Resistance of Alkali-Activated Binders to Organic Acids Found in Agri-Food Effluents
Publication: Journal of Materials in Civil Engineering
Volume 33, Issue 4
Abstract
Organic acids, such as acetic and lactic acids, are prevalent in agricultural and food effluents. They pose a considerable pollution threat and must be collected and stored safely before treatment and release. They cause significant damage to cementitious materials, reducing the service life of structures. In this study, the resistance of alkali-activated fly ash and slag-blended binders to organic acids was studied, and a comparison with ordinary portland cement binders was carried out. The findings demonstrate that alkali-activated binders with increased fly ash content have marginally better resistance to acetic acid, but mixes with increased slag content have better resistance to lactic acid. This is due to the solubility of the calcium and aluminum salts of acetic and lactic acids. Overall, the performance of the alkali-activated binders was better than that of the ordinary portland cement binder, with a lower mass and strength losses observed. This was attributed to their lower calcium content with less vulnerable phases, such as calcium hydroxide and ettringite. Instead, the calcium-silicate-hydrate (C-S-H) type gels in alkali-activated binders suffered decalcification and dealumination but left behind a silicon-rich gel, which helped to resist further acid attack.
Get full access to this article
View all available purchase options and get full access to this article.
Data Availability Statement
All data, models, and code generated or used during the study appear in the published article.
Acknowledgments
The authors would like to acknowledge the facilities provided by the School of Natural and Built Environment, Queen’s University Belfast. The research studentship provided by the Department of Finance, Northern Ireland, is also gratefully acknowledged. The authors also appreciate the support received and useful discussions had with Prof. Marios Soutsos.
References
Aiken, T. A. 2017. “Durability of geopolymer materials in aggressive aqueous environments—Acid attack, steel reinforcement corrosion and freeze-thaw attack.” Ph.D. thesis, School of Natural and Built Environment, Queen’s Univ. Belfast.
Aiken, T. A., J. Kwasny, W. Sha, and M. N. Soutsos. 2018. “Effect of slag content and activator dosage on the resistance of fly ash geopolymer binders to sulfuric acid attack.” Cem. Concr. Res. 111 (Sep): 23–40. https://doi.org/10.1016/j.cemconres.2018.06.011.
Aiken, T. A., J. Kwasny, and W. Sha. 2020. “Resistance of fly ash geopolymer binders to organic acids.” Mater. Struct. 53: 115. https://doi.org/10.1617/s11527-020-01549-x.
Aiken, T. A., W. Sha, J. Kwasny, and M. N. Soutsos. 2017. “Resistance of geopolymer and portland cement based systems to silage effluent attack.” Cem. Concr. Res. 92 (Feb): 56–65. https://doi.org/10.1016/j.cemconres.2016.11.015.
Allahverdi, A., and F. Škvára. 2001. “Nitric acid attack on hardened paste of geopolymeric cements. Part 1.” Ceramics 45 (3): 81–88.
Allahverdi, A., and F. Škvára. 2005. “Sulfuric acid attack on hardened paste of geopolymer cements. Part 1. Mechanism of corrosion at relatively high concentrations.” Ceramics 49 (4): 225–229.
Aragón, P., R. A. Robayo-Salazar, and R. Mejía de Gutiérrez. 2020. “Alkali-activated concrete based on natural volcanic pozzolan: Chemical resistance to sulfate attack.” J. Mater. Civ. Eng. 32 (5): 4020106. https://doi.org/10.1061/(ASCE)MT.1943-5533.0003161.
ASTM. 2006. Standard test method for density, absorption and voids in hardened concrete. ASTM C642. West Conshohocken, PA: ASTM.
ASTM. 2012. Standard test methods for chemical resistance of mortars, grouts, and monolithic surfacings and polymer concretes. ASTM C267-01. West Conshohocken, PA: ASTM.
Bakharev, T. 2005. “Geopolymeric materials prepared using class F fly ash and elevated temperature curing.” Cem. Concr. Res. 35 (6): 1224–1232. https://doi.org/10.1016/j.cemconres.2004.06.031.
