Materiales de Construcción 72 (348)
October–December 2022, e298
ISSN-L: 0465-2746, eISSN: 1988-3226
https://doi.org/10.3989/mc.2022.00422

A mini guideline study for fly ash-based alkali activated foam masonry units

Un mini estudio de guía para unidades de mampostería de espuma activada con base de cenizas activadas alcalinamente

C. Kurtulus

Dept. of Chemical Engineering, Afyon Kocatepe University, (Afyonkarahisar, Turkiye)

https://orcid.org/0000-0002-0758-5844

M.S. Baspinar

Dept. of Metallurgy and Materials Engineering, Afyon Kocatepe University, (Afyonkarahisar, Turkiye)

https://orcid.org/0000-0003-2086-1935

ABSTRACT

This study examined the preparation of fly ash-based foam geopolymer recipes with the experimental design method and data analysis with the SPSS program. A total of 54 prescriptions were used in the studies, which investigated six different variables. Strength, density, and thermal conductivity analyses were performed. Values were in the range of 0.57-2.75 MPa for strength, 344-592 kg/m3 for density, and 0.089-0.132 for thermal conductivity. Three variables were identified with each having the most significant effect on strength and density values. H2O2, curing temperature, and expanded perlite had the most effect on strength, while H2O2, curing temperature, and alkali concentration had the most significant effect on density. Most influential parameters are plotted on ternary graphs to ensure that the foam concrete (CLC) masonry units used in all types of masonry walls, whether load-bearing or not, can operate under the specified performance conditions.

KEY WORDS: 
Foam Geopolymer; Experimental Design; SPSS; Masonry Unit.
RESUMEN

Este estudio examinó la preparación de mezclas de geopolímeros de espuma a base de cenizas volantes con el método de diseño experimental y el análisis de datos con el programa SPSS. Se utilizaron un total de 54 prescripciones en los estudios, investigándose seis variables diferentes. Se realizaron análisis de resistencia, densidad y conductividad térmica. Los valores estuvieron en el rango de 0,57-2,75 MPa para resistencia, 344-592 kg/m3 para densidad y 0,089-0,132 para conductividad térmica. Se identificaron tres variables, teniendo cada una el efecto más significativo sobre los valores de fuerza y densidad. El H2O2, la temperatura de curado y la perlita expandida tuvieron el mayor efecto sobre la resistencia, mientras que el H2O2, la temperatura de curado y la concentración de álcali tuvieron el efecto más significativo sobre la densidad. Los parámetros más influyentes se trazan en gráficos ternarios para garantizar que las unidades de mampostería de hormigón celular (CLC) utilizadas en todos los tipos de muros de mampostería, ya sea que soporten carga o no, puedan operar bajo las condiciones de desempeño especificadas.

PALABRAS CLAVE: 
Geopolímero de espuma; Diseño experimental; SPSS; Unidad de mampostería.

Received: 10  January  2022; Accepted: 16  June  2022; Available on line: 13 October 2022

Citation/Citar como: Kurtulus, C.; Baspinar, M.S. (2022) A mini guideline study for fly ash-based alkali activated foam masonry units. Mater. construcc. 72 [348], e298 https://doi.org/10.3989/mc.2022.00422

CONTENT

1. INTRODUCTION

 

The construction sector is growing at an unprecedented rate around the world, and this trend is anticipated to continue. This rapid growth in the construction industry in recent years, together with the need for technically superior characteristics and values for building materials, has resulted in the use and application of a large number of novel building materials (11. Vairagade, V.S.; Parbat, K.; Dhale, S.A. (2015) Fly ash as sustainable material for green concrete - A state of art. Int. J. Res. Eng. Sci. Technol. 1 [2] , 17-24.
). Over the next 40 years, the world is forecast to add 230 billion square feet of new construction, with the building and construction industry accounting for 39% of worldwide final carbon dioxide (CO2) emissions (22. Dean, B.; Dulac, J.; Petrichenko, K.; Graham P. (2016) Towards a zero-emission, efficient, and resilient buildings and construction sector. Global Status Report. 1-48.
). Concrete, a common construction material composed of aggregates and cement to bind them together, is the third-largest source of human-induced greenhouse gas emissions, behind the transportation industry, for the main pollutant of carbon dioxide in the atmosphere (3-93. Jaya, N.A.; Yun-Ming, L.; Cheng-Yong H.; Abdullah, M.M.AB.; Hussin K. (2020) Correlation between pore structure, compressive strength and thermal conductivity of porous metakaolin geopolymer. Construc. Build. Mater. 247, 118641. https://doi.org/10.1016/j.conbuildmat.2020.118641.
4. Rifaai, Y.; Yahia, A.; Mostafa, A.; Aggoun, S.; Kadri, E.H. (2019) Rheology of fly ash-based geopolymer: Effect of NaOH concentration. Construc. Build. Mater. 223, 583-94. https://doi.org/10.1016/j.conbuildmat.2019.07.028.
5. Cai, J.; Tan, J.; Li, X. (2020) Thermoelectric behaviors of fly ash and metakaolin based geopolymer. Construc. Build. Mater. 237, 117757. https://doi.org/10.1016/j.conbuildmat.2019.117757.
6. Singh, N.B.; Middendorf, B. (2020) Geopolymers as an alternative to Portland cement: An overview. Construc. Build. Mater. 237, 117455. https://doi.org/10.1016/j.conbuildmat.2019.117455.
7. Ling, Y.; Wang, K.; Wang, X.; Hua, S. (2019) Effects of mix design parameters on heat of geopolymerization, set time, and compressive strength of high calcium fly ash geopolymer. Construc. Build. Mater. 228, 116763. https://doi.org/10.1016/j.conbuildmat.2019.116763.
8. Wu, J.; Zhang, Z.; Zhang, Y.; Li, D. (2018) Preparation and characterization of ultra-lightweight foamed geopolymer (UFG) based on fly ash-metakaolin blends. Construc. Build. Mater. 168, 771-779. https://doi.org/10.1016/j.conbuildmat.2018.02.097.
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). As a result of this predicament, it is imperative that sustainable alternatives to cement and building materials containing cement be utilized in construction in order to preserve the long-term viability of the environment (1111. Srividya, T.; Kannan, P.R.; Sivasakthi, M.; Sujitha, A.; Jeyalakshmi, R. (2022) A state-of-the-art on development of geopolymer concrete and its field applications. Case Stud. Construc. Mater. 16, e00812. https://doi.org/10.1016/j.cscm.2021.e00812.
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Alkali-activated materials (AAM), generally called geopolymers, are a relatively new class of attractive construction material that offer a solution to limit the adverse results of cement manufacturing. These materials are gaining popularity due to their environmental and performance advantages over standard Portland cement concrete and cement-based construction materials (1313. Glasby, T.; Day, J.; Genrich, R.; Kemp, M. (2015) Commercial scale geopolymer concrete construction. The Saudi International Building and Constructions Technology Conference 1-11.
). Alkali activated concretes (AAC) have become an issue of great importance due to their widely accepted identification as “environmentally friendly” or “green” construction materials compared to cement-based concretes due to their low CO2 emission potential and ensuring recycling of industrial by-products (14-1814. Dong, M.; Feng, W.; Elchalakani, M.; Li, G.K.; Karrech, A.; Sheikh, M.N. (2020) Material and glass-fibre-reinforced polymer bond properties of geopolymer concrete. Mag. Concr. Res. 72 [10] , 509-525. https://doi.org/10.1680/jmacr.18.00273.
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4. Rifaai, Y.; Yahia, A.; Mostafa, A.; Aggoun, S.; Kadri, E.H. (2019) Rheology of fly ash-based geopolymer: Effect of NaOH concentration. Construc. Build. Mater. 223, 583-94. https://doi.org/10.1016/j.conbuildmat.2019.07.028.
5. Cai, J.; Tan, J.; Li, X. (2020) Thermoelectric behaviors of fly ash and metakaolin based geopolymer. Construc. Build. Mater. 237, 117757. https://doi.org/10.1016/j.conbuildmat.2019.117757.
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7. Ling, Y.; Wang, K.; Wang, X.; Hua, S. (2019) Effects of mix design parameters on heat of geopolymerization, set time, and compressive strength of high calcium fly ash geopolymer. Construc. Build. Mater. 228, 116763. https://doi.org/10.1016/j.conbuildmat.2019.116763.
8. Wu, J.; Zhang, Z.; Zhang, Y.; Li, D. (2018) Preparation and characterization of ultra-lightweight foamed geopolymer (UFG) based on fly ash-metakaolin blends. Construc. Build. Mater. 168, 771-779. https://doi.org/10.1016/j.conbuildmat.2018.02.097.
).

