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Characterization of C–S–H formed in coupled CO2–water cured Portland cement pastes

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Abstract

The coupled CO2–water curing technique has been used for curing Portland cement-based materials, enabling the cement/concrete products with rapid strength development and lower carbon footprints. However, there is still a lack of convincing understanding on the mechanism of the accelerated carbonation reactions of cement. This current work mainly focused on characterizing the C–S–H gel formed in the bulk cement paste prepared with a low water to cement ratio (w/c = 0.18) subjected to a coupled CO2–water curing regime, by using solid state 29Si NMR and infrared spectroscopy together with other common tools. The results indicated that the CO2 curing process led to the formation of C–S–H gel containing more Q2 species than that in the corresponding hydrated pastes. Prolonged CO2 curing incorporated more Al tetrahedra into the C–S–H gel. Meanwhile, both the amorphous carbonates and calcite were formed during the accelerated carbonation reactions, and the calcite crystals could serve as nuclei to accelerate the cement hydration at the early age. Excessive CO2 curing resulted in a deficiency of lime in solution, yielding a structurally modified C–S–H with the absence of interlayered Ca(OH)2, and longer silicate chains as well as a higher polymerization degree when compared to the C–S–H formed in the normally hydrated cement samples.

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References

  1. Guerrero A, Goni S, Moragues A, Dolado JS (2005) Microstructure and mechanical performance of belite cements from high calcium coal fly ash. J Am Ceram Soc 88:1845–1853

    Article  Google Scholar 

  2. Glasser FP, Zhang L (2001) High-performance cement matrices based on calcium sulfoaluminate-belite compositions. Cem Concr Res 31:1881–1886

    Article  Google Scholar 

  3. Arjunan P, Silsbee MR (1999) Sulfoaluminate-belite cement from low-calcium fly ash and sulfur-rich and other industrial by-products. Cem Concr Res 29:1305–1311

    Article  Google Scholar 

  4. Palomo A, Grutzeck MW, Blanco MT (1999) Alkali-activated fly ashes—a cement for the future. Cem Concr Res 29:1323–1329

    Article  Google Scholar 

  5. Bernal SA, Provis JL (2014) Durability of alkali-activated materials: progress and perspectives. J Am Ceram Soc 97:997–1008

    Article  Google Scholar 

  6. Alonso S, Palomo A (2001) Alkaline activation of metakaolin and calcium hydroxide mixtures: influence of temperature, activator concentration and solids ratio. Mater Lett 47:55–62

    Article  Google Scholar 

  7. Palomo A, Fernández-Jiménez A, Kovalchuk G, Ordoñez LM, Naranjo MC (2007) Opc-fly ash cementitious systems: study of gel binders produced during alkaline hydration. J Mater Sci 42:2958–2966

    Article  Google Scholar 

  8. Monkman S, Shao Y (2006) Assessing the carbonation behavior of cementitious materials. J Mater Civ Eng 18:768–776

    Article  Google Scholar 

  9. Zhan BJ, Poon CS, Shi CJ (2013) CO2 curing for improving the properties of concrete blocks containing recycled aggregates. Cem Concr Compos 42:1–8

    Article  Google Scholar 

  10. Klemm WA, Berger RL (1972) Accelerated curing of cementitious systems by carbon dioxide. Part I. Portland cement. Cem Concr Res 2:567–576

    Article  Google Scholar 

  11. Klemm WA, Berger RL (1972) Accelerated curing of cementitious systems by carbon dioxide. Part II. Hydraulic calcium silicates and aluminates. Cem Concr Res 2:647–652

    Article  Google Scholar 

  12. Young JF, Berger RL, Breese J (1974) Accelerated curing of compacted calcium silicate mortars on exposure to CO2. J Am Ceram Soc 57:394–397

    Article  Google Scholar 

  13. Goodbrake CJC, Young JF, Berger RL (1979) Reaction of beta-dicalcium silicate and tricalcium silicate with carbon dioxide and water vapor. J Am Ceram Soc 62:168–171

    Article  Google Scholar 

  14. Ortaboy S, Li J, Geng G, Myers RJ, Monteiro PJM, Maboudian R, Carraro C (2017) Effects of CO2 and temperature on the structure and chemistry of C–(A–)S–H investigated by Raman spectroscopy. RSC Adv 7:48925–48933