Bascarevic, Z., M. Komljenovic, Z. Miladinovic, V. Nikolic, N. Marjanovic, Z. Zujovic, and R. Petrovic. 2013. “Effects of the concentrated solution on mechanical properties and structure of the fly ash based geopolymers.” Constr. Build. Mater. 41 (3): 570–579. https://doi.org/10.1016/j.conbuildmat.2012.12.067.
Beddoe, R. E., and H. W. Dorner. 2005. “Modelling acid attack on concrete: Part I. The essential mechanisms.” Cem. Concr. Res. 35 (12): 2333–2339. https://doi.org/10.1016/j.cemconres.2005.04.002.
Ben Haha, M., G. Le Saout, F. Winnefeld, and B. Lothenbach. 2011. “Influence of activator type on hydration kinetics, hydrate assemblage and microstructural development of alkali activated blast-furnace slags.” Cem. Concr. Res. 41 (3): 301–310. https://doi.org/10.1016/j.cemconres.2010.11.016.
Bernal, S. A., J. L. Provis, B. Walkley, R. San Nicolas, J. D. Gehman, D. G. Brice, A. R. Kilcullen, P. Duxson, and J. S. J. van Deventer. 2013. “Gel nanostructure in alkali-activated binders based on slag and fly ash, and effects of accelerated carbonation.” Cem. Concr. Res. 53 (Nov): 127–144. https://doi.org/10.1016/j.cemconres.2013.06.007.
Bernal, S. A., E. D. Rodríguez, R. M. de Gutierrez, and J. L. Provis. 2012. “Performance of alkali-activated slag mortars exposed to acids.” J. Sustainable Cem.-Based Mater. 1 (3): 138–151. https://doi.org/10.1080/21650373.2012.747235.
Bertron, A. 2013. “Methods for testing cementitious materials exposed to organic acids.” In Performance of cement-based materials in aggressive aqueous environments, edited by M. Alexander, A. Bertron, and N. De Belie, 355–387. Dordrecht, Netherlands: Springer.
Bertron, A., J. Duchesne, and G. Escadeillas. 2005a. “Accelerated tests of hardened cement pastes alteration by organic acids: Analysis of the pH effect.” Cem. Concr. Res. 35 (1): 155–166. https://doi.org/10.1016/j.cemconres.2004.09.009.
Bertron, A., and J. Duchesne. 2013. “Attack of cementitious materials by organic acids in agricultural and agrofood effluents.” In Performance of cement-based materials in aggressive aqueous environments, edited by M. Alexander, A. Bertron, and N. De Belie, 131–173. Dordrecht, Netherlands: Springer.
Bertron, A., J. Duchesne, and G. Escadeillas. 2005b. “Attack of cement pastes exposed to organic acids in manure.” Cem. Concr. Compos. 27 (9–10): 898–909. https://doi.org/10.1016/j.cemconcomp.2005.06.003.
Bertron, A., G. Escadeillas, and J. Duchesne. 2004. “Cement pastes alteration by liquid manure organic acids: Chemical and mineralogical characterization.” Cem. Concr. Res. 34 (10): 1823–1835. https://doi.org/10.1016/j.cemconres.2004.01.002.
BSI (British Standards Institution). 1989. Testing aggregates. Method for determination of particle size distribution. BS EN 812-103.2. London: BSI.
BSI (British Standards Institution). 1995. Testing aggregates. Methods for determination of density. BS 812-2. London: BSI.
BSI (British Standards Institution). 2006. Ground granulated blast furnace slag for use in concrete, mortar and grout. Definitions, specifications and conformity criteria. BS EN 15167-1. London: BSI.
BSI (British Standards Institution). 2011. Cement part 1: Composition, specifications and conformity criteria for common cements. BS EN 197-1. London: BSI.
BSI (British Standards Institution). 2012. Fly ash for concrete. Definition, specifications and conformity criteria. BS EN 450-1. London: BSI.
Burciaga-Díaz, O., and J. I. Escalante-García. 2012. “Strength and durability in acid media of alkali silicate-activated metakaolin geopolymers.” J. Am. Ceram. Soc. 95 (7): 2307–2313. https://doi.org/10.1111/j.1551-2916.2012.05249.x.