The term geopolymer was first used by the French scientist Joseph Davidovits to measure the tridimensional structure of inorganic polymers, which are formed by low-temperature polycondensation of aluminosilicates (1919. Davidovits, J. (2008) Geopolymer chemistry and applications. Institut Géopolymère, Saint-Quentin, (2008).
). There are a wide variety of potential solid aluminosilicate raw materials for the synthesis of inorganic polymers such as fly ash, blast furnace slag, metakaolin, construction and demolition wastes, and red mud (19-2219. Davidovits, J. (2008) Geopolymer chemistry and applications. Institut Géopolymère, Saint-Quentin, (2008).
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). Geopolymer-based inorganic materials have a wide variety of application areas, including fire-resistant materials, thermal insulation, building materials, water purification, and so on (1919. Davidovits, J. (2008) Geopolymer chemistry and applications. Institut Géopolymère, Saint-Quentin, (2008).
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).

Masonry units are an ancient and fundamental construction and building material used all over the world. Earth masonry units (adobe or compressed earth blocks) account for a significant portion of the built environment today. Earth-based buildings house from one-third to half of the world’s population (2525. Pacheco-torgal, F.; Lourenȯ, P.B.; Labrincha, J.A.; Kumar, S. (2014) Eco-efficient masonry bricks and blocks design, properties and durability. Woodhead Publishing, UK, (2014).
) mainly for houses and apartment buildings. These construction technologies are extensively employed world- wide both in developed and developing countries, sometimes due to strong cultural aspects, long time tradition or even as a symbol of solid construction. Moreover the good performance of masonries is well known by the users, including its strength, ther- mal and acoustical properties. In developing countries besides the former reasons, brickwork or blockwork are the only suitable methods for self-construction in non- industrialized circumstances. However the traditional masonry units are usually non-eco-friendly products, mainly because of their high energy consuming components due to their production method (fired-clay bricks. Bricks can be composed of a variety of materials, including calcium silicate, concrete, and clay, while clay and concrete bricks are the most common. Clay brick manufacture, on the other hand, necessitates high-temperature (900-1000oC) kiln burning, which emits a significant amount of greenhouse gases (2626. Ahmari, S.; Zhang, L. (2012) Production of eco-friendly bricks from copper mine tailings through geopolymerization. Construc. Build. Mater. 29, 323-331. https://doi.org/10.1016/j.conbuildmat.2011.10.048.
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). In light of all this information, sustainable concretes should be created with readily available resources on earth, recycled materials with low energy requirements, and generated with little or no waste, in order to have the least possible environmental impact (28-3028. Ahmed, H.U.; Mohammed, A.A.; Rafiq, S.; Mohammed, A.S.; Mosavi A.; Sor N.H.; Qaidi, S.M.A. (2021) Compressive strength of sustainable geopolymer concrete composites: A state-of-the-art review. Sustain. 13 [24] , 13502. https://doi.org/10.3390/su132413502.
29. Luhar, I.; Luhar, S.; Abdullah, M.M.A.B.; Razak, R.A.; Vizureanu, P.; Sandu, A.V.; Matasaru, P-D. (2021) A state-of-the-art review on innovative geopolymer composites designed for water and wastewater treatment. Materials. 14 [23] , 7456. https://doi.org/10.3390/ma14237456.
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). Mined raw materials and non-renewable energy are used in the cement industry. The utilization of industrial by-products can greatly reduce the amount of energy used in these processes, as well as waste management. Through the use of waste materials, geopolymer technology reduces greenhouse gas emissions and lowers raw material costs (1111. Srividya, T.; Kannan, P.R.; Sivasakthi, M.; Sujitha, A.; Jeyalakshmi, R. (2022) A state-of-the-art on development of geopolymer concrete and its field applications. Case Stud. Construc. Mater. 16, e00812. https://doi.org/10.1016/j.cscm.2021.e00812.
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Economic and environmental restrictions are becoming more prevalent nowadays, and one of the implications for the construction sector will be a demand for more energy-efficient building and construction materials (3232. Malhotra, M.V. (2002) Introduction: sustainable development and concrete technology. ACI Conc. Int. 24 [7] , 22.
). When it comes to energy leaks in buildings, it’s estimated that the walls account for about 40% of the heat loss (33-3533. Asadi, I.; Shafigh, P.; Abu Hassan, Z.F.B.; Mahyuddin, N.B. (2018) Thermal conductivity of concrete - A review. J. Build. Eng. 20, 81-93. https://doi.org/10.1016/j.jobe.2018.07.002.
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). Geopolymer foams have drawn the attention of researchers and studies were carried out for many years due to better properties (thermal stability, inflammability, and green production process) compared to conventional building insulation materials (42-4642. Samson, G.; Cyr, M. (2017) Porous structure optimisation of flash-calcined metakaolin / fly ash geopolymer foam concrete geopolymer foam concrete. Eur. J. Env. Civil Eng. 22 [12] , 1482-1498. https://doi.org/10.1080/19648189.2017.1304285.
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). Porous materials are created by adding air into a suspension or liquid medium through direct foaming processes. The amount of gas contained in the geopolymer slurry influences overall porosity, and pore size is linked to setting characteristics (5353. Studart, A.R.; Gonzenbach, U.T.; Tervoort, E.; Gauckler, L.J. (2006) Processing routes to macroporous ceramics: A review. J. Am. Cer. Soc. 89 [6] , 1771-1789. https://doi.org/10.1111/j.1551-2916.2006.01044.x.
). The size and distribution of the cured foams are influenced by the blowing agent used and the amount added (5454. Masi, G.; Rickard, W.D.A.; Vickers, L.; Bignozzi, M.C.; Van Riessen, A. (2014) A comparison between different foaming methods for the synthesis of light weight geopolymers. Ceram. Int. 40 [9] , 13891-13902. https://doi.org/10.1016/j.ceramint.2014.05.108.
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), metallic Al (4040. Zhang, Z.; Provis, J.L.; Reid, A.; Wang, H. (2014) Geopolymer foam concrete: An emerging material for sustainable construction. Construc. Build. Mater. 56, 113-127. https://doi.org/10.1016/j.conbuildmat.2014.01.081.
), metallic Si (5555. Medri, V.; Papa, E.; Dedecek, J.; Jirglova, H.; Benito, P.; Vaccari, A.; Landi, E. (2013) Effect of metallic Si addition on polymerization degree of in situ foamed alkali-aluminosilicates. Ceram. Int. 39 [7] , 7657-7668. https://doi.org/10.1016/j.ceramint.2013.02.104.
), and sodium perborate (5656. Svingala, F.R. (2009) Alkali activated aerogels, Rochester Institute of Technology, Rochester (2009).
) into the geopolymer sludge. The degradation of the additives in the alkaline sludge results in the formation of a bubble and a porous layer. In Equations [1] , [2] , and [3] , a bubble and porous structure are created because of the degradation of the additives in the alkaline sludge:

2 H 2 O 2 2 H 2 O + O 2  [1]
A l + 3 H 2 O + O H A l ( O H ) 4 + 3 / 2 H 2  [2]
S i + 4 H 2 O 2 H 2 + S i ( O H ) 4  [3]

Due to the general high gas-liquid contact area, liquid foams are thermodynamically unstable. As a result, several physical processes like drainage, creaming, and Ostwald ripening destabilize the slurry, causing large pores to form. Surfactants are required to maintain system stability, manage the pore size distribution, and lower the angle at the gas-liquid interface. Surfactants keep gas bubbles stable in the system by preventing them from aggregating. Surfactants such as butyric acid, valeric acid, butyl gallate, propyl gallate, hexylamine, and calcium stearate are commonly utilized (57-6257. Gonzenbach, U.T.; Studart, A.R.; Tervoort, E.; Gauckler, L.J. (2006) Stabilization of foams with inorganic colloidal particles. J. Am. Cer. Soc. 22 [26] , 10983-10988. https://doi.org/10.1021/la061825a.
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60. Maryoto, A. (2015) Improving microstructures of concrete using Ca(C18H35O2)2. Procedia Eng. 125, 631-637. https://doi.org/10.1016/j.proeng.2015.11.086.
61. Kurtulus, C.; Baspınar, M.S. (2020) Effect of calcium stearate on the thermal conductivity of geopolymer foam. J. Turkish Chem. Soc. 7 [2] , 535-544. https://doi.org/10.18596/jotcsa.660727.
62. Zhang, X.; Bai, C.; Qiao, Y.; Wang, X.; Jia, D.; Li, H.; Colombo, P. (2021) Porous geopolymer composites: A review. Comp. Part A: App. Sci. Manufac. 150, 106629.
).

