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Chemical evolution of alkali–silicate reaction (ASR) products: a Raman spectroscopic investigation

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Abstract

The objective of this study was to use Raman spectroscopy to study the morphology and chemical changes of alkali–silicate reaction (ASR) products over time. The reaction products induced by ASR on soda-lime glass slides in a high temperature alkaline environment (1 N NaOH at 80 °C) enriched with calcium hydroxide were studied at 0, 1, 4, 7, 14 and 28 days. The results show that the morphology of the granular-like and fan-like fascicles structure that formed at early ages was more ordered in terms of polymerization and dominated by Q3 and Q2 units. This information implies that the ASR products were probably of mainly alkali silica composition with low content of calcium in the structure. As the reaction proceeded the products depolymerized, forming a cloud-like morphology of decreased structural order which surrounded the initial product particles. It can be hypothesized that more calcium ions in the soak solution entered into the particle structure, promoting a depolymerization and possible formation of a C–S–H phase which was indicated by the dominant presence of Q1 units after 7 days of exposure. To corroborate the interpretation of Raman spectra, 28-day ASR products were verified by Fourier transform infrared.

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References

  1. Stanton TE (1940) Expansion of concrete through reaction between cement and aggregate. Proc Am Soc Civ Eng 66(10):1781–1811

    Google Scholar 

  2. Thomas MDA, Fournier B, Folliard K, Ideker J, Shehata M (2006) Test methods for evaluating preventive measures for controlling expansion due to alkali–silica reaction in concrete. Cem Concr Res 36:1842–1856

    Article  Google Scholar 

  3. Lindgård J, Andiç-Çakır Ö, Fernandes I, Rønning TF, Thomas MDA (2012) Alkali–silica reactions (ASR): literature review on parameters influencing laboratory performance testing. Cem Concr Res 42:223–243

    Article  Google Scholar 

  4. Lindgård J, Andiç-Çakıre Ö, Fernandesc I, Rønning TF, Thomas MDA (2012) Alkali–silica reactions (ASR): literature review on parameters influencing laboratory performance testing. Cem Concr Res 42(2):223–243

    Article  Google Scholar 

  5. Lindgård J, Thomas MDA, Sellevold EJ, Pedersen B, Andiç-Çakıre Ö, Justnes H, Rønning TF (2013) Alkali–silica reaction (ASR)—performance testing: influence of specimen pre-treatment, exposure conditions and prism size on alkali leaching and prism expansion. Cem Concr Res 53:68–90

    Article  Google Scholar 

  6. Lindgård J, Sellevold EJ, Thomas MDA, Pedersen B, Justnes H, Rønning TF (2013) Alkali–silica reaction (ASR)—performance testing: influence of specimen pre-treatment, exposure conditions and prism size on concrete porosity, moisture state and transport properties. Cem Concr Res 53:145–167

    Article  Google Scholar 

  7. Detwiler R (1997) The role of fly ash composition in reducing alkali–silica reaction. Portland Cement Association (PCA) R&D Series No. 2092

  8. Cong X-D, Kirkpatrick RJ (1993) 29Si MAS NMR spectroscopic investigation of alkali silica reaction product gels. Cem Concr Res 23(4):811–823

    Article  Google Scholar 

  9. Hou XQ, Struble LJ, Kirkpatrick RJ (2004) Formation of ASR gel and the roles of C–S–H and portlandite. Cem Concr Res 34:1683–1696

    Article  Google Scholar 

  10. Hou XQ, Kirkpatrick RJ, Struble LJ, Monteiro PJM (2005) Structural investigations of alkali silicate gels. J Am Ceram Soc 88(4):943–949

    Article  Google Scholar 

  11. Kurtis KE, Monteiro PJM, Brown JT, Meyer-Ilse W (1998) Imaging of ASR gel by soft X-ray microscopy. Cem Concr Res 28(3):411–442

    Article  Google Scholar 

  12. Garg N, Wang K, Martin SW (2013) A Raman spectroscopic study of the evolution of sulfates and hydroxides in cement–fly ash pastes. Cem Concr Res 53:91–103

    Article  Google Scholar 

  13. Torrens-Martin D, Fernandez-Carrasco L, Martinez-Ramirez S (2013) Hydration of calcium aluminates and calcium sulfoaluminate studied by Raman spectroscopy. Cem Concr Res 47:43–50

    Article  Google Scholar 

  14. Garbev K, Stemmermann P, Black L, Breen C, Yarwood J, Gasharova B (2007) Structural features of C–S–H(I) and its carbonation in air—a Raman spectroscopic study. Part I: fresh phases. J Am Ceram Soc 90(3):900–907

    Article  Google Scholar 

  15. Black L, Breen C, Yarwood J, Garbev K, Stemmermann P, Gasharova B (2007) Structural features of C–S–H(I) and its carbonation in air—A Raman spectroscopic study. Part II: carbonated phases. J Am Ceram Soc 90(3):908–917

    Article  Google Scholar 

  16. Potgieter-Vermaak SS, Potgieter JH, Van Grieken R (2006) The application of Raman spectrometry to investigate and characterize cement, Part I: a review. Cem Concr Res 36:656–662

    Article  Google Scholar 

  17. Skibsted J, Hall C (2008) Characterization of cement minerals, cements and their reaction products at the atomic and nano scale. Cem Concr Res 38:205–225

