Potential utilization of class C fly ash-based geopolymer in oil well cementing operations

The early age compressive strength development of class C fly ash-based geopolymers under high pressure and high temperatures of curing is considered as an alternative to well cements. Uniaxial compressive strength (UCS) results show how the curing temperature affects the early compressive strength development. As the temperature rises from 87 to 125 °C, a consecutive reaction seems to take place at the higher concentrations of NaOH, which decrease the compressive strength at the higher temperature. The taken scanning electron microscope (SEM) images show a change in the morphology of the samples at 125 °C with the higher concentrations of NaOH. Ultrasonic cement analyzers (UCA) were employed to investigate the instantaneous strength development of the geopolymeric slurries. As the common cement models were not able to assess the compressive strength development, the custom algorithm option in the UCA software was applied. The developed empirical correlations were not able to accurately estimate the sonic strength of the slurries remarkably at 125 °C. The rheological measurements of the prepared geopolymeric slurries showed a Newtonian like behavior.     

Alkali-activated fly ash-based geopolymers with zeolite or bentonite as additives

Geopolymers were synthesized by using fly ash as the main starting material, zeolite or bentonite as supplementary materials, and NaOH and CaO together as activator. An orthogonal array testing protocol was used to analyze the influence of the mix proportion on the properties of the geopolymers. The results indicate that the concentration of NaOH solution and the CaO content play an important role on the strength of the materials. Especially, with zeolite as additive, the fly ash-based geopolymer shows the highest strength and the best sulfate resistance. Infrared spectroscopy, X-ray, and SEM–EDX demonstrate that supplementary zeolite may involve the process of geopolymerization to form a stable zeolitic structure and improve the properties of the geopolymer. Bentonite simply acts as a filler to make the geopolymer more compact, but shows no improvement on the compositions and the microstructures of the geopolymer.     

Effect of fire exposure on cracking,spalling and residual strength of fly ash geopolymer concrete

Fly ash based geopolymer is an emerging alternative binder to cement for making concrete. The cracking, spalling and residual strength behaviours of geopolymer concrete were studied in order to understand its fire endurance, which is essential for its use as a building material. Fly ash based geopolymer and ordinary portland cement (OPC) concrete cylinder specimens were exposed to fires at different temperatures up to 1000 °C, with a heating rate of that given in the International Standards Organization (ISO) 834 standard. Compressive strength of the concretes varied in the range of 39–58 MPa. After the fire exposures, the geopolymer concrete specimens were found to suffer less damage in terms of cracking than the OPC concrete specimens. The OPC concrete cylinders suffered severe spalling for 800 and 1000 °C exposures, while there was no spalling in the geopolymer concrete specimens. The geopolymer concrete specimens generally retained higher strength than the OPC concrete specimens. The Scanning Electron Microscope (SEM) images of geopolymer concrete showed continued densification of the microstructure with the increase of fire temperature. The strength loss in the geopolymer concrete specimens was mainly because of the difference between the thermal expansions of geopolymer matrix and the aggregates.     

Sustainable utilization of pre-treated and nano fly ash powder for the development of durable geopolymer mortars

Developments in geopolymer construction are gaining more interest nowadays due to the elimination of cement and the consequent effects such as carbon dioxide emission, greenhouse effect, etc. Although the use of fly ash as a binder in the geopolymer system acts as a key solution for the major hazardous effects like land dumping, soil contamination, groundwater pollution, and respiratory diseases, the slow reactivity of the fly ash resulted in the considerable reduction in the strength. In this paper, a novel pretreatment method was employed on the fly ash binder in terms of thermal and mechanical means. Also, a cost-effective nano fly ash powder was synthesized and used as filler material on the geopolymer system. The efficiency of the fabricated geopolymer mortar was assessed by examining the workability, compressive strength, and resistance against chloride ion penetration. The geopolymer mortars with pre-treated fly ash exhibited a highly workable mix of 130% improved flow rate without adding any superplasticizer. Further, the addition of 1% nano fly ash, exhibited the highest compressive strength of 71.22 MPa, confirmed almost nil chloride ion permeability, and sustained 90% residual strength after immersing in the brine solution for 60 days which explored the development of sustainable and cost-effective geopolymer construction in the marine environment.     

Effects of NaOH concentrations on physical and electrical properties of high calcium fly ash geopolymer paste

The effects of sodium hydroxide (NaOH) concentration on setting time, compressive strength and electrical properties at the frequencies of 100 Hz–10 MHz of high calcium fly ash geopolymer pastes were investigated. Five NaOH concentrations (8, 10, 12, 15 and 18 molar) were studied. The liquid to ash ratio of 0.4, sodium silicate to sodium hydroxide ratio of 0.67 and low temperature curing at 40 °C were selected in making geopolymer pastes. The results showed that NaOH concentration had significant influence on the physical and electrical properties of geopolymer paste. The pastes with high NaOH concentrations showed increased setting time and compressive strength due to a high degree of geopolymerization as a result of the increased leaching of silica and alumina from fly ash. The dielectric constant and conductivity increased with NaOH concentration while tan δ decreased due to an increase in geopolymerization. At the frequency of 10³ Hz, the dielectric constants of all pastes were approximately 10⁴ S/cm and decreased with increased frequency. The relaxation peaks of tan δ reduced with an increase in NaOH concentration and ranged between 2.5 and 4.5. The AC conductivity behavior followed the universal power law and the values were in the range of 3.7 × 10⁻³–1.5 × 10⁻² at 10⁵–10⁶ Hz.     

Sorptivity and acid resistance of ambient-cured geopolymer mortars containing nano-silica

This study investigated the effects of nano-silica on flowability, strength development, sorptivity and acid resistance properties of fly ash geopolymer mortars cured at 20 °C. The changes in mass, compressive strength and microstructure of the specimens after immersion in acid solutions for different durations were determined. The microstructures were studied by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) analysis. It was found that addition of nano-silica in geopolymer mortars based on fly ash alone or fly ash blended with 15% GGBFS or 10% OPC improved the compactness of microstructure by reducing porosity. Thus, the nano-silica reduced sorptivity and increased compressive strength of the mixes. The average mass loss after 90 days of immersion in acid solutions reduced from 6.0% to 1.9% by addition of 2% nano-silica. Similarly, significant reduction in strength loss after immersion in acid solution was observed in the specimens by using nano-silica.     

Compressive strength and microstructural analysis of fly ash/palm oil fuel ash based geopolymer mortar

This paper presents the effects and adaptability of palm oil fuel ash (POFA) as a replacement material in fly ash (FA) based geopolymer mortar from the aspect of microstructural and compressive strength. The geopolymers developed were synthesized with a combination of sodium hydroxide and sodium silicate as activator and POFA and FA as high silica–alumina resources. The development of compressive strength of POFA/FA based geopolymers was investigated using X-ray florescence (XRF), X-ray diffraction (XRD), Fourier transform infrared (FTIR), and field emission scanning electron microscopy (FESEM). It was observed that the particle shapes and surface area of POFA and FA as well as chemical composition affects the density and compressive strength of the mortars. The increment in the percentages of POFA increased the silica/alumina (SiO₂/Al₂O₃) ratio and that resulted in reduction of the early compressive strength of the geopolymer and delayed the geopolymerization process.     

The effects of ground granulated blast-furnace slag blending with fly ash and activator content on the workability and strength properties of geopolymer concrete cured at ambient temperature

Inclusion of ground granulated blast-furnace slag (GGBFS) with class F fly-ash can have a significant effect on the setting and strength development of geopolymer binders when cured in ambient temperature. This paper evaluates