Another technique to improve energy efficiency in buildings is to incorporate lightweight aggregates to increase porosity and acquire low density construction material at the same time. One of the materials used for this is expanded perlite (4949. Vaou, V.; Panias, D. (2010) Thermal insulating foamy geopolymers from perlite. Minerals Eng. 23 [14] , 1146-1151. https://doi.org/10.1016/j.mineng.2010.07.015.
, 63-6563. Demir, İ.; Baspınar, S.; Kahraman, E. (2018) Production of insulations and construction materials from expanded perlite. Lecture Notes Civil Eng. 6, 24-32.
64. Sriwattanapong, M.; Sinsiri, T.; Pantawee, S. (2013) A study of lightweight concrete admixed with perlite. Suranaree J. Sci. Technol. 20 [3] , 227-234.
65. Sengul, O.; Azizi, S.; Karaosmanoglu, F.; Tasdemir, M.A. (2011) Effect of expanded perlite on the mechanical properties and thermal conductivity of lightweight concrete. Energy Build. 43 [2-3] , 671-676. https://doi.org/10.1016/j.enbuild.2010.11.008.
). Expanded perlite is a siliceous volcanic glass with a large volume that expands significantly when heated. Its volume grows 4-20 times when heated above 870 oC (6666. Chandra, S.; Berntsson, L. (2002) Lightweight aggregate, Noyes Publications, New York, (2002).
). The thermal insulation qualities of expanded perlite are greatly improved as a result of this increase in volume and porous structure. Furthermore, compared to the density of conventional perlite, expanded perlite has very low density. Compared to alternative materials including exfoliated vermiculite, expanded clay or shale, pumice, and mineral wool, the low cost of expanded perlite may be a significant advantage (6565. Sengul, O.; Azizi, S.; Karaosmanoglu, F.; Tasdemir, M.A. (2011) Effect of expanded perlite on the mechanical properties and thermal conductivity of lightweight concrete. Energy Build. 43 [2-3] , 671-676. https://doi.org/10.1016/j.enbuild.2010.11.008.
).

The current consensus is that there are many variables affecting the properties and performances of fresh and hardened geopolymeric materials, including alkaline concentration, curing temperature, curing duration, Na2O/SiO2 ratio, SiO2/Al2O3 ratio, H2O/Na2O ratio, and additives (1919. Davidovits, J. (2008) Geopolymer chemistry and applications. Institut Géopolymère, Saint-Quentin, (2008).
, 67-6967. Gunasekara, C.M. (2016) Influence of properties of fly ash from different sources on the mix design and performance of geopolymer concrete, Engineering and Health RMIT University, Australia, (2016).
68. Tchakouté, H.K.; Rüscher, C.H. (2017) Mechanical and microstructural properties of metakaolin-based geopolymer cements from sodium waterglass and phosphoric acid solution as hardeners: A comparative study. App. Clay Sci. 140, 81-87. https://doi.org/10.1016/j.clay.2017.02.002.
69. De Vargas, A.S.; Dal Molin, D.C.C.; Vilela, A.C.F.; da Silva, F.J.; Pavão, B.; Veit, H. (2011) The effects of Na2O/SiO2 molar ratio, curing temperature and age on compressive strength, morphology and microstructure of alkali-activated fly ash-based geopolymers. Cem. Conc. Comp. 33 [6] , 653-660. https://doi.org/10.1016/j.cemconcomp.2011.03.006.
). Although many studies were performed about improving the mechanical properties of geopolymer materials and geopolymer foams, different foam forming methods (4949. Vaou, V.; Panias, D. (2010) Thermal insulating foamy geopolymers from perlite. Minerals Eng. 23 [14] , 1146-1151. https://doi.org/10.1016/j.mineng.2010.07.015.
, 7070. Medri, V.; Papa, E.; Mazzocchi, M.; Laghi, L.; Morganti, M.; Francisconi, J.; Landi, E. (2015) Production and characterization of lightweight vermiculite/geopolymer-based panels. Mater. Des. 85, 266-274. https://doi.org/10.1016/j.matdes.2015.06.145.
, 7171. Zhang, Z.; Wang, H. (2016) The pore characteristics of geopolymer foam concrete and their impact on the compressive strength and modulus. Front. Mat. 3, 38. https://doi.org/10.3389/fmats.2016.00038.
), stabilizing foam cells (7272. Bai, C.; Colombo, P. (2017) High-porosity geopolymer membrane supports by peroxide route with the addition of egg white as surfactant. Ceram. Int. 43 [2] , 2267-2273. https://doi.org/10.1016/j.ceramint.2016.10.205.
, 7373. Cui, Y.; Wang, D.; Zhao, J.; Li, D.; Ng, S.; Rui, Y. (2018) Effect of calcium stearate based foam stabilizer on pore characteristics and thermal conductivity of geopolymer foam material. J. Build. Eng. 20, 21-29. https://doi.org/10.1016/j.jobe.2018.06.002.
), and examining the thermal properties of geopolymer foams (6161. Kurtulus, C.; Baspınar, M.S. (2020) Effect of calcium stearate on the thermal conductivity of geopolymer foam. J. Turkish Chem. Soc. 7 [2] , 535-544. https://doi.org/10.18596/jotcsa.660727.
, 7474. Bai, C.; Colombo, P. (2018) Processing, properties and applications of highly porous geopolymers : A review. Ceram. Int. 44 [14] , 16103-16118. https://doi.org/10.1016/j.ceramint.2018.05.219.
), there are no guidelines and comprehensive publications examining the mechanical, physical and thermal properties of many samples.

So far, investigations of alkali activated materials generated utilizing slag and fly ash as raw materials has continued, significantly in relation to microstructures, workability, mechanical performance, and durability (1717. Zhang, J.; Li, S.; Li, Z.; Gao, Y.; Liu, C.; Qi, Y. (2021) Workability and microstructural properties of red-mud-based geopolymer with different particle sizes. Adv. Cem. Res. 33 [5] , 210-223. https://doi.org/10.1680/jadcr.19.00085.
, 7575. Abdollahnejad, Z.; Nazari, A.; Pacheco-Torgal, F.; Sanjayan, J.G.; Barroso de Aguiar, J.L. (2015) Prediction of the compressive strength of one-part geopolymers. Int. Con.f Eng. 1226-1234.
, 7676. Shill, S.K.; Al-Deen, S.; Ashraf, M.; Hutchison, W. (2020) Resistance of fly ash based geopolymer mortar to both chemicals and high thermal cycles simultaneously. Construc. Build. Mater. 239, 117886. https://doi.org/10.1016/j.conbuildmat.2019.117886.
). Alkali activated materials were used in some real situations in Asia, Australia, and Europe with established technical specifications (11. Vairagade, V.S.; Parbat, K.; Dhale, S.A. (2015) Fly ash as sustainable material for green concrete - A state of art. Int. J. Res. Eng. Sci. Technol. 1 [2] , 17-24.
, 1414. Dong, M.; Feng, W.; Elchalakani, M.; Li, G.K.; Karrech, A.; Sheikh, M.N. (2020) Material and glass-fibre-reinforced polymer bond properties of geopolymer concrete. Mag. Concr. Res. 72 [10] , 509-525. https://doi.org/10.1680/jmacr.18.00273.
, 1515. Aziz, I.H.; Al Bakri Abdullah, M.M.; Heah, C.Y.; Liew, Y.M. (2020) Behaviour changes of ground granulated blast furnace slag geopolymers at high temperature. Adv. Cem. Res. 32 [10] , 465-475. https://doi.org/10.1680/jadcr.18.00162.
). Nevertheless, due to a shortage of clear guidelines that may be extensively recognized, alkali activated blend formulation is almost always difficult to evaluate and recreate. For this reason, determining the working range with a detailed study is important research for alkali activated concrete. The properties and necessary performance conditions of foam concrete (CLC) masonry units used in all types of masonry walls, whether load bearing or not, are presented in TS13655 (Turkish Standard). According to this standard, the strength value of all kinds of walls, including monolithic walls, sandwich (double-layer walls) walls, partition walls, retaining walls and foundations, as well as general applications underground, should be >1 MPa and <450-550 kg/m3 density property.