Castillo Lara, R., and G. Chagas Cordeiro. 2019. “Effect of rice husk ash as supplementary cementitious material on the performance of cement-based pastes continuously exposed to organic acid solution (Vinasse).” J. Mater. Civ. Eng. 31 (7): 04019102. https://doi.org/10.1061/(ASCE)MT.1943-5533.0002739.
Chang, C.-F., and J.-W. Chen. 2006. “The experimental investigation of concrete carbonation depth.” Cem. Concr. Res. 36 (9): 1760–1767. https://doi.org/10.1016/j.cemconres.2004.07.025.
Chinchón-Payá, S., C. Andrade, and S. Chinchón. 2016. “Indicator of carbonation front in concrete as substitute to phenolphthalein.” Cem. Concr. Res. 82 (Apr): 87–91. https://doi.org/10.1016/j.cemconres.2015.12.010.
Collins, F. G., and J. G. Sanjayan. 1999. “Workability and mechanical properties of alkali activated slag concrete.” Cem. Concr. Res. 29 (3): 455–458. https://doi.org/10.1016/S0008-8846(98)00236-1.
De Belie, N., M. Debruyckere, D. Van Nieuwenburg, and B. De Blaere. 1997. “Attack of concrete floors in pig houses by feed acids: Influence of fly ash addition and cement-bound surface layers.” J. Agric. Eng. Res. 68 (2): 101–108. https://doi.org/10.1006/jaer.1997.0185.
De Belie, N., H. J. Verselder, B. De Blaere, D. Van Nieuwenburg, and R. Verschoore. 1996. “Influence of the cement type on the resistance of concrete to feed acids.” Cem. Concr. Res. 26 (11): 1717–1725. https://doi.org/10.1016/S0008-8846(96)00155-X.
El-Hassan, H., and S. Elkholy. 2019. “Performance evaluation and microstructure characterization of steel fiber-reinforced alkali-activated slag concrete incorporating fly ash.” J. Mater. Civ. Eng. 31 (10): 04019223. https://doi.org/10.1061/(ASCE)MT.1943-5533.0002872.
Gallé, C. 2001. “Effect of drying on cement-based materials pore structure as identified by mercury intrusion porosimetry: A comparative study between oven-, vacuum-, and freeze-drying.” Cem. Concr. Res. 31 (Oct): 1467–1477. https://doi.org/10.1016/S0008-8846(01)00594-4.
García-Lodeiro, I., A. Fernández-Jiménez, M. T. Blanco, and A. Palomo. 2008. “FTIR study of the sol-gel synthesis of cementitious gels: C-S-H and N-A-S-H.” J. Sol-Gel Sci. Technol. 45 (1): 63–72. https://doi.org/10.1007/s10971-007-1643-6.
García Lodeiro, I., D. E. Macphee, A. Palomo, and A. Fernández-Jiménez. 2009. “Effect of alkalis on fresh C-S-H gels. FTIR analysis.” Cem. Concr. Res. 39 (3): 147–153. https://doi.org/10.1016/j.cemconres.2009.01.003.
Gruyaert, E., P. Van Den Heede, M. Maes, and N. De Belie. 2012. “Investigation of the influence of blast-furnace slag on the resistance of concrete against organic acid or sulphate attack by means of accelerated degradation tests.” Cem. Concr. Res. 42 (1): 173–185. https://doi.org/10.1016/j.cemconres.2011.09.009.
Gu, L., P. Visintin, and T. Bennett. 2020. “Sulphuric acid resistance of cementitious materials: Multiscale approach to assessing the degradation.” J. Mater. Civ. Eng. 32 (7): 04020171. https://doi.org/10.1061/(ASCE)MT.1943-5533.0003261.
Ismail, I., S. A. Bernal, J. L. Provis, S. Hamdan, and J. S. J. Van Deventer. 2013. “Drying-induced changes in the structure of alkali-activated pastes.” J. Mater. Sci. 48 (9): 3566–3577. https://doi.org/10.1007/s10853-013-7152-9.
