chloride binding is typically studied by exposing a certain quantity of powdered hydrated cement paste to chloride salt solutions, and by comparing the differences in final and initial chloride concentrations after equilibrium is achieved. Chloride concentrations are generally determined by titrating the solutions using manual or automatic titration. Chloride-binding isotherms are obtained by repeating this process for a range of chloride concentrations. While titration produces accurate results, the process can be labor-and time-intensive. In this work, chloride-binding isotherms are obtained by testing chloride solutions using a calibrated X-ray fluorescence (XRF) device and were evaluated by comparison with titration. Testing was performed on a cement paste with a water-cement ratio of 0.42, exposed to sodium chloride salt solutions ranging from 0 to 5 mol/L at 23°C. Chloride concentrations determined by titration and XRF were similar (differences averaged approximately 3% for the various solutions tested); however, chloride-binding isotherms obtained using the two methods showed significant differences (differences averaged approximately 49% for different chloride binding contents) due to assumptions regarding solution density. When the solution density was accurately measured using a pycnometer, chloride-binding isotherms obtained using titration and XRF were very similar, with differences averaging less than 6%. The importance of accurate density measurements for such calculations is demonstrated mathematically. While these results are preliminary and need to be verified for other salt solutions and cementitious paste compositions, they suggest that the use of XRF may provide a promising alternative to determine chloride-binding isotherms in cementitious materials.
Related References:
1. Apostolopoulos, C. A., and Papadakis, V. G., “Consequences of Steel Corrosion on the Ductility Properties of Reinforcement Bar,” Construction and Building Materials, V. 22, No. 12, 2008, pp. 2316-2324. doi: 10.1016/j.conbuildmat.2007.10.006
2. Angst, U.; Elsener, B.; Larsen, C. K.; and Vennesland, Ø., “Critical Chloride Content in Reinforced Concrete—A Review,” Cement and Concrete Research, V. 39, No. 12, 2009, pp. 1122-1138. doi: 10.1016/j.cemconres.2009.08.006
3. Beaudoin, J. J.; Ramachandran, V. S.; and Feldman, R. F., “Interaction of Chloride and C-S-H,” Cement and Concrete Research, V. 20, No. 6, 1990, pp. 875-883. doi: 10.1016/0008-8846(90)90049-4
4. Birnin-Yauri, U. A., and Glasser, F. P., “Friedel’s Salt, Ca2Al(OH)6 (Cl,OH)·2H2O: Its Solid Solutions and Their Role in Chloride Binding,” Cement and Concrete Research, V. 28, No. 12, 1998, pp. 1713-1723. doi: 10.1016/S0008-8846(98)00162-8
5. Mesbah, A.; François, M.; Cau-dit-Coumes, C.; Frizon, F.; Filinchuk, Y.; Leroux, F.; Ravaux, J.; and Renaudin, G., “Crystal Structure of Kuzel’s Salt 3CaO·Al2O3·1/2CaSO4·1/2CaCl2·11H2O Determined by Synchrotron Powder Diffraction,” Cement and Concrete Research, V. 41, No. 5, 2011, pp. 504-509. doi: 10.1016/j.cemconres.2011.01.015
6. Glass, G. K., and Buenfeld, N. R., “The Influence of Chloride Binding on the Chloride Induced Corrosion Risk in Reinforced Concrete,” Corrosion Science, V. 42, No. 2, 2000, pp. 329-344. doi: 10.1016/S0010-938X(99)00083-9
7. Justnes, H., “A Review of Chloride Binding in Cementitious Systems,” Nordic Concrete Research, V. 21, 1998, pp. 48-63.