Experimental design methods have gained popularity in recent years for various reasons, including obtaining more information with less laboratory effort, saving time and raw materials, and examining the variables that influence the critical attributes. When an investigation is conducted without employing the experimental design approach, modifications are made to the first variable assumed to influence the outcome, and the first variable is used until the best values are found. When trying to find the best values for the second variable, there will be a shift from the first variable’s optimum value. Every modification performed at the variable level will lead to changes at all levels. Although the influence level of each variable will be understood separately, the process will not be fully understood, and the effects of the variables on one another will not be resolved. The effect of one variable can be evaluated with varying degrees of other variables in studies that follow the experimental design method, and more data can be gathered with fewer experiments (7777. Kathirvel, P.; Kaliyaperumala, S.R.M. (2017) Probabilistic modeling of geopolymer concrete using response surface methodology. Comput. Concr. 19 [6] , 737-744. https://doi.org/10.12989/cac.2017.19.6.737.
, 7878. Ferreira, S.L.C.; Bruns, R.E.; Ferreira, H.S.; Matos, G.D.; David, J.M.; Brandão, G.C.; et al. (2007) Box-Behnken design: An alternative for the optimization of analytical methods. Anal. Chim. Acta. 597 [2] , 179-186. https://doi.org/10.1016/j.aca.2007.07.011.
).

For the subject of geopolymers, there are many researchers who obtained findings using different experimental design methods. In their studies, they generally focused on critical parameters such as water/binder ratio, fly ash/alkali ratio, alkaline concentration, and raw material ratio. Li et al. worked on slag-based concrete using the Taguchi method (7979. Li, N.; Shi, C.; Zhang, Z.; Zhu, D.; Hwang, H.J.; Zhu, Y.; Sun, T. (2018) A mixture proportioning method for the development of performance-based alkali-activated slag-based concrete. Cem. Conc. Comp. 93, 163-174. https://doi.org/10.1016/j.cemconcomp.2018.07.009.
). In addition, Nazari et al. prepared geopolymers containing rice husk ash and fly ash using the Taguchi method and determined the optimum mix compositions (8080. Nazari, A.; Sanjayan, J.G. (2015) Hybrid effects of alumina and silica nanoparticles on water absorption of geopolymers: Application of Taguchi approach. Measurement. 60, 240-246. https://doi.org/10.1016/j.measurement.2014.10.004.
). Hadi et al. conducted studies on geopolymer-based concretes using the multiple regression model with four variables related to strength abd slump set time, and developed formulations including alkali /binder, sodium silicate/sodium hydroxide, and water/binder ratios (8181. Hadi, M.N.S.; Zhang, H.; Parkinson, S. (2019) Optimum mix design of geopolymer pastes and concretes cured in ambient condition based on compressive strength, setting time and workability. J. Build. Eng. 23, 301-313. https://doi.org/10.1016/j.jobe.2019.02.006.
). Lokuge et al. studied fly ash-geopolymer concrete using a multivariate adaptive regression spline model. During their studies, they collected all the literature on the subject and analyzed the variables of water/binder, alkali/binder, sodium silicate/sodium hydroxide, and alkaline concentration (8282. Lokuge, W.; Wilson, A.; Gunasekara, C.; Law, D.W.; Setunge, S. (2018) Design of fly ash geopolymer concrete mix proportions using multivariate adaptive regression spline model. Construc. Build. Mater. 166, 472-81. https://doi.org/10.1016/j.conbuildmat.2018.01.175.
). Onoue et al. performed an experimental design about fly ash-based geopolymers using the Taguchi method. They studied the sodium silicate/sodium hydroxide ratio, alkaline concentration, fly ash-slag ratio, mixing time, curing temperature, and cumulative temperature with two different fly ash types purchased from different lots (8383. Onoue, K.; Iwamoto, T.; Sagawa, Y. (2019) Optimization of the design parameters of fly ash-based geopolymer using the dynamic approach of the Taguchi method. Construc. Build. Mater. 219, 1-10. https://doi.org/10.1016/j.conbuildmat.2019.05.177.
).

This article presents comprehensive results about the physical properties, mechanical properties, and thermal conductivity properties, which will guide the preparation phase of fly ash-based geopolymer foams that are planned to be used as building materials. This study is also crucial in terms of evaluating fly ash, which is a thermal power plant waste, in the context of the circular economy and transforming it into a value-added product in the field of construction.

2. MATERIALS AND METHODS

 

Solid main raw materials used for the preparation of foam geopolymers are fly ash and metakaolin. Fly ash was supplied by Seyitömer Thermal Power Plant (Kütahya/Turkiye). It is classified as Class F according to the ASTM-C618 (8484. ASTM C618-03 (2003) Standard specification for coal fly ash and raw or calcined natural pozzolan for use in concrete. Annu B ASTM Standard C, 3-6.
). Metakaolin powder (MEFISTO L05) was purchased from the Czech Republic. Sodium silicate solution and sodium hydroxide particulates were used in the preparation of alkaline solution. In the foam formation phase, hydrogen peroxide (30% concentration) was used as a foaming agent. and calcium stearate was used as a surfactant. Additionally, chopped polypropylene fiber (1 cm long and 30 µm diameter) and expanded perlite (1-3 mm diameter) were added to samples. To improve the geopolymerization properties of the solutions, a small amount of metakaolin was added. To abide by the circular economy goal while also improving geopolymerization, a maximum of 15% metakaolin was added (8585. Luukkonen, T.; Abdollahnejad, Z.; Yliniemi, J.; Kinnunen, P.; Illikainen, M. (2018) One-part alkali-activated materials: A review. Cem. Conc. Res. 103, 21-34. https://doi.org/10.1016/j.cemconres.2017.10.001.
, 8686. Görhan, G.; Aslaner, R.; Şinik, O. (2016) The effect of curing on the properties of metakaolin and fly ash-based geopolymer paste. Compos. Part B. Eng. 97, 329-335. https://doi.org/10.1016/j.compositesb.2016.05.019.
). Calcium stearate was chosen due to its outstanding surfactant properties while being affordable, odorless, and having low toxicity (8787. Izaguirre, A.; Lanas, J.; Álvarez, J.I. (2009) Effect of water-repellent admixtures on the behaviour of aerial lime-based mortars Cem. Concr. Res. 39 [11] , 1095-1104. https://doi.org/10.1016/j.cemconres.2009.07.026.
). It is a white powder, that is slippery and insoluble in water. Chopped polypropylene fiber was added to the samples to prevent cracks that may occur during drying (88-9488. Ranjbar, N.; Talebian, S.; Mehrali, M.; Kuenzel, C.; Cornelis, M.H.S.; Jumaat, M.Z. (2016) Mechanisms of interfacial bond in steel and polypropylene fiber reinforced geopolymer composites. Composites Sci. Tech. 122, 73-81. https://doi.org/10.1016/j.compscitech.2015.11.009.
89. Abdollahnejad, Z.; Mastali, M.; Dalvand, A. (2017) Comparative study on the effects of recycled glass-fiber on drying shrinkage rate and mechanical properties of the self-compacting mortar and fly ash-slag geopolymer mortar. J. Mat. Civil Eng. 29 [8] , 1-11. https://doi.org/10.1061/(ASCE)MT.1943-5533.0001918
90. Ranjbar, N.; Zhang, M. (2020) Fiber-reinforced geopolymer composites : A review. Cem. Conc. Comp. 107, 103498. https://doi.org/10.1016/j.cemconcomp.2019.103498.
91. Sukontasukkul, P.; Pongsopha, P.; Chindaprasirt, P.; Songpiriyakij, S. (2018) Flexural performance and toughness of hybrid steel and polypropylene fibre reinforced geopolymer. Construc. Build. Mater. 161, 37-44. https://doi.org/10.1016/j.conbuildmat.2017.11.122.
92. Mastali, M.; Kinnunen, P.; Dalvand, A.; Mohammadi Firouz, R.; Illikainen, M. (2018) Drying shrinkage in alkali-activated binders-A critical review. Construc. Build. Mater. 190, 533-550. https://doi.org/10.1016/j.conbuildmat.2018.09.125.
93. Kheradmand, M.; Abdollahnejad, Z.; Pacheco-Torgal, F. (2020) Drying shrinkage of fly ash geopolymeric mortars reinforced with polymer hybrid fibres. Proc. Inst. Civ. Eng. Constr. Mater. 173 [1] , 28-40. https://doi.org/10.1680/jcoma.16.00077.
94. Amran, Y.H.M.; Farzadnia, N.; Ali, A.A.A. (2015) Properties and applications of foamed concrete; a review. Construc. Build. Mater. 101 [1] , 990-1005. https://doi.org/10.1016/j.conbuildmat.2015.10.112.
), and expanded perlite was added to improve the thermal insulation properties (4949. Vaou, V.; Panias, D. (2010) Thermal insulating foamy geopolymers from perlite. Minerals Eng. 23 [14] , 1146-1151. https://doi.org/10.1016/j.mineng.2010.07.015.
, 6363. Demir, İ.; Baspınar, S.; Kahraman, E. (2018) Production of insulations and construction materials from expanded perlite. Lecture Notes Civil Eng. 6, 24-32.
, 6565. Sengul, O.; Azizi, S.; Karaosmanoglu, F.; Tasdemir, M.A. (2011) Effect of expanded perlite on the mechanical properties and thermal conductivity of lightweight concrete. Energy Build. 43 [2-3] , 671-676. https://doi.org/10.1016/j.enbuild.2010.11.008.
, 9595. Jedidi, M.; Benjeddou, O.; Soussi, C. (2015) Effect of expanded perlite aggregate dosage on properties of lightweight concrete. Jordan J. of Civ. Eng. 9 [3] , 278-291. https://doi.org/10.14525/jjce.9.3.3071.
).