    Article  Google Scholar 

  18. Martínez-Ramírez S, Fernández-Carrasco L (2011) Raman spectroscopy: application to cementitious systems. In: Doyle SG (ed) Construction and building: design, materials, and techniques. Nova Science Publishers, New York, pp 233–244

    Google Scholar 

  19. Martinez-Ramirez S, Sanchez-Cortes S, Garcia-Ramos JV, Domingo C, Fortes C, Blanco-Varela MT (2003) Micro-Raman spectroscopy applied to depth profiles of carbonates formed in lime mortar. Cem Concr Res 33:2063–2068

    Article  Google Scholar 

  20. Balachandran C, Muñoz JF, Arnold T (2017) Characterization of alkali silica reaction gels using Raman spectroscopy. Cem Concr Res 92:66–74

    Article  Google Scholar 

  21. Leemann A (2017) Raman microscopy of alkali–silica reaction (ASR) products formed in concrete. Cem Concr Res 102:41–47

    Article  Google Scholar 

  22. Hernandez RJ, Faria T, Trujillo G (2007) Characterization of a soda-lime glass using thermal and diffractometry techniques and a thermal chamber. Am Ceram Soc Bull 86(1):51–54

    Google Scholar 

  23. Kurtis KE, Collins CL, Monteiro PJM (2002) The surface chemistry of the alkali–silica reaction: a critical evaluation and x-ray microscopy. Concr Sci Eng 4:2–11

    Google Scholar 

  24. Kurtis KE, Monteiro PJM, Brown JT, Meyer-Ilse W (1999) High resolution transmission soft X-ray microscopy of deterioration products developed in large concrete dams. J Microsc 196:288–298

    Article  Google Scholar 

  25. Gartner E, Kurtis KE, Monteiro PJM (2000) Proposed mechanism of C–S–H growth tested by soft X-ray microscopy. Cem Concr Res 30(5):817–822

    Article  Google Scholar 

  26. Taylor HFW (1990) Cement chemistry. Academic Press, London

    Google Scholar 

  27. Maraghechi H, Rajabipour F, Pantano CG, Burgos WD (2016) Effect of calcium on dissolution and precipitation of amorphous silica at high alkalinity. Cem Concr Res 87:1–13

    Article  Google Scholar 

  28. Leemann A, Le Saout G, Winnefeld F, Rentsch D, Lothenbach B (2011) Alkali–silica reaction: the influence of calcium on silica dissolution and the formation of reaction products. J Am Ceram Soc 94(4):1243–1249

    Article  Google Scholar 

  29. McMillan P (1984) Structural studies of silicate glasses and melts—applications and limitations of Raman spectroscopy. Am Miner 69:622–644

    Google Scholar 

  30. Kamitsos EI, Kapoutsis JA, Jain H, Hsieh CH (1994) Vibrational study of the role of trivalent ions in sodium trisilicate glass. J Non-Cryst Solids 171:31–45

    Article  Google Scholar 

  31. Kirkpatrick RJ, Yarger JL, McMillan PF, Ping Y, Cong X (1997) Raman spectroscopy of CSH, tobermorite, and jennite. Adv Cem Based Mater 5:93–99

    Article  Google Scholar 

  32. McMillan P (1984) A Raman spectroscopic study of glasses in the system CaO–MgO–SiO2. Am Miner 69:645–659

    Google Scholar 

  33. McMillan P, Piriou B (1983) Raman spectroscopic studies of silicate and related glass structure—a review. Bull Minéral 106:57–75

    Google Scholar 

  34. Neuville DR, Mysen BO (1996) Role of aluminium in the silicate network: in situ, high-temperature study of glasses and melts on the join SiO2–NaAlO2. Geochim Cosmochim Acta 60:1727–1737

    Article  Google Scholar 

  35. Liem NQ, Sagon G, Quang VX, Tan HV, Colomban P (2000) Raman study of the microstructure, composition and processing of ancient Vietnamese (proto) porcelains and celadons (13–16th centuries). J Raman Spectrosc 31:933–942

    Article  Google Scholar 

  36. Leemann A, Katayama T, Fernandes I, Broekmans MATM (2016) Types of alkali-aggregate reactions and the products formed. Proc Inst Civ Eng Constr Mater 169(3):128–135

    Article  Google Scholar 

  37. Schneider JF, Hasparyk NP, Silva DA, Monteiro PJM (2008) Effect of lithium nitrate on the alkali–silica reaction gel. J Am Ceram Soc 91(10):3370–3374

    Article  Google Scholar 

  38. Yu P, Kirkpatrick RJ, Poe B, McMillan PF, Cong X (1999) Structure of calcium silicate hydrate (C–S–H): near-, mid-, and far-Infrared spectroscopy. J Am Ceram Soc 82(3):742–748

    Article  Google Scholar 

Download references

Acknowledgements

The first author would like to thank the National Research Council (NRC) Research Associateship Program (RAP) for funding supports.

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Correspondence to Tung-Chai Ling.

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The authors do not have any conflicts of interest that could inappropriately influence this work. The conclusions are the professional opinion of the authors, and do not represent any official policy of FHWA.

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Ling, TC., Balachandran, C., Munoz, J.F. et al. Chemical evolution of alkali–silicate reaction (ASR) products: a Raman spectroscopic investigation. Mater Struct 51, 23 (2018). https://doi.org/10.1617/s11527-018-1151-x

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