8. Bu, Y.; Luo, D.; and Weiss, J., “Using Fick’s Second Law and Nernst-Planck Approach in Prediction of Chloride Ingress in Concrete Materials,” Advances in Civil Engineering Materials, V. 3, No. 1, 2014, pp. 566-585. doi: 10.1520/ACEM20140018
9. De Weerdt, K.; Colombo, A.; Coppola, L.; Justnes, H.; and Geiker, M. R., “Impact of the Associated Cation on Chloride Binding of Portland Cement Paste,” Cement and Concrete Research, V. 68, 2015, pp. 196-202. doi: 10.1016/j.cemconres.2014.01.027
10. Qiao, C.; Suraneni, P.; and Weiss, J., “Phase Diagram and Volume Change of the Ca(OH)2-CaCl2-H2O System for Varying Ca(OH)2/CaCl2 Molar Ratios,” Journal of Materials in Civil Engineering, ASCE, V. 30, No. 2, 2018, p. 04017281 doi: 10.1061/(ASCE)MT.1943-5533.0002145
11. Tang, L., and Nilsson, L.-O., “Chloride Binding Capacity and Binding Isotherms of OPC Pastes and Mortars,” Cement and Concrete Research, V. 23, No. 2, 1993, pp. 247-253. doi: 10.1016/0008-8846(93)90089-R
12. Thomas, M. D. A.; Hooton, R. D.; Scott, A.; and Zibara, H., “The Effect of Supplementary Cementitious Materials on Chloride Binding in Hardened Cement Paste,” Cement and Concrete Research, V. 42, No. 1, 2012, pp. 1-7. doi: 10.1016/j.cemconres.2011.01.001
13. Shi, Z.; Geiker, M. R.; De Weerdt, K.; Østnor, T. A.; Lothenbach, B.; Winnefeld, F.; and Skibsted, J., “Role of Calcium on Chloride Binding in Hydrated Portland Cement–Metakaolin–Limestone Blends,” Cement and Concrete Research, V. 95, 2017, pp. 205-216. doi: 10.1016/j.cemconres.2017.02.003
14. Trejo, D.; Shakouri, M.; Vaddey, N. P.; and Isgor, O. B., “Development of Empirical Models for Chloride Binding in Cementitious Systems Containing Admixed Chlorides,” Construction and Building Materials, V. 189, 2018, pp. 157-169. doi: 10.1016/j.conbuildmat.2018.08.197
15. De Weerdt, K.; Colombo, A.; Coppola, L.; Justnes, H.; and Geiker, M. R., “Impact of the Associated Cation on Chloride Binding of Portland Cement Paste,” Cement and Concrete Research, V. 68, 2015, pp. 196-202. doi: 10.1016/j.cemconres.2014.01.027
16. Qiao, C.; Suraneni, P.; and Weiss, J., “Damage in Cement Pastes Exposed to NaCl Solutions,” Construction and Building Materials, V. 171, 2018, pp. 120-127. doi: 10.1016/j.conbuildmat.2018.03.123
17. De Weerdt, K.; Orsáková, D.; and Geiker, M. R., “The Impact of Sulphate and Magnesium on Chloride Binding in Portland Cement Paste,” Cement and Concrete Research, V. 65, 2014, pp. 30-40. doi: 10.1016/j.cemconres.2014.07.007
18. Saillio, M.; Baroghel-Bouny, V.; and Barberon, F., “Chloride Binding in Sound and Carbonated Cementitious Materials with Various Types of Binder,” Construction and Building Materials, V. 68, 2014, pp. 82-91. doi: 10.1016/j.conbuildmat.2014.05.049
19. Baroghel-Bouny, V.; Wang, X.; Thiery, M.; Saillio, M.; and Barberon, F., “Prediction of Chloride Binding Isotherms of Cementitious Materials by Analytical Model or Numerical Inverse Analysis,” Cement and Concrete Research, V. 42, No. 9, 2012, pp. 1207-1224. doi: 10.1016/j.cemconres.2012.05.008
20. Tsui-Chang, M.; Suraneni, P.; Isgor, O. B.; Trejo, D.; and Weiss, W. J., “Using X-Ray Fluorescence to Assess the Chemical Composition and Resistivity of Simulated Cementitious Pore Solutions,” International Journal of Advances in Engineering Sciences and Applied Mathematics, V. 9, No. 3, 2017, pp. 136-143. doi: 10.1007/s12572-017-0181-x
21. Tsui-Chang, M.; Montanari, L.; Suraneni, P.; and Weiss, W. J., “Expression of Cementitious Pore Solution and the Analysis of its Chemical Composition and Resistivity Using X-Ray Fluorescence,” Journal of Visualized Experiments, V. 139, 2018, p. e58432.
22. Tsui-Chang, M.; Suraneni, P.; Montanari, L.; Munoz, J. F.; and Weiss, W. J., “Determination of Chemical Composition and Electrical Resistivity of Expressed Cementitious Pore Solutions Using X-Ray Fluorescence,” ACI Materials Journal, V. 116, No. 1, Jan. 2019, pp. 155-164. doi: 10.14359/51712242
23. Cao, Y.; Zavaterri, P.; Youngblood, J.; Moon, R.; and Weiss, W. J., “The Influence of Cellulose Nanocrystal Additions on the Performance of Cement Paste,” Cement and Concrete Composites, V. 56, 2015, pp. 73-83. doi: 10.1016/j.cemconcomp.2014.11.008
24. Todd, N. T., “Assessing Risk Reduction of High Early Strength Concrete Mixtures,” MS thesis, Purdue University, West Lafayette, IN, 2015.
25. Qiao, C.; Suraneni, P.; Then, N. W. Y.; Choudhary, A.; and Weiss, W. J., “Chloride Binding of Cement Pastes with Fly Ash Exposed to CaCl2 Solutions at 5 and 23 °C,” Cement and Concrete Composites, V. 97, 2019, pp. 43-53. doi: 10.1016/j.cemconcomp.2018.12.011
26. Kaasa, R. I., “Calibration Technique for Quantitative Chloride Measurements with µ-XRF in Cementitious Materials,” MS thesis, Norweigian University of Science and Technology, Trondheim, Norway, 2018.
27. Archer, D. G., “Thermodynamic Properties of the NaCl+H2O System. II. Thermodynamic Properties of NaCl(aq), NaCl·2H2O(cr), and Phase Equilibria,” Journal of Physical and Chemical Reference Data, V. 21, No. 4, 1992, pp. 793-829. doi: 10.1063/1.555915