Table 1 summarizes the chemical compositions of solid raw materials measured by XRF, and Table 2 gives specific surface area and specific weight of raw materials, respectively. The specific surface area of fly ash and metakaolin were detected by the BET method. Density values of aluminosilicate raw materials were measured with a pycnometer.

Table 1.  Chemical composition of aluminosilicate raw materials.
SiO2 Al2O3 CaO Fe2O3 MgO K2O
Fly Ash (%) 50.30 19.10 4.55 12.40 4.67 2.16
Metakaolin (%) 54.10 41.10 0.13 1.10 0.18 0.80
Table 2.  Physical properties of aluminosilicate raw materials.
Properties Fly Ash Metakaolin
Specific Surface Area (kg/m 2 ) 7.91 17.08
Density (kg/m 3 ) 2.58 2.50

In order to prepare the alkaline solution, NaOH plates were completely dissolved in sodium silicate solution. To ensure the homogeneous distribution, the fibers added to the alkaline mixture were mixed for another one minute. Solid content was homogeneously mixed by adding calcium stearate into the mixture containing metakaolin and fly ash. The alkaline solution was poured onto the solid mixture without waiting for it to cool and the geopolymer content was mixed for five minutes. After that, H2O2 was added to the geopolymer mixture and the blend was mixed vigorously for 1 minute. Finally, the geopolymer mixture was poured into 10x10x10 cm molds and cured for 24 hours in an oven (Figure 1). The hardened geopolymers were demolded and stored at room temperature for 28 days.

medium/medium-MC-72-348-e298-gf1.png
Figure 1.  Schematic presentation of the synthesis of fly ash-based porous geopolymers.

The samples prepared for thermal conductivity analysis were produced as presented in the flow chart in Figure 1. Since the authors preferred the guarded hot plate method for thermal conductivity analysis, the samples were produced with 30x30x5 cm dimensions.

Compressive strength, bulk density, and thermal conductivity analyses of the prepared foam samples were performed on the 28th day. Analysis of the large amount of data obtained was performed with the SPSS program, and the results obtained were confirmed with statistical data.

2.1 Experimental design procedure

 

Geopolymer experiments were conducted with Box Behnken experimental design method. A detailed study was carried out to obtain comprehensive information about compressive strength, density, and thermal conductivity properties of fly ash-based foam geopolymers. The maximum (1), minimum (-1) and average (0) values for six variables were determined for the experiment design. Maximum and minimum values were provided by using preliminary studies. The average value (0) represents the mean of the maximum and minimum value. The values determined for the experiment design are presented in Appendix 1. Oxide molar ratios of all mix design compositions of samples are shown in Table 3. Contour plots were used to interpret the complex data collected.

Table 3.  Oxide molar ratios of geopolymer pastes.
Fly Ash-Metakaolin Ratio (%) Alkaline Concentration H2O/Na2O SiO2/Al2O3 Na2O/SiO2 Na2O/Al2O3
85-15 6M 13.42 5.19 0.28 1.40
8M 11.75 5.19 0.33 1.63
10M 10.47 5.19 0.37 1.85
90-10 6M 13.40 5.44 0.28 1.47
8M 11.73 5.44 0.33 1.71
10M 10.45 5.44 0.37 1.95
95-5 6M 13.37 5.72 0.28 1.55
8M 11.71 5.72 0.33 1.80
10M 10.44 5.72 0.37 2.05

2.2 Instrumentation

 

Compressive strength was tested with 10x10x10 cm specimens. Samples were cured at room temperature (25 ºC±1 and 50±5% relative humidity) for 28 days. The strength of geopolymer foams was tested with a loading rate of 3 kN/s. Bulk densities of samples cured at room temperature for 28 days were measured in accordance with ASTM C642. At least three samples were examined, and average values were recorded. Scanning electron microscopy (SEM) with back-scattered electron (BSE) images were performed to analyze the surfaces of the specimens and investigate porosity on a LEO 1430 VP device. Secondary electron images were obtained with an acceleration voltage of 20 kV. Information about bonds formed in geopolymer samples and their amounts were obtained by the FTIR method. FTIR analysis was performed to correlate with drying shrinkage. The samples were characterized by diamond ATR spectroscopy and absorption spectra in the 4000-400 cm-1 spectrum range. The thermal conductivity of samples was tested using a TA Instruments FOX 314 Thermal Conductivity Analyzer. The guarded hot plate method was used to measure the thermal conductivity of low conductivity construction and insulation materials at a temperature of 25 °C. The samples were dried in an oven at 105 °C until they attained a consistent weight for thermal conductivity analysis.

All samples were subjected to strength and density tests. Thermal conductivity investigation was done on samples chosen from among those that showed the best strength and density performance. As a result of these analyses, contour plots were created. Only selected samples were subjected to XRD, SEM and FTIR analyses. The formulations of the selected samples are depicted in the figures that accompany the analysis findings.

3. RESULTS AND DISCUSSION

 

3.1 Compressive strength analysis

 

In the study, the effects of all variables on strength were examined with the help of contour graphics and the results are presented in Table 4 and Figure 2. As the indicator on the right side of the graphics turns from cold colors to warm colors, the strength value increases. As shown in all figures, the strength values vary between 0.57 MPa and 2.75 MPa. The graphs with the most transitions between colors were examined visually, and H2O2, expanded perlite, and curing temperature were the variables that have the most effect on strength.

Table 4.  Statistical analysis of variable data thought to affect strength.
Model B value Standard Error Beta value p-value R2 Binary r
Constant 0.614 0.767 <0.001 0.424
H2O2 (%) -0.779 0.177 -0.479 -0.624
Curing Temperature (oC) 0.022 0.009 0.269 0.518
Alkaline concentration (M) 0.101 0.044 0.248 0.340
Expanded Perlite (%) -0.073 0.032 -0.248 -0.616
medium/medium-MC-72-348-e298-gf2.png
Figure 2.  Contour charts of all measured strength values. a) Hydrogen peroxide vs. calcium stearate b) Hydrogen peroxide vs. perlite, c) Hydrogen peroxide vs. curing temperature vs., d) Alkaline concentration vs. temperature e) Fly ash vs. alkaline concentration.

Data obtained from compressive strength tests were analyzed using statistical analysis methods. Multiple regression was carried out with the help of stepwise linear regression in order to investigate which variables used in geopolymer composition contributed more to strength development (Table 4). Stepwise linear regression is a method of regressing multiple variables while simultaneously removing those that aren’t important. SPSS ordered the variables in the model according to their correlation strengths with the dependent variable, as shown in Table 4. The model was constructed by measuring the effect of each variable entered into the model. The model shows that H2O2, curing temperature, alkaline concentration, and expanded perlite amount all influenced strength. The beta value describes the effect of the independent variable on the dependent in multiple regression. Regardless of sign, large numbers represent the most impactful parameter on the property. The relative importance of the variables on strength, according to the standardized regression coefficient (β), were H2O2 amount, curing temperature, alkaline concentration, and expanded perlite quantity. H2O2 and expanded perlite were negatively connected to strength and strength was positively related to curing temperature and alkaline concentration. A positive relationship suggests that the change is directly proportional, while a negative relationship shows that the change is inversely proportional. When the significance (p-value) of the variables and models is assessed, the association between the variables was statistically significant because the values are less than 0.05.