    Article  Google Scholar 

  15. Sevelsted TF, Skibsted J (2015) Carbonation of C–S–H and C–A–S–H samples studied by 13C, 27Al and 29Si MAS NMR spectroscopy. Cem Concr Res 71:56–65

    Article  Google Scholar 

  16. Berger R, Young J, Leung K (1972) Acceleration of hydration of calcium silicates by carbon dioxide treatment. Nat Phys Sci 240:16–18

    Article  Google Scholar 

  17. RostamiV ShaoY, BoydAJ HeZ (2012) Microstructure of cement paste subject to early carbonation curing. Cem Concr Res 42:186–193

    Article  Google Scholar 

  18. Zhan BJ, Xuan DX, Poon CS, Shi CJ (2016) Effect of curing parameters on CO2 curing of concrete blocks containing recycled aggregates. Cem Concr Compos 71:122–130

    Article  Google Scholar 

  19. Shtepenko O, Hills C, Brough A, Thomas M (2006) The effect of carbon dioxide on β-dicalcium silicate and Portland cement. Chem Eng J 118:107–118

    Article  Google Scholar 

  20. Shi C, Liu M, Zou Q, He F (2011) A study on factors influencing compressive strength of CO2-cured concrete. In: Leung C, Wan KT (eds) Proceeding of international RILEM conference on advances in construction materials though science and engineering. RILEM Publications SARL, Hong Kong, pp 703–711

    Google Scholar 

  21. Wang T, Huang H, Hu X, Fang M, Luo Z, Guo R (2017) Accelerated mineral carbonation curing of cement paste for CO2 sequestration and enhanced properties of blended calcium silicate. Chem Eng J 323:320–329

    Article  Google Scholar 

  22. Shao Y, Mirza MS, Wu X (2006) CO2 sequestration using calcium-silicate concrete. Can J Civ Eng 33:776–784

    Article  Google Scholar 

  23. Sorochkin M, Shchrov A, Safonov I (1975) Study of the possibility of using carbon dioxide for accelerating the hardening of products made from Portland cement. J Appl Chem 48:1211–1217

    Google Scholar 

  24. Sevelsted TF, Herfort D, Skibsted J (2013) 13C chemical shift anisotropies for carbonate ions in cement minerals and the use of 13C, 27Al and 29Si MAS NMR in studies of Portland cement including limestone additions. Cem Concr Res 52:100–111

    Article  Google Scholar 

  25. Glasser FP, Macphee DE, Lachowski EE (1988) Polymerization effects in C–S–H: implications for Portland cement hydration. Adv Cem Res 1:131–137

    Article  Google Scholar 

  26. Skibsted J, Jakobsen HJ, Hall C (1995) Quantification of calcium silicate phases in portland cements by 29Si MAS NMR spectroscopy. J Chem Soc, Faraday Trans 91:4423–4430

    Article  Google Scholar 

  27. Poulsen SL, Kocaba V, LeSaoût G, Jakobsen HJ, Scrivener KL, Skibsted J (2009) Improved quantification of alite and belite in anhydrous Portland cements by 29Si MAS NMR: effects of paramagnetic ions. Solid State Nucl Magn Reson 36:32–44

    Article  Google Scholar 

  28. Engelhardt G (2007) Silicon-29 NMR of solid silicates. In: Harris RK (ed) Encyclopedia of magnetic resonance. Wiley, Chichester

    Google Scholar 

  29. Lippmaa E, Mägi M (1980) Structural studies of silicates by solid-state high-resolution silicon-29NMR. J Am Ceram Soc 102:4889–4893

    Google Scholar 

  30. Masse S, Zanni H, Lecourtier J, Roussel JC, Rivereau A (1993) 29Si solid state NMR study of tricalcium silicate and cement hydration at high temperature. Cem Concr Res 23:1169–1177

    Article  Google Scholar 

  31. Hjorth J, Skibsted J, Jakobsen HJ (1988) 29Si MAS NMR studies of Portland cement components and effects of microsilica on the hydration reaction. Cem Concr Res 18:789–798

    Article  Google Scholar 

  32. Skibsted J, Andersen MD (2013) The effect of alkali ions on the incorporation of aluminum in the calcium silicate hydrate (C–S–H) phase resulting from Portland cement hydration studied by 29Si MAS NMR. J Am Ceram Soc 96:651–656

