Geopolymers are known as high strength and durable construction materials but have a brittle fracture. In practice, this results in a sudden collapse at ultimate load, without any chance of preventing the breakdown of parts or of withstanding the stress for some time. Glass fiber usage as a total anisotropic shape acting as a compact structure component should hinder the fracture mechanism. The optimized compositions in this study led to a significant reinforcement, especially in the case of flexural strength, but also in terms of the compressive strength and notch toughness. The positive and negative influence of the fibers on the complex composite properties provided chemical stability. Full article

The effective activation and utilization of metakaolin as an alkali activated geopolymer precursor and its use in concrete surface protection is of great interest. In this paper, the formula of alkali activated metakaolin-based geopolymers was studied using an orthogonal experimental design. It was found that the optimal geopolymer was prepared with metakaolin, sodium hydroxide, sodium silicate and water, with the molar ratio of SiO₂:Al₂O₃:Na₂O:NaOH:H₂O being 3.4:1.1:0.5:1.0:11.8. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR) were adopted to investigate the influence of curing conditions on the mechanical properties and microstructures of the geopolymers. The best curing condition was 60 °C for 168 h, and this alkali activated metakaolin-based geopolymer showed the highest compression strength at 52.26 MPa. In addition, hollow micro-sphere glass beads were mixed with metakaolin particles to improve the thermal insulation properties of the alkali activated metakaolin-based geopolymer. These results suggest that a suitable volume ratio of metakaolin to hollow micro-sphere glass beads in alkali activated metakaolin-based geopolymers was 6:1, which achieved a thermal conductivity of 0.37 W/mK and compressive strength of 50 MPa. By adjusting to a milder curing condition, as-prepared alkali activated metakaolin-based geopolymers could find widespread applications in concrete thermal protection. Full article

Alkali Activated Concrete (AAC) is an alternative kind of concrete that uses fly ash as a total replacement of Portland cement. Fly ash combined with alkaline solution and cured at high temperature reacts to form a binder. Four point bending tests on two full scale beams made with AAC are described in this paper. Companion small material specimens were also casted with the aim of properly characterizing this new tailored material. The beam’s length was 5000 mm and the cross section was 200 mm × 300 mm. The AAC consisted of fly ash, water, sand 0–4 mm and coarse aggregate 6–10 mm; and the alkaline solution consisted of sodium hydroxide mixed with sodium silicate. No cement was utilized. The maximum aggregate size was 10 mm; fly ash was type F, containing a maximum calcium content of 2%. After a rest period of two days, the beam was cured at 60 °C for 24 h. Data collected and critically discussed included beam deflection, crack patterns, compressive and flexural strength and elastic modulus. Results show how AAC behavior is comparable with Ordinary Portland Cement (OPC) based materials. Nonlinear numerical analyses are finally reported, promoting a better understanding of the structural response. Full article

Ambient temperature geopolymerization of paper sludge ashes (PS-ashes) discharged from paper mills was studied by means of scanning electron microscopy (SEM), X-ray diffraction (XRD), induction coupled plasma atomic emission spectrometry (ICP-AES), and X-ray absorption near edge structure (XANES). Two varieties of alkaline liquors were used in the PS-ash based geopolymers, corresponding to aqueous Na-metasilicate and Na-disilicate compositions. PS-ashes were found to be semi-crystalline and to have porous structures that make it possible to absorb much liquor. Flexural strengths of PS-ash-based geopolymers with liquor/filler ratios (L/F) of 1.0–1.5 ranged from 0.82 to 1.51 MPa at 4 weeks age, depending on PS-ashes and liquors used. The reaction process of the constituent minerals of the PS-ash is discussed. Furthermore, we attempted to solidify hazardous water contaminated with radioisotopes. Non-radioactive strontium and cesium nitrates were added as surrogates at a dosage of 1% into the PS-ash-based geopolymers. Generally, high immobilization ratios up to 99.89% and 98.77% were achieved for Sr²⁺ and Cs⁺, respectively, depending on the source of PS-ashes, alkaline liquors, and material ages. However, in some cases, poor immobilization ratios were encountered, and we further discussed the causes of the instability of derived geopolymer gels on the basis of XANES spectra. Full article