The negative and moderate value (r=-0.624) correlation between H2O2 and strength values was obtained using binary correlations between the strength value and the variables. The curing temperature and strength values were found to have a positive and moderate binary (r=0.518) correlation. The alkaline concentration and strength values were found to have a moderate (r=0.340) positive binary interaction. Finally, a moderate binary (r=0.616) negative association was calculated between expanded perlite content and strength development.

The table shows that H2O2 and expanded perlite reduce strength, whereas curing temperature and alkaline concentration enhance strength. The numerical size of the beta value, regardless of sign, also provides the most information about the effect of variables on strength. This means that H2O2, curing temperature, alkaline concentration, and expanded perlite all impact compressive strength.

In this context, the authors created a ternary strength graph by selecting three different variables that have the greatest impact on strength. In this case, the authors chose three variables that had the greatest impact on strength and created a ternary strength graph to estimate the operating range.

The area covered by red, yellow, and green on the triangle graph suggests that strength values at and above the intended value (1 MPa) can be obtained, which was determined at the start of the study. As an outcome, samples made at maximum 1.0% H2O2, minimum 70 ºC, and containing any amount of expanded perlite can achieve >1.0 MPa strength. The coloring changes to turquoise and dark blue in locations where the curing temperature is lower than the established value and the H2O2 amount is higher than the indicated value, where strength values below the target value are feasible.

While the maximum compressive strength was achieved at 80 °C, the minimum compressive strength was obtained at 60 °C, and the strength gradually varied as the temperature was increased. The compressive strength increased when the curing temperature was raised, according to this finding. Although Hardjito et al. (9696. Hardjito, D.; (2005) Development and properties of low-calcium fly ash-based geopolymer concrete, Curtin University of Technology, Australia, (2005).
) asserted that increasing the curing temperature over 60 °C does not considerably increase compressive strength, temperature increased strength in fly ash-based geopolymer foams in our work.

The degree of porosity mainly controls the mechanical strength of the geopolymer foam (5555. Medri, V.; Papa, E.; Dedecek, J.; Jirglova, H.; Benito, P.; Vaccari, A.; Landi, E. (2013) Effect of metallic Si addition on polymerization degree of in situ foamed alkali-aluminosilicates. Ceram. Int. 39 [7] , 7657-7668. https://doi.org/10.1016/j.ceramint.2013.02.104.
). The increase in H2O2 contributes to thinning and weakening of the pore walls and decreasing bulk density values cause a decrease in strength. Geopolymer foams containing 1.0% H2O2 reached a strength value of >2.5 MPa. While the strength values of samples containing 1.5% H2O2 decreased to 1.5-2.0 MPa, it even falls below 1.0 MPa for samples containing 2.0% H2O2.

When expanded perlite is added to a geopolymer mixture, its porous and weak structure causes weak zones (9797. Tsaousi, G.M.; Douni, I.; Panias, D. (2016) Characterization of the properties of perlite geopolymer pastes. Mater. Construcc. 66 [324] , e102. https://doi.org/10.3989/mc.2016.10415.
). As a result, expanded perlite in the combination has a negative impact on the mechanical characteristics. While samples without any expanded perlite can reach a strength value of about 1.5 MPa, when 2.5% expanded perlite is added to the mixture, the strength value drops from one to 0.5 MPa.

Using the triple chart in Figure 3, H2O2 must be less than 1.5%, curing temperature must be greater than 70 °C, and perlite must be less than 2.75% to achieve strengths greater than 1 MPa required by the TS13655 standard.

medium/medium-MC-72-348-e298-gf3.png
Figure 3.  Presentation of the most effective variables on strength in ternary graphs and working range detection. (Values used in the study were normalized out of 100 among themselves. So 0=1.0%, 50=1.5%, 100=2.0% for hydrogen peroxide, 0=60ºC, 50=70ºC, and 100=80ºC for the curing temperature, and 0=0%, 50=2.75%, 100=5.5% values for expanded perlite amount).

3.2 Density analysis

 

The findings for density analysis are shown in Appendix 1, statistical results in Table 5, and the contour plots in Figure 4 were utilized to observe the variables that affect sample densities. Figure 4a reveals that, regardless of the amount of calcium stearate used, sample densities vary directly with the amount of hydrogen peroxide. Figure 4b shows that hydrogen peroxide has a greater effect on density values than expanded perlite. The density values were somewhat affected by the temperature increase in Figures 4c and 4d, and the density values may increase with the increase in alkaline concentration. Figure 4e demonstrates that the amount of fly ash has little effect on the density values.

Table 5.  Statistical study of variable data to help determine density.
Model B value Standard Error Beta value p-value R2 Binary r
Constant 687.370 56.011 0.000 0.874
H2O2 (%) -148.667 12.983 -0.788 -0.789
Alkaline concentration (M) 15.667 3.246 0.332 0.332
Curing Temperature (ºC) -1.667 0.649 -0.177 0.177
medium/medium-MC-72-348-e298-gf4.png
Figure 4.  Contour charts of measured density values. a) Hydrogen peroxide vs. calcium stearate b) Hydrogen peroxide vs. perlite, c) Curing temperature vs. hydrogen peroxide, d) Curing temperature vs. alkaline concentration, e) Fly ash vs. alkaline concentration.

Multiple regression was performed using the stepwise linear regression approach, as in the compressive strength study, to determine the variables impacting the density of the foam geopolymers. Table 5 shows the parameters that have the greatest impact on density. The most effective variables on density in this model were peroxide, curing temperature, and alkaline concentration. When the significance (p-value) of the variables and models presented in the table are examined, the relationship between the variables was statistically significant since the values are less than 0.05. Along with low density, expanded perlite is commonly used in manufacturing lightweight concrete (9898. ASTM C332-17 (2017) Standard specification for lightweight aggregates for insulating concrete.
, 9999. ASTM C330 (2017) Standard specification for lightweight aggregates for structural concrete, Annual book of ASTM Standards.
). Even though expanded perlite was employed in the study, it was not one of the variables affecting density in the SPSS analysis. The small amount in the composition is considered the main cause. As a result, as can be followed by the beta values, hydrogen peroxide, curing temperature, and alkaline concentration all had a greater impact on the density value, respectively.

As presented in Table 5, the variables of hydrogen peroxide, curing temperature, and alkaline concentration had a significant and robust relationship (R2=0.874 and p<0.05). Together, these three variables explain approximately 87.4% of the total variance of the density values. There was a negative and robust (r=-0.789) relationship between H2O2 and density values. There was a positive and low binary correlation (r=0.177) between the curing temperature and the density values. A moderate (r=0.332) positive binary correlation was calculated between alkaline concentration and density values. Thanks to model three, a ternary diagram was drawn, and the operating range was determined by considering the parameters that most affected the density value (Figure 5).

medium/medium-MC-72-348-e298-gf5.png
Figure 5.  Presentation of the most effective variables on density in ternary graphs and determination of working range. (Values used in the study were normalized out of 100 among themselves. So 0=1.0%, 50=1.5%, 100=2.0% for hydrogen peroxide, 0=60ºC, 50=70ºC, and 100=80ºC for the curing temperature, and 0=6 M, 50=8 M, 100=10 M values for alkaline concentration).

Although Hardjito et al. (100100. Hardjito, D.; Wallah, S.E.; Sumajouw, D.M.J. Rangan, B.V. (2004) On the development of fly ash-based geopolymer concrete. Am. Conc. Instit. Mater. J. 101 [6] , 467-472.
) claimed that raising the curing temperature above 60 °C does not increase the compressive strength significantly, in this study, the temperature increased the strength of fly ash-based geopolymer foams.

To produce a sample with the density of 450-550 kg/m3 required by the TS13655 standard, the triple graph in the figure indicates that H2O2 must be less than 1.75%, curing temperature must be higher than 70 °C, and alkaline concentration must be greater than 8 M.