    Google Scholar 

  33. Richardson I, Groves G (1997) The structure of the calcium silicate hydrate phases present in hardened pastes of white Portland cement/blast-furnace slag blends. J Mater Sci 32:4793–4802

    Article  Google Scholar 

  34. Šauman Z (1971) Carbonization of porous concrete and its main binding components. Cem Concr Res 1:645–662

    Article  Google Scholar 

  35. Andersen MD, Jakobsen HJ, Skibsted J (2004) Characterization of white Portland cement hydration and the C–S–H structure in the presence of sodium aluminate by 27Al and 29Si MAS NMR spectroscopy. Cem Concr Res 34:857–868

    Article  Google Scholar 

  36. Dai Z, Tran TT, Skibsted J (2014) Aluminum incorporation in the C–S–H phase of white Portland cement-metakaolin blends studied by 27Al and 29Si MAS NMR spectroscopy. J Am Ceram Soc 97:2662–2671

    Article  Google Scholar 

  37. Poulsen SL (2009) Methodologies for measuring the degree of reaction in Portland cement blends with supplementary cementitious material by 29Si and 27Al MAS NMR spectroscopy. Aarhus University, Aarhus C

    Google Scholar 

  38. Brunet F, Charpentier T, Chao CN, Peycelon H, Nonat A (2010) Characterization by solid-state NMR and selective dissolution techniques of anhydrous and hydrated CEM V cement pastes. Cem Concr Res 40:208–219

    Article  Google Scholar 

  39. Barnes J, Clague A (1985) Hydration of Portland cement followed by 29Si solid-state NMR spectroscopy. J Mater Sci Lett 4:1293–1295

    Article  Google Scholar 

  40. Skibsted J (1990) Correlation between 29Si NMR chemical shifts and mean Si–O bond lengths for calcium silicates. Chem Phys Lett 172:279–283

    Article  Google Scholar 

  41. Edwards CL, Morgan R, Norman L, Funkhouser GP, Barron AR (2008) Correlation of cement performance property measurements with C3S/C2S ratio determined by solid state 29Si NMR measurements. Ind Eng Chem Res 47(15):5456–5463

    Article  Google Scholar 

  42. Taylor HFW (1989) Modification of the Bogue calculation. Adv Cem Res 2:73–77

    Article  Google Scholar 

  43. Lippmaa E, Mägi M, Tarmak M (1982) A high resolution 29Si NMR study of the hydration of tricalciumsilicate. Cem Concr Res 12:597–602

    Article  Google Scholar 

  44. Engelhardt G, Michel D (1987) High-resolution solid-state NMR of silicates and zeolites. Wiley, Chichester

    Google Scholar 

  45. Chen JJ, Thomas JJ, Taylor HFW, Jennings HM (2004) Solubility and structure of calcium silicate hydrate. Cem Concr Res 34:1499–1519

    Article  Google Scholar 

  46. Hirljac J, Wu Z, Young JF (1983) Silicate polymerization during the hydration of alite. Cem Concr Res 13:877–886

    Article  Google Scholar 

  47. Rodger S, Groves G (1988) Hydration of tricalcium silicate followed by 29Si NMR with cross-polarization. J Am Ceram Soc 71:91–96

    Article  Google Scholar 

  48. Cappelletto E, Borsacchi S, Geppi M, Ridi F, Fratini E, Baglioni P (2013) Comb-shaped polymers as nanostructure modifiers of calcium silicate hydrate: a 29Si solid-state NMR investigation. J Phys Chem C 117:22947–22953

    Article  Google Scholar 

  49. Al-Dulaijan SU, Parry-Jones G, Al-TayyibA HJ, Al-Mana AI (1990) 29Si magic-angle-spinning nuclear magnetic resonance study of hydrated cement paste and mortar. J Am Ceram Soc 73:736–739

    Article  Google Scholar 

  50. Sáez del Bosque IF, Martínez-Ramírez S, Martín-Pastor M, Blanco-Varela MT (2013) Effect of temperature on C–S–H gel nanostructure in white cement. Mater Struct 47:1867–1878

    Article  Google Scholar 

  51. Sáez del Bosque IF, Martín-Pastor M, Martínez-Ramírez S, Blanco-Varela MT (2013) Effect of temperature on C3S and C3S + nanosilica hydration and C–S–H structure. J Am Ceram Soc 96:957–965