In hybrid alkaline fly ash cements, a new generation of binders, hydration, is characterized by features found in both ordinary portland cement (OPC) hydration and the alkali activation of fly ash (AAFA). Hybrid alkaline fly ash cements typically have a high fly ash (70 wt % to 80 wt %) and low clinker (20 wt % to 30 wt %) content. The clinker component favors curing at ambient temperature. A hydration mechanism is proposed based on the authors’ research on these hybrid binders over the last five years. The mechanisms for OPC hydration and FA alkaline activation are summarized by way of reference. In hybrid systems, fly ash activity is visible at very early ages, when two types of gel are formed: C–S–H from the OPC and N–A–S–H from the fly ash. In their mutual presence, these gels tend to evolve, respectively, into C–A–S–H and (N,C)–A–S–H. The use of activators with different degrees of alkalinity has a direct impact on reaction kinetics but does not modify the main final products, a mixture of C–A–S–H and (N,C)–A–S–H gels. The proportion of each gel in the mix does, however, depend on the alkalinity generated in the medium. Full article

There is no standardized procedure for producing geopolymers; therefore, many researchers develop their own procedures for mixing and curing to achieve good workability and strength development. The curing scheme adopted is important in achieving maximum performance of resultant geopolymers. In this study, we evaluated the impact of sealed and unsealed curing on mechanical strength of geopolymers. Fly ash-based geopolymers cured in sealed and unsealed moulds clearly revealed that retention of water during curing resulted in superior strength development. The average compressive strength of sealed-cured geopolymers measured after 1 day of curing was a modest 50 MPa, while after 7 day curing the average compressive strength increased to 120~135 MPa. In the unsealed specimens the average compressive strength of geopolymers was lower; ranging from 60 to 90 MPa with a slight increase as the curing period increased. Microcracking caused by dehydration is postulated to cause the strength decrease in the unsealed cured samples. These results show that water is a crucial component for the evolution of high strength three-dimensional cross-linked networks in geopolymers. Full article

Present concerns about global warming due to the greenhouse emissions in the atmosphere have pushed the cement industry to research alternatives to ordinary Portland cement (OPC). Geopolymer binder may constitute a possible breakthrough in the development of sustainable materials: understanding the effectiveness and the influences of superplasticizers on geopolymer systems is one of the essential requirements for its large-scale implementation. This study aims to investigate the possibility of using commercially available chemical admixtures designed for OPC concrete, to improve fresh properties of fly ash-based geopolymers and mortars. A special emphasis is laid upon evaluating their influence on mechanical and microstructural characteristics of the hardened material realized under room-temperature curing conditions. Results indicate that the addition of a polycarboxylic ether-based superplasticizer, in the amount of 1.0 wt. % by mass of fly ash, promotes an improvement in workability without compromising the final strength of the hardened material. Moreover, the addition of the polycarboxylic ether- and acrylic-based superplasticizers induces a refinement in the pore structure of hardened mortar leading to a longer water saturation time. Full article