Ismail, I., S. A. Bernal, J. L. Provis, R. San Nicolas, S. Hamdan, and J. S. J. Van Deventer. 2014. “Modification of phase evolution in alkali-activated blast furnace slag by the incorporation of fly ash.” Cem. Concr. Compos. 45 (Jan): 125–135. https://doi.org/10.1016/j.cemconcomp.2013.09.006.
Koenig, A., and F. Dehn. 2016. “Main considerations for the determination and evaluation of the acid resistance of cementitious materials.” Mater. Struct. 49: 1693–1703. https://doi.org/10.1617/s11527-015-0605-7.
Kwasny, J., T. A. Aiken, M. N. Soutsos, D. J. Cleland, and J. A. Mcintosh. 2018a. “Comparison of lithomarge and cement-based mortars performance in aggressive aqueous environments.” In Proc., 6th Int. Conf. on the Durability of Concrete Structures, edited by P. A. M. Basheer, K. Yang, E. Garcia-Taengua, S. Adu-Amankwah, and S. Nanukuttan, 72–79. Caithness, UK: Whittles Publishing. http://eprints.whiterose.ac.uk/140898/.
Kwasny, J., T. A. Aiken, M. N. Soutsos, J. A. Mcintosh, and D. J. Cleland. 2018b. “Sulfate and acid resistance of lithomarge-based geopolymer mortars.” Constr. Build. Mater. 166 (Mar): 537–553. https://doi.org/10.1016/j.conbuildmat.2018.01.129.
Kwasny, J., M. N. Soutsos, J. A. McIntosh, and D. J. Cleland. 2018c. “Comparison of the effect of mix proportion parameters on behaviour of geopolymer and portland cement mortars.” Constr. Build. Mater. 187 (Oct): 635–651. https://doi.org/10.1016/j.conbuildmat.2018.07.165.
Lee, N. K., and H. K. Lee. 2016. “Influence of the slag content on the chloride and sulfuric acid resistances of alkali-activated fly ash/slag paste.” Cem. Concr. Compos. 72 (Sep): 168–179. https://doi.org/10.1016/j.cemconcomp.2016.06.004.
Liu, E., M. Ghandehari, C. Brückner, G. Khalil, J. Worlinsky, W. Jin, A. Sidelev, and M. A. Hyland. 2017. “Mapping high pH levels in hydrated calcium silicates.” Cem. Concr. Res. 95 (May): 232–239. https://doi.org/10.1016/j.cemconres.2017.02.001.
Lloyd, R. R., J. L. Provis, and J. S. J. van Deventer. 2012. “Acid resistance of inorganic polymer binders. 1. Corrosion rate.” Mater. Struct. 45 (1–2): 1–14. https://doi.org/10.1617/s11527-011-9744-7.
Ma, H. 2014. “Mercury intrusion porosimetry in concrete technology: Tips in measurement, pore structure parameter acquisition and application.” J. Porous Mater. 21: 207–215. https://doi.org/10.1007/s10934-013-9765-4.
Nath, P., and P. K. Sarker. 2014. “Effect of GGBFS on setting, workability and early strength properties of fly ash geopolymer concrete cured in ambient condition.” Constr. Build. Mater. 66 (Sep): 163–171. https://doi.org/10.1016/j.conbuildmat.2014.05.080.
National Institute of Standards and Technology. 2018. “Calcium lactate.” Accessed April 22, 2020. https://webbook.nist.gov/cgi/cbook.cgi?ID=C5743475&Mask=80#IR-Spec.
Provis, J. L., G. C. Lukey, and J. S. J. van Deventer. 2005. “Do geopolymers actually contain nanocrystalline zeolites? A reexamination of existing results.” Chem. Mater. 17 (12): 3075–3085. https://doi.org/10.1021/cm050230i.
Rafeet, A. 2016. “Mix design, fresh and hardened properties and microstructural characterization of alkali-activated concrete based on PFA/GGBS blends.” Ph.D. thesis, School of Natural and Built Environment, Queen’s Univ. Belfast.
Rafeet, A., R. Vinai, M. Soutsos, and W. Sha. 2017. “Guidelines for mix proportioning of fly ash/GGBS based alkali activated concretes.” Constr. Build. Mater. 147 (Aug): 130–142. https://doi.org/10.1016/j.conbuildmat.2017.04.036.