    Article  Google Scholar 

  52. Richardson IG (2000) The nature of the hydration products in hardened cement pastes. Cem Concr Compos 22:97–113

    Article  Google Scholar 

  53. Richardson IG (1999) Nature of C–S–H in hardened cements. Cem Concr Res 29:1131–1147

    Article  Google Scholar 

  54. Myneni SCB, Traina SJ, Waychunas G, Logan TJ (1998) Vibrational spectroscopy of functional group chemistry and arsenate coordination in ettringite. Geochim Cosmochim Acta 62:3499–3514

    Article  Google Scholar 

  55. Liu F, Asce SM, Sun Z, Qi C (2005) Raman spectroscopy study on the hydration behaviors of Portland cement pastes during setting. J Mater Civ Eng 27:1–10

    Google Scholar 

  56. Yu P, Kirkpatrick RJ, Poe B, McMillan P, Cong X (1999) Structure of calcium silicate hydrate (C–S–H): near-, mid-, and far-infrared spectroscopy. J Am Ceram Soc 82:742–748

    Article  Google Scholar 

  57. Gunasekaran S, Anbalagan G, Pandi S (2006) Raman and infrared spectra of carbonates of calcite structure. J Raman Spectrosc 37:892–899

    Article  Google Scholar 

  58. Gabrielli C, Jaouhari R, Joiret S, Maurin G (2000) In situ Raman spectroscopy applied to electrochemical scaling. Determination of the structure of vaterite. J Raman Spectrosc 31:497–501

    Article  Google Scholar 

  59. Ylmén R, Jäglid U, Steenari BM, Panas I (2009) Early hydration and setting of Portland cement monitored by IR, SEM and Vicat techniques. Cem Concr Res 39:433–439

    Article  Google Scholar 

  60. Hughes TL, Methven CM, Jones TGJ, Pelham SE, Fletcher P, Hall C (1995) Determining cement composition by Fourier transform infrared spectroscopy. Adv Cem Based Mater 2:91–104

    Article  Google Scholar 

  61. Gao XF, Lo Y, Tam CM, Chung CY (1999) Analysis of the infrared spectrum and microstructure of hardened cement paste. Cem Concr Compos 29:805–812

    Article  Google Scholar 

  62. Renaudin G, Russias J, Leroux F, Cau-dit-Coumes C, Frizon F (2009) Structural characterization of C–S–H and C–A–S–H samples—part II: local environment investigated by spectroscopic analyses. J Solid State Chem 182:3320–3329

    Article  Google Scholar 

  63. Renaudin G, Bertrand A, Dubois M, Gomes S, Chevalier P, Labrosse A (2008) A study of water releases in ground (GCC) and precipitated (PCC) calcium carbonates. J Phys Chem Solids 69:1603–1614

    Article  Google Scholar 

  64. Mollah MYA, Lu F, Cocke DL (1998) An X-ray diffraction (XRD) and Fourier transform infrared spectroscopic (FT-IR) characterization of the speciation of arsenic (V) in Portland cement type-V. Sci Total Environ 224:57–68

    Article  Google Scholar 

  65. García Lodeiro I, Macphee DE, Palomo A, Fernández-Jiménez A (2009) Effect of alkalis on fresh C–S–H gels. FTIR analysis. Cem Concr Res 39:147–153

    Article  Google Scholar 

  66. Wagh A, Singh D, Knox L (1994) Rapid setting of Portland cement by greenhouse carbon dioxide capture. In: Proceedings of the 96th annual meeting of the American ceramic society. Indianapolis

  67. Shi C, Zou Q (2009) Use of CO2 as an accelerated curing agent for concrete blocks. Key Eng Mater 400–402:81–87

    Google Scholar 

  68. Owens K, Basheer P, Gupta BS (2007) Utilisation of carbon dioxide from flue gases to improve physical and microstructural properties of cement and concrete systems. In: Kraus RN, Naik TR, Peter Claisse S-P (eds) Proceeding of 1st international conference: sustainable construction materials and technologies. UW Milwaukee CBU, Coventry, pp 59–68

  69. Monkman S, Shao Y (2010) Carbonation curing of slag-cement concrete for binding CO2 and improving performance. J Mater Civ Eng 22:296–304

    Article  Google Scholar 

  70. Junior AN, Toledo Filho RD, Fairbairn EMR, Dweck J (2015) The effects of the early carbonation curing on the mechanical and porosity properties of high initial strength Portland cement pastes. Constr Build Mater 77:448–454