Geopolymers are inorganic polymers formed from the alkaline activation of amorphous alumino-silicate materials resulting in a three-dimensional polymeric network. As a class of materials, it is seen to have the potential of replacing ordinary Portland cement (OPC), which for more than a hundred years has been the binder of choice for structural and building applications. Geopolymers have emerged as a sustainable option vis-à-vis OPC for three reasons: (1) their technical properties are comparable if not better; (2) they can be produced from industrial wastes; and (3) within reasonable constraints, their production requires less energy and emits significantly less CO₂. In the Philippines, the use of coal ash, as the alumina- and silica- rich geopolymer precursor, is being considered as one of the options for sustainable management of coal ash generation from coal-fired power plants. However, most geopolymer mixes (and the prevalent blended OPC) use only coal fly ash. The coal bottom ash, having very few applications, remains relegated to dumpsites. Rice hull ash, from biomass-fired plants, is another silica-rich geopolymer precursor material from another significantly produced waste in the country with only minimal utilization. In this study, geopolymer samples were formed from the mixture of coal ash, using both coal fly ash (CFA) and coal bottom ash (CBA), and rice hull ash (RHA). The raw materials used for the geopolymerization process were characterized using X-ray fluorescence spectroscopy (XRF) for elemental and X-ray diffraction (XRD) for mineralogical composition. The raw materials’ thermal stability and loss on ignition (LOI) were determined using thermogravimetric analysis (TGA) and reactivity via dissolution tests and inductively-coupled plasma mass spectrometry (ICP) analysis. The mechanical, thermal and microstructural properties of the geopolymers formed were analyzed using compression tests, Fourier transform infra-red spectroscopy (FTIR), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). Using a Scheffé-based mixture design, targeting applications with low thermal conductivity, light weight and moderate strength and allowing for a maximum of five percent by mass of rice hull ash in consideration of the waste utilization of all three components, it has been determined that an 85-10-5 by weight ratio of CFA-CBA-RHA activated with 80-20 by mass ratio of 12 M NaOH and sodium silicate (55% H₂O, modulus = 3) produced geopolymers with a compressive strength of 18.5 MPa, a volumetric weight of 1660 kg/m³ and a thermal conductivity of 0.457 W/m-°C at 28-day curing when pre-cured at 80 °C for 24 h. For this study, the estimates of embodied energy and CO₂ were all below 1.7 MJ/kg and 0.12 kg CO₂/kg, respectively. Full article

This study followed the first 20 h of flyash geopolymerization at 70 °C using time resolved Wide Angle X-ray Scattering (WAXS). The extent of dissolution of the amorphous phase of the flyash was determined to range from 29% to 54% for the different formulations trialed. The dissolution rate of the flyash significantly reduced after the first 5 h for all samples. During the formation stage of the geopolymer there were significant temporal variations in the chemistry of the dissolved solution due to the rate of flyash dissolution, with a relative standard deviation of 20%, 57% and 24% for the Si/Al, Na/Al and H/Si ratios, respectively. Utilizing the Power Law, scattering in the low angle region of the WAXS pattern combined with the geopolymer peak area yielded a measure which correlated with the compressive strength—providing a new method to measure the flyash dissolution and geopolymer formation processes independently. The evolution of several zeolite-like phases was followed, noting there are different formation mechanisms involved even within the same sample. Four samples were examined with compressive strengths ranging from 14(2)–50(9) MPa, each was synthesized with flyash from Collie Power Station (Western Australia) activated with sodium silicate solution of varying concentrations. Full article

Geopolymers are generally appreciated for their good resistance against high temperatures. This paper compares the influence of thermal treatment with temperatures ranging from 200 to 1200 °C on the mechanical properties and microstructure of geopolymers based on two different aluminosilicate precursors, metakaolin and fly ash. Moreover, the paper is also aimed at characterizing the effect of chamotte aggregate on the performance of geopolymers subjected to high temperatures. Thermal treatment leads to a deterioration in the strength of metakaolin geopolymer, whereas fly ash geopolymer gains strength upon heating. The formation of albite above 900 °C is responsible for the fusion of geopolymer matrix during exposure to 1200 °C, which leads to the deformation of the geopolymer samples. Chamotte aggregate improves the performance of geopolymer material by increasing the thermal stability of geopolymers via sintering of the aggregate particles with the geopolymer matrix in the contact zone. Full article

The fixation of heavy metals (Ba, Cu, Pb) in an alkali-activated matrix was investigated. The matrix consisted of fly ash and blast furnace slag (BFS). The mixture of NaOH and Na-silicate was used as alkaline activator. Three analytical techniques were used to describe the fixation of heavy metals—X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS), and X-ray powder diffraction (XRD). All heavy metals formed insoluble salts after alkaline activation. Ba was fixed as BaSO₄, and only this product was crystalline. EDS mapping showed that Ba was cumulated in some regions and formed clusters. Pb was present in the form of Pb(OH)₂ and was dispersed throughout the matrix on the edges of BFS grains. Cu was fixed as Cu(OH)₂ and also was cumulated in some regions and formed clusters. Cu was present in two different chemical states; apart from Cu(OH)₂, a Cu–O bond was also identified. Full article