Rafeet, A., R. Vinai, M. Soutsos, and W. Sha. 2019. “Effects of slag substitution on physical and mechanical properties of fly ash-based alkali activated binders (AABs).” Cem. Concr. Res. 122 (Aug): 118–135. https://doi.org/10.1016/j.cemconres.2019.05.003.
Rakhimova, N. R., and R. Z. Rakhimov. 2019. “Literature review of advances in materials used in development of alkali-activated mortars, concretes, and composites.” J. Mater. Civ. Eng. 31 (11): 3119002. https://doi.org/10.1061/(ASCE)MT.1943-5533.0002899.
Sedlarik, V., N. Saha, I. Kuritka, I. Emri, and P. Saha. 2006. “Modification of poly(vinyl alcohol) with lactose and calcium lactate: Potential filler from dairy industry.” Plast. Rubber Compos. 35 (9): 355–359. https://doi.org/10.1179/174328906X149682.
Shearer, C. R., J. L. Provis, S. A. Bernal, and K. E. Kurtis. 2016. “Alkali-activation potential of biomass-coal co-fired fly ash.” Cem. Concr. Compos. 73 (Oct): 62–74. https://doi.org/10.1016/j.cemconcomp.2016.06.014.
Shi, C., B. Qu, and J. L. Provis. 2019. “Recent progress in low-carbon binders.” Cem. Concr. Res. 122 (Aug): 227–250. https://doi.org/10.1016/j.cemconres.2019.05.009.
Shi, C., and J. A. Stegemann. 2000. “Acid corrosion resistance of different cementing materials.” Cem. Concr. Res. 30 (5): 803–808. https://doi.org/10.1016/S0008-8846(00)00234-9.
Singh, N. B., S. Prabha, and A. K. Singh. 1986. “Effect of lactic acid on the hydration of portland cement.” Cem. Concr. Res. 16 (4): 545–553. https://doi.org/10.1016/0008-8846(86)90092-X.
Song, X., H. Wang, X. Yang, F. Liu, S. Yu, and S. Liu. 2014. “Hydrolysis of poly(lactic acid) into calcium lactate using ionic liquid [Bmim][OAc] for chemical recycling.” Polym. Degrad. Stab. 110 (Dec): 65–70. https://doi.org/10.1016/j.polymdegradstab.2014.08.020.
Tian, S., Y. Hou, W. Wu, S. Ren, C. Wang, and J. Qian. 2015. “Reversible absorption of from simulated flue gas by aqueous calcium lactate solution.” J. Taiwan Inst. Chem. Eng. 54 (Sep): 71–75. https://doi.org/10.1016/j.jtice.2015.03.026.
Vinai, R., A. Rafeet, M. Soutsos, and W. Sha. 2016. “The role of water content and paste proportion on physico-mechanical properties of alkali activated fly ash-ggbs concrete.” J. Sustainable Metall. 2 (1): 51–61. https://doi.org/10.1007/s40831-015-0032-6.
Wang, S. D., and K. L. Scrivener. 1995. “Hydration products of alkali activated slag cement.” Cem. Concr. Res. 25 (3): 561–571. https://doi.org/10.1016/0008-8846(95)00045-E.
Yu, P., R. J. Kirkpatrick, B. Poe, P. F. McMillan, and X. Cong. 1999. “Structure of calcium silicate hydrate (C-S-H): Near-, mid-, and far-infrared spectroscopy.” J. Am. Ceram. Soc. 82 (3): 742–748. https://doi.org/10.1111/j.1151-2916.1999.tb01826.x.
Information & Authors
Information
Published In
Journal of Materials in Civil Engineering
Volume 33 • Issue 4 • April 2021
Copyright
© 2021 American Society of Civil Engineers.
History
Received: Jun 9, 2020
Accepted: Aug 31, 2020
Published online: Jan 22, 2021
Published in print: Apr 1, 2021
Discussion open until: Jun 22, 2021
Authors
Metrics & Citations
Metrics
Citations
Download citation
If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download.