    Article  Google Scholar 

  71. Bonavetti VL, Rahhal VF, Irassar EF (2001) Studies on the carboaluminate formation in limestone filler-blended cements. Cem Concr Res 31:853–859

    Article  Google Scholar 

  72. Mollah MYA, Yu W, Schennach R, Cocke DL (2000) A Fourier transform infrared spectroscopic investigation of the early hydration of Portland cement and the influence of sodium lignosulfonate. Cem Concr Res 30:267–273

    Article  Google Scholar 

  73. Róg G, Kozłowska-Róg A (1983) Determination of the standard Gibbs free energies of formation of the calcium silicates by e.m.f. measurements. J Chem Thermodyn 15:107–110

    Article  Google Scholar 

  74. Moghaddam SE, Hejazi V, Hwang SH, Sreenivasan S, Miller J, Shi B, Zhao S, Rusakova I, Alizadeh AR, Whitmire KH, Shahsavari R (2017) Morphogenesis of cement hydrate. J Mater Chem A 5:3798–3811

    Article  Google Scholar 

  75. Berodier E, Scrivener K (2014) Understanding the filler effect on the nucleation and growth of C–S–H. J Am Ceram Soc 10:1–10

    Google Scholar 

  76. Young JF, Tongh S, Berger RL (1977) Compositions of solutions in contact with hydrating tricalcium silicate pastes. J Am Ceram Soc 60:193–198

    Article  Google Scholar 

  77. Grangeon S, Claret F, Roosz C, Sato T, Gaboreau S, Linard Y (2016) Structure of nanocrystalline calcium silicate hydrates: insights from X-ray diffraction, synchrotron X-ray absorption and nuclear magnetic resonance. J Appl Crystallogr 49:771–783

    Article  Google Scholar 

  78. Faucon P, Delagrave A, Petit JC, Marchand JM, Zanni H (1999) Aluminum incorporation in calcium silicate hydrates (C–S–H) depending on their Ca/Si ratio. J Phys Chem B 103:7796–7802

    Article  Google Scholar 

  79. Soyer-Uzun S, Chae SR, Benmore CJ, Wenk HR, Monteiro PJM (2012) Compositional evolution of calcium silicate hydrate (C–S–H) structures by total X-ray scattering. J Am Ceram Soc 95:793–798

    Article  Google Scholar 

  80. Geng G, Myers RJ, Qomi MJA, Monteiro PJM (2017) Densification of the interlayer spacing governs the nanomechanical properties of calcium–silicate–hydrate. Sci Rep 7:10986

    Article  Google Scholar 

  81. Geng G, Myers RJ, Li J, Maboudian R, Carraro C, Shapiro DA, Monteiro PJM (2017) Aluminum-induced dreierketten chain cross-links increase the mechanical properties of nanocrystalline calcium aluminosilicate hydrate. Sci Rep 7:1–10

    Article  Google Scholar 

  82. Pelisser F, Gleize PJP, Mikowski A (2012) Effect of the Ca/Si molar ratio on the micro/nanomechanical properties of synthetic C–S–H measured by nanoindentation. J Phys Chem C 116:17219–17227

    Article  Google Scholar 

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Acknowledgements

The authors wish to thank the Hong Kong Polytechnic University (Project of Strategic Importance and Research Institute for Sustainable Urban Development) for funding support. The use of the Solid-State NMR Spectroscopy facility at the College of Materials Science and Engineering, Nanjing Technical University which is supported by Prof. Wang Xiao-Jun, is acknowledged.

Funding

This study was funded by Project of Strategic Importance and Research Institute for Sustainable Urban Development of the Hong Kong Polytechnic University.

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  1. Department of Civil and Environmental Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, China

    Bao Jian Zhan, Dong Xing Xuan & Chi Sun Poon

  2. Key Laboratory of Building Safety and Energy Efficiency (Ministry of Education), College of Civil Engineering, Hunan University, Changsha, China

    Cai Jun Shi

  3. College of Civil Engineering, Shenzhen University, Shenzhen, Guangdong, China

    Shi Cong Kou

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  1. Bao Jian Zhan
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Zhan, B.J., Xuan, D.X., Poon, C.S. et al. Characterization of C–S–H formed in coupled CO2–water cured Portland cement pastes. Mater Struct 51, 92 (2018). https://doi.org/10.1617/s11527-018-1211-2

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