This study presents an experimental overview for the development of photocatalytic materials based on geopolymer binders as catalyst support matrices. Particularly, geopolymer matrices obtained from different solid precursors (fly ash and metakaolin), composite systems (siloxane-hybrid, foamed hybrid), and curing temperatures (room temperature and 60 °C) were investigated for the same photocatalyst content (i.e., 3% TiO₂ by weight of paste). The geopolymer matrices were previously designed for different applications, ranging from insulating (foam) to structural materials. The photocatalytic activity was evaluated as NO degradation in air, and the results were compared with an ordinary Portland cement reference. The studied matrices demonstrated highly variable photocatalytic performance depending on both matrix constituents and the curing temperature, with promising activity revealed by the geopolymers based on fly ash and metakaolin. Furthermore, microstructural features and titania dispersion in the matrices were assessed by scanning electron microscopy (SEM) and energy dispersive X-ray (EDS) analyses. Particularly, EDS analyses of sample sections indicated segregation effects of titania in the surface layer, with consequent enhancement or depletion of the catalyst concentration in the active sample region, suggesting non-negligible transport phenomena during the curing process. The described results demonstrated that geopolymer binders can be interesting catalyst support matrices for the development of photocatalytic materials and indicated a large potential for the exploitation of their peculiar features. Full article

This paper assesses the feasibility of two industrial wastes, fly ash (FA) and rice husk ash (RHA), as raw materials for the production of geopolymeric pastes. Three typologies of samples were thus produced: (i) halloysite activated with potassium hydroxide and nanosilica, used as the reference sample (HL-S); (ii) halloysite activated with rice husk ash dissolved into KOH solution (HL-R); (iii) FA activated with the alkaline solution realized with the rice husk ash (FA-R). Dense and porous samples were produced and characterized in terms of mechanical properties and environmental impact. The flexural and compressive strength of HL-R reached about 9 and 43 MPa, respectively. On the contrary, the compressive strength of FA-R is significantly lower than the HL-R one, in spite of a comparable flexural strength being reached. However, when porous samples are concerned, FA-R shows comparable or even higher strength than HL-R. Thus, the current results show that RHA is a valuable alternative to silica nanopowder to prepare the activator solution, to be used either with calcined clay and fly ash feedstock materials. Finally, a preliminary evaluation of the global warming potential (GWP) was performed for the three investigated formulations. With the mix containing FA and RHA-based silica solution, a reduction of about 90% of GWP was achieved with respect to the values obtained for the reference formulation. Full article

Significant drying shrinkage is one of the main limitations for the wider utilization of alkali-activated slag (AAS). Few previous works revealed that it is possible to reduce AAS drying shrinkage by the use of shrinkage-reducing admixtures (SRAs). However, these studies were mainly focused on SRA based on polypropylene glycol, while as it is shown in this paper, the behavior of SRA based on 2-methyl-2,4-pentanediol can be significantly different. While 0.25% and 0.50% had only a minor effect on the AAS properties, 1.0% of this SRA reduced the drying shrinkage of waterglass-activated slag mortar by more than 80%, but it greatly reduced early strengths simultaneously. This feature was further studied by isothermal calorimetry, mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM). Calorimetric experiments showed that 1% of SRA modified the second peak of the pre-induction period and delayed the maximum of the main hydration peak by several days, which corresponds well with observed strength development as well as with the MIP and SEM results. These observations proved the certain incompatibility of SRA with the studied AAS system, because the drying shrinkage reduction was induced by the strong retardation of hydration, resulting in a coarsening of the pore structure rather than the proper function of the SRA. Full article

The preparation and characterization of composite materials based on geopolymers obtained from fly ash and epoxy resins are reported for the first time. These materials have been prepared through a synthetic method based on the concurrent reticulation of the organic and inorganic components that allows the formation of hydrogen bonding between the phases, ensuring a very high compatibility between them. These new composites show significantly improved mechanical properties if compared to neat geopolymers with the same composition and comparable performances in respect to analogous geopolymer-based composites obtained starting from more expensive raw material such as metakaolin. The positive combination of an easy synthetic approach with the use of industrial by-products has allowed producing novel low cost aluminosilicate binders that, thanks to their thixotropicity and good adhesion against materials commonly used in building constructions, could be used within the field of sustainable building. Full article