3.3 Thermal conductivity analysis

 

The Figure 6 shows contour plots created from the thermal conductivity analysis findings. The thermal conductivity values of fly ash-based geopolymer foams ranged between 0.089 to 0.1328 W/mK, according to the results of the investigation. The effect of H2O2 and Ca-stearate on thermal conductivity is seen in Figure 6a. Ca-stearate and H2O2 both appear to improve the insulating capabilities gradually. The decrease in heat conductivity was induced by the presence of more air gaps in the geopolymer matrix caused by the increased amount of H2O2 (3939. Zhao, Y.; Jow, J.; Cai, X.; Lai, S. (2015) Fly ash-based geopolymer foam technology for thermal insulation and fire protection applications. World of Coal Ash (WOCA) Conference.
, 101101. Feng, J.; Zhang, R.; Gong, L.; Li, Y.; Cao, W.; Cheng, X. (2015) Development of porous fly ash-based geopolymer with low thermal conductivity. Mater. Des. 65, 529-533. https://doi.org/10.1016/j.matdes.2014.09.024.
, 102102. Zhu, M.; Ji, R.; Li, Z.; Wang, H.; Liu, L.L.; Zhang, Z. (2016) Preparation of glass ceramic foams for thermal insulation applications from coal fly ash and waste glass. Construc. Build. Mater. 112, 398-405. https://doi.org/10.1016/j.conbuildmat.2016.02.183.
) and the reduction of pore diameters generated by Ca-stearate (7373. Cui, Y.; Wang, D.; Zhao, J.; Li, D.; Ng, S.; Rui, Y. (2018) Effect of calcium stearate based foam stabilizer on pore characteristics and thermal conductivity of geopolymer foam material. J. Build. Eng. 20, 21-29. https://doi.org/10.1016/j.jobe.2018.06.002.
, 103-105103. Jaya, N.A.; Yun-Ming, L.; Cheng-Yong, H.; Abdullah, M.M.A.B.; Hussin, K. (2020) Correlation between pore structure, compressive strength and thermal conductivity of porous metakaolin geopolymer. Construc. Build. Mater. 247, 118641. https://doi.org/10.1016/j.conbuildmat.2020.118641.
104. Sumirat, I.; Ando, Y.; Shimamura, S. (2006) Theoretical consideration of the effect of porosity on thermal conductivity of porous materials. J. Porous Mater. 13, 439-443. https://doi.org/10.1007/s10934-006-8043-0.
105. Skibinski, J.; Cwieka, K.; Ibrahim, S.H.; Wejrzanowski, T. (2019) Influence of pore size variation on thermal conductivity of open-porous foams. Materials. 12 [12] , 2017. https://doi.org/10.3390/ma12122017.
) in the composition. The effect of fly ash and calcium stearate on thermal conductivity is seen in Figure 6b. The amount of fly ash was found to influence thermal conductivity, initially decreasing and later boosting it. Figure 6c demonstrates that when the alkali concentration increases, the thermal conductivity values drop; however, the expanded perlite additive enhances insulation. The thermal insulation qualities of the structure increased because expanded perlite enhances the total porosity of the structure (6565. Sengul, O.; Azizi, S.; Karaosmanoglu, F.; Tasdemir, M.A. (2011) Effect of expanded perlite on the mechanical properties and thermal conductivity of lightweight concrete. Energy Build. 43 [2-3] , 671-676. https://doi.org/10.1016/j.enbuild.2010.11.008.
, 106106. Demirboǧa, R.; Gül, R. (2003) The effects of expanded perlite aggregate, silica fume and fly ash on the thermal conductivity of lightweight concrete. Cem. Concr. Res. 33 [5] 723-727. https://doi.org/10.1016/S0008-8846(02)01032-3.
). The thermal conductivity value is thought to increase when the alkali content in the geopolymer density values rises (107107. Karaaslan, C.; Yener, E. (2021) The effect of alkaline activator components on the properties of fly ash added pumice based geopolymer. J. Inst. Sci. Technol. 11 [2] , 1255-1269. https://doi.org/10.21597/jist.840872.
, 108108. Jaya, N.A.; Yun-Ming, L.; Abdullah, M.M.A.B.; Cheng-Yong, H.; Hussin, K. (2018) Effect of sodium hydroxide molarity on physical, mechanical and thermal conductivity of metakaolin geopolymers. IOP Conf. Ser. Mater. Sci. Eng. 343, 012015. https://doi.org/10.1088/1757-899X/343/1/012015.
).

medium/medium-MC-72-348-e298-gf6.png
Figure 6.  Contour charts for measured thermal conductivity values. a) Hydrogen peroxide vs. calcium stearate, b) Fly ash vs. calcium stearate, c) Alkali concentration vs. perlite.

3.4 SEM analysis

 

Figure 7 presents the microstructure properties of the synthesized fly ash-based geopolymers as evaluated by SEM. The microstructure of foam geopolymers generated with different concentration levels of alkaline activator is shown in Figures 7a-7b. Increasing concentrations of alkaline activator create more pores and reduce the pore sizes in the areas examined at equal magnifications. The viscosity of the geopolymer mixture increases as the alkalinity rises. The increased external pressure around the pores inhibits their growth and development (3434. Yatsenko, E.A.; Goltsman, B.M.; Smoliy, V.A.; Kosarev A.S. (2016) Investigation of a porous structure formation mechanism of a foamed slag glass based on the glycerol foaming mixture. Res. J. Phar, Bio. Chem. Sci. 7 [5] , 1073-1081.
, 109109. Kadoi, K.; Nakae, H. (2011) Relationship between foam stabilization and physical properties of particles on aluminum foam production. Mater. Trans. 52 [10] , 1912-1919. https://doi.org/10.2320/matertrans.F-M2011817.
). As a result, the pores formed in geopolymer compositions with lower alkalinity are smaller. In Figure 7c-7d, the pore size of the foam geopolymer grows as the amount of H2O2 increases. As the amount of dissociated O2 increased in tandem with the amount of H2O2, the pores enlarged and more porosity occurred (4949. Vaou, V.; Panias, D. (2010) Thermal insulating foamy geopolymers from perlite. Minerals Eng. 23 [14] , 1146-1151. https://doi.org/10.1016/j.mineng.2010.07.015.
). The pore size distribution in geopolymer foams at different foaming temperatures is shown in Figures 7e and 7f. As the foaming temperature increased, the number of large pores reduced, and the distribution of pores became more uniform. The fundamental reason for this is that as the temperature goes up, the geopolymerization process accelerates, and the gas generated as a result of the decomposition of H2O2 in the composition remains trapped in the structure as it begins to harden and is unable to join with other pores and expand (110110. Gu, G.; Xu, F.; Huang, X.; Ruan, S.; Peng, C.; Lin, J. (2020) Foamed geopolymer: The relationship between rheological properties of geopolymer paste and pore-formation mechanism. J. Clean Prod. 277, 123238. https://doi.org/10.1016/j.jclepro.2020.123238.
). Figure 7g presents scanning electron microscopy images of the geopolymer containing expanded perlite, which appears to have high porosity. Expanded perlite, which has high porosity, is exceptionally light, and it is inevitable that it causes a severe decrease in density depending on the amount added to the final product (6565. Sengul, O.; Azizi, S.; Karaosmanoglu, F.; Tasdemir, M.A. (2011) Effect of expanded perlite on the mechanical properties and thermal conductivity of lightweight concrete. Energy Build. 43 [2-3] , 671-676. https://doi.org/10.1016/j.enbuild.2010.11.008.
). Excess expanded perlite content, which has low strength, in the mixture causes deterioration in the mechanical properties of the final product, as it will cause the formation of porous and low strength areas.

medium/medium-MC-72-348-e298-gf7.png
Figure 7.  SEM Images of geopolymer samples. a)6M-90UK-0.15CS-70C-7H2O2 b) 10M-90UK-0.15CS-70C-7H2O2 c) 8M-90UK-0.15CS-70C-4H2O2 d) 8M-90UK-0.15CS-70C-7H2O2 e) 10M-90UK-0.45CS-60C-5.5H2O2 f) 10M-90UK-0.45CS-80C-5.5H2O2 g) 10M-90UK-0.45CS-80C-5.5H2O2.

3.5 FTIR analysis

 

The influence of curing temperature, alkali concentration and aluminosilicate raw material combinations on the structural alterations and reaction products of fly ash-based foam geopolymers was investigated using FTIR experiments. For the FTIR study, a Bruker Vertex 70V type spectrometer device (400-4000 cm-1) was used. The results of FTIR spectroscopy are represented graphically as transmittance vs. wavenumber. The spectra lines of foam geopolymer samples are shown in Fig. 7. The H-OH bending and -OH symmetric and asymmetric stretching functional groups are apparent in the broad and strong peaks at 3600-3000 and 1650 for foam geopolymer samples. The water and potential -OH groups in the oligomeric solute species are responsible for these bands. The significant peaks detected in FTIR analyses of geopolymers between 1000 and 600 cm-1 are known to be connected with asymmetric vibrations of T-O-Si bonds (T = Si or Al) (111111. Puertas, F.; Torres-Carrasco, M. (2014) Use of glass waste as an activator in the preparation of alkali-activated slag. Mechanical strength and paste characterisation. Cem. Concr. Res. 57, 95-104. https://doi.org/10.1016/j.cemconres.2013.12.005.
). The peak at 970-800 cm-1 is linked to Al-O-Si bond bending vibrations, while the peak at 420 cm-1 is linked to Si-O-Si bending vibrations (112112. Tchakouté, H.K.; Rüscher, C.H.; Kong, S.; Kamseu, E.; Leonelli, C. (2016) Geopolymer binders from metakaolin using sodium waterglass from waste glass and rice husk ash as alternative activators: A comparative study. Construc. Build. Mater. 114, 276-89. https://doi.org/10.1016/j.conbuildmat.2016.03.184.
). The slight changes in the wavenumber 2200-1800 cm-1 detected in the geopolymer compositions with added organic surfactant reveal the symmetrical and asymmetrical vibrations of CH2 due to the organic surfactant component (113113. Monich, P.R.; Romero, A.R.; Höllen, D.; Bernardo, E. (2018) Porous glass-ceramics from alkali activation and sinter-crystallization of mixtures of waste glass and residues from plasma processing of municipal solid waste. J. Clean. Prod. 188, 871-878. https://doi.org/10.1016/j.jclepro.2018.03.167.
). In addition, carbonyl stretching peaks (COO-) from the chemical structure of Ca-stearate were detected at 1600 cm-1. The peak for the Si-O-Ca vibration can be seen at 750 cm-1 (114114. Husain, S.; Permitaria, A.; Haryanti, N.H.; Suryajaya, S. (2019) Effect calcination temperature on formed of calcium silicate from rice husk ash and snail shell. J. Neutrino. J. Fisika dan Apl. 11 [2] , 45-51.
).

medium/medium-MC-72-348-e298-gf8.png
Figure 8.  FTIR studies of geopolymer foam compositions. (Abbreviations: UK: Fly ash, CS: Calcium stearate, M: Alkaline Concentration, C: Degrees Celsius).

3.6 XRD analysis

 

Figure 9 shows the results of X-ray diffraction investigations of geopolymer foam samples. The examination results for all fly ash-based samples revealed the presence of quartz phase. The effects of varying the amount of fly ash, alkaline concentration, and the curing temperature were all noticed. The characteristic hump (2Θ = 20-40°) of amorphous gels was detected due to the creation of a geopolymer structure generated during the dissolution of the fly ash glassy phase (6262. Zhang, X.; Bai, C.; Qiao, Y.; Wang, X.; Jia, D.; Li, H.; Colombo, P. (2021) Porous geopolymer composites: A review. Comp. Part A: App. Sci. Manufac. 150, 106629.
, 115115. Abdulkareem, O.A. (2017) Effects of high activator content on fly ash-based geopolymers exposed to elevated temperatures. J. Mater. Appl. 6 [1] , 1-12.
). Because the regions beneath the characteristic hump curves were comparable with width and quartz peak positions, it was assumed that all samples would react similarly.

medium/medium-MC-72-348-e298-gf9.png
Figure 9.  XRD analyses of samples made with various alkaline concentrations, curing temperatures, and fly ash concentrations.

4. CONCLUSIONS

 

A guideline study was conducted using the experimental design program to investigate the impacts of six distinct variables on compressive strength, density, and thermal conductivity including fly ash-metakaolin ratio, alkalinity, curing temperature, calcium stearate, H2O2, and expanded perlite. The study findings were statistically assessed, and the three most effective variables on density and strength were chosen, with ternary graphs made as a guide. The variation of thermal conductivity values was also analyzed with the help of contour plots. In this case, H2O2 and curing temperature were identified as the variables that had a combined effect on the strength and density values. Pearlite and alkaline concentration, respectively, were the third and fourth variables that influenced the strength and density values. The data for the technical needs stated in TS13655 were collected for non-load-bearing wall elements, and the working ranges that may be utilized as a guide were identified. Working with less than 1.75% H2O2, a curing temperature greater than 70 °C, an alkali concentration greater than 8 M, and expanded perlite less than 2.75% will match the predicted values when the operating ranges for both density and strength are examined together.

ACKNOWLEDGEMENTS

 

The authors wish to express their appreciation for financial support provided by individuals Afyon Kocatepe University under Grant number 19.Fen.Bil.01 as Scientific Research Project and also supported by TUBITAK under Grant number 218M778 for this work.

AUTHOR CONTRIBUTIONS:

 

Conceptualization: C. Kurtulus. Data curation: C. Kurtulus. Formal analysis: Investigation: C. Kurtulus. Methodology: C. Kurtulus, M. Serhat Baspınar. Project administration: C. Kurtulus, M. S. Baspınar. Supervision: C. Kurtulus, M. S. Baspınar Validation: C. Kurtulus. Visualization: C. Kurtulus. Writing - original draft: C. Kurtulus. Review & editing: C. Kurtulus, M. S. Baspınar.

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Appendix 1. Variables used in experiment design and analysis results.

 
No Fly ash (%) Metakaolin (%) Ca-Stearate (%) Expanded pearlite (%) Alkaline concentration (M) H2O2 (%) Curing temperature (oC) Compressive strength (MPa) Density (kg/m3)
1 85 15 0,45 0 6 1,5 70 1,59 450
2 85 15 0,45 0 10 1,5 70 1,672 540
3 95 5 0,45 0 6 1,5 70 0,676 432
4 95 5 0,45 0 10 1,5 70 1,779 567
5 85 15 0,45 20 6 1,5 70 0,576 445
6 85 15 0,45 20 10 1,5 70 1,668 527
7 95 5 0,45 20 6 1,5 70 1,605 473
8 95 5 0,45 20 10 1,5 70 1,505 475
9 85 15 0,15 10 8 1,5 60 1,451 515
10 95 5 0,15 10 8 1,5 60 1,455 452
11 85 15 0,75 10 8 1,5 60 1,014 431
12 95 5 0,75 10 8 1,5 60 2,018 528
13 85 15 0,15 10 8 1,5 80 1,192 472
14 95 5 0,15 10 8 1,5 80 1,125 435
15 85 15 0,75 10 8 1,5 80 1,191 481
16 95 5 0,75 10 8 1,5 80 1,481 458
17 90 10 0,15 0 8 1 70 2,612 537
18 90 10 0,75 0 8 1 70 2,656 563
19 90 10 0,15 20 8 1 70 1,304 526
20 90 10 0,75 20 8 1 70 0,578 465
21 90 10 0,15 0 8 2 70 1,794 432
22 90 10 0,75 0 8 2 70 1,259 415
23 90 10 0,15 20 8 2 70 0,623 344
24 90 10 0,75 20 8 2 70 1,119 385
25 90 10 0,45 0 6 1,5 60 1,44 475
26 90 10 0,45 0 10 1,5 60 1,864 560
27 90 10 0,45 20 6 1,5 60 1,22 450
28 90 10 0,45 20 10 1,5 60 2,011 535
29 90 10 0,45 0 6 1,5 80 0,658 414
30 90 10 0,45 0 10 1,5 80 1,872 472
31 90 10 0,45 20 6 1,5 80 1,61 475
32 90 10 0,45 20 10 1,5 80 1,208 480
33 85 15 0,45 10 8 1 60 2,485 568
34 95 5 0,45 10 8 1 60 2,747 566
35 85 15 0,45 10 8 1 80 1,196 461
36 95 5 0,45 10 8 1 80 2,006 567
37 85 15 0,45 10 8 2 60 1,152 398
38 95 5 0,45 10 8 2 60 1,203 382
39 85 15 0,45 10 8 2 80 0,682 367
40 95 5 0,45 10 8 2 80 0,732 378
41 90 10 0,15 10 6 1 70 2,61 557
42 90 10 0,15 10 10 1 70 2,15 590
43 90 10 0,75 10 6 1 70 2,109 511
44 90 10 0,75 10 10 1 70 2,134 592
45 90 10 0,15 10 6 2 70 1,576 394
46 90 10 0,15 10 10 2 70 1,864 432
47 90 10 0,75 10 6 2 70 1,22 367
48 90 10 0,75 10 10 2 70 2,011 425
49 90 10 0,45 10 8 1,5 70 1,8 535
50 90 10 0,45 10 8 1,5 70 1,8 444
51 90 10 0,45 10 8 1,5 70 1,8 445
52 90 10 0,45 10 8 1,5 70 1,8 450
53 90 10 0,45 10 8 1,5 70 1,8 449
54 90 10 0,45 10 8 1,5 70 1,8 457