In situ elevated temperature investigations using fly ash based geopolymers filled with alumina aggregate were undertaken. Compressive strength and short term creep tests were carried out to determine the onset temperature of viscous flow. Fire testing using the standard cellulose curve was performed. Applying a load to the specimen as the temperature increased reduced the temperature at which viscous flow occurred (compared to test methods with no applied stress). Compressive strength increased at the elevated temperature and is attributed to viscous flow and sintering forming a more compact microstructure. The addition of alumina aggregate and reduction of water content reduced the thermal conductivity. This led to the earlier onset and shorter dehydration plateau duration times. However, crack formation was reduced and is attributed to smaller thermal gradients across the fire test specimen. Full article

An alkali-activated blend of aluminum cement and class F fly ash is an attractive solution for geothermal wells where cement is exposed to significant thermal shocks and aggressive environments. Set-control additives enable the safe cement placement in a well but may compromise its mechanical properties. This work evaluates the effect of a tartaric-acid set retarder on phase composition, microstructure, and strength development of a sodium-metasilicate-activated calcium aluminate/fly ash class F blend after curing at 85 °C, 200 °C or 300 °C. The hardened materials were characterized with X-ray diffraction, thermogravimetric analysis, X-ray computed tomography, and combined scanning electron microscopy/energy-dispersive X-ray spectroscopy and tested for mechanical strength. With increasing temperature, a higher number of phase transitions in non-retarded specimens was found as a result of fast cement hydration. The differences in the phase compositions were also attributed to tartaric acid interactions with metal ions released by the blend in retarded samples. The retarded samples showed higher total porosity but reduced percentage of large pores (above 500 µm) and greater compressive strength after 300 °C curing. Mechanical properties of the set cements were not compromised by the retarder. Full article

Amorphous silica and alumina of metakaolin are used to adjust the bulk composition of black (BSS) and white (WSS) steel slag to prepare alkali-activated (AAS) mortars consolidated at room temperature. The mix-design also includes also the addition of semi-crystalline matrix of river sand to the metakaolin/steel powders. The results showed that high strength of the steel slag/metakaolin mortars can be achieved with the geopolymerization process which was particularly affected by the metallic iron present into the steel slag. The corrosion of the Fe particles was found to be responsible for porosity in the range between 0.1 and 10 µm. This class of porosity dominated (~31 vol %) the pore network of B compared to W samples (~16 vol %). However, W series remained with the higher cumulative pore volume (0.18 mL/g) compared to B series, with 0.12 mL/g. The maximum flexural strength was 6.89 and 8.51 MPa for the W and B series, respectively. The fracture surface ESEM observations of AAS showed large grains covered with the matrix assuming the good adhesion bonds between the gel-like geopolymer structure mixed with alkali activated steel slag and the residual unreacted portion. The correlation between the metallic iron/Fe oxides content, the pore network development, the strength and microstructure suggested the steel slag's significant action into the strengthening mechanism of consolidated products. These products also showed an interesting adsorption/desorption behavior that suggested their use as coating material to maintain the stability of the indoor relative humidity. Full article

In recent years, the utilization of different non-traditional cements and composites has been increasing. Alkali-activated cementitious materials, especially those based on the alkali activation of blast furnace slag, have considerable potential for utilization in the building industry. However, alkali-slag cements exhibit very rapid setting times, which are too short in some circumstances, and these materials cannot be used for some applications. Therefore, it is necessary to find a suitable retarding admixture. It was shown that the sodium phosphate additive has a strong effect on the heat evolution during alkali activation and effectively retards the hydration reaction of alkali-activated blast furnace slag. The aim of the work is the suggestion of a reaction mechanism of retardation mainly based on Raman and X‑ray photoelectron spectroscopy. Full article

The Bayer process utilises high concentrations of caustic and elevated temperature to liberate alumina from bauxite, for the production of aluminium and other chemicals. Within Australia, this process results in 40 million tonnes of mineral residues (Red mud) each year. Over the same period, the energy production sector will produce 14 million tonnes of coal combustion products (Fly ash). Both industrial residues require impoundment storage, yet combining some of these components can produce geopolymers, an alternative to cement. Geopolymers derived from Bayer liquor and fly ash have been made successfully with a compressive strength in excess of 40 MPa after oven curing. However, any product from these industries would require large volume applications with robust operational conditions to maximise utilisation. To facilitate potential unconfined large-scale production, Bayer derived fly ash geopolymers have been optimised to achieve ambient curing. Fly ash from two different power stations have been successfully trialled showing the versatility of the Bayer liquor-ash combination for making geopolymers. Full article

Mineral wools are the most common insulation materials in buildings worldwide. However, mineral wool waste is often considered unrecyclable because of its fibrous nature and low density. In this paper, rock wool (RW) and glass wool (GW) were studied as alkali-activated material precursors without any additional co-binders. Both mineral wools were pulverized by a vibratory disc mill in order to remove the fibrous nature of the material. The pulverized mineral wools were then alkali-activated with a sodium aluminate solution. Compressive strengths of up to 30.0 MPa and 48.7 MPa were measured for RW and GW, respectively, with high flexural strengths measured for both (20.1 MPa for RW and 13.2 MPa for GW). The resulting alkali-activated matrix was a composite-type in which partly-dissolved fibers were dispersed. In addition to the amorphous material, sodium aluminate silicate hydroxide hydrate and magnesium aluminum hydroxide carbonate phases were identified in the alkali-activated RW samples. The only crystalline phase in the GW samples was sodium aluminum silicate. The results of this study show that mineral wool is a very promising raw material for alkali activation. Full article

The present study investigated aluminosilicate gel in alkali-activated fly ash exposed to a CO₂-rich environment by means of NMR spectroscopy. The alkali-activated fly ash was exposed to an atmospheric CO₂ concentration of 10% after curing at 80 °C initially for 24 h. Under high concentrations of CO₂, highly reactive components Na and Al, which completely reacted within the first few hours, were unaffected by carbonation, while Si, with relatively slower reactivity, behaved differently. Despite a lower degree of the reaction in the carbonated sample, the monomeric silicates rapidly became of higher polymerization, meaning that exposure to high concentrations of CO₂ caused Si to form a binding gel phase. Consequently, the carbonated sample possessed a higher amount of binding gel. The obtained results may be useful to understand the fundamental chemistry and behavior of aluminosilicate gel under high concentrations of CO₂. Full article

Improvements of soft soils by mechanically mixing cementitious additives have been widely practised for construction of infrastructure. Mixing of additives improves strength and compressibility properties of soils through the development of soil structure. This study investigates the 1-D compression behaviour of alkali-activated slag treated acid sulphate soils (ASS) cured up to 365 days. The void ratio-logarithm of pressure (e-logσ′) behaviour of treated ASS, including the destructuration behaviour, with additive contents and curing time have been analysed. X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses have been undertaken to explain the observed variations of the 1-D compression behaviour. This paper presents the results of these analyses in view of obtaining an insight into the 1-D compression behaviour of treated ASS with the help of mineralogical analysis. Full article

Microstructural and mechanical properties of alkali activated binders based on blends of Colombian granulated blast furnace slag (GBFS) and fly ash (FA) were investigated. The synthesis of alkali activated binders was conducted at 85 °C for 24 h with different slag/fly ash ratios (100:0, 80:20, 60:40, 40:60, 20:80, and 0:100). Mineralogical and microstructural characterization was carried out by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX) and Nuclear magnetic resonance (NMR). Mechanical properties were evaluated through the compressive strength, modulus of elasticity and Poisson’s ratio. The results show that two different reaction products were detected in the slag/fly ash mixtures, a calcium silicate hydrate with Al in its structure (C-A-S-H gel) and a sodium aluminosilicate hydrate (N-A-S-H gel) with higher number of polymerized species and low content in Ca. It was found that with the increase of the amount of added slag, the amount of C-A-S-H gel increased and the amount of N-A-S-H gel decreased. The matrix was more dense and compact with almost absence of pores. The predominance of slag affected positively the compressive strength, Young’s modulus and Poisson’s ratio, with 80% slag and 20% fly ash concrete being the best mechanical performance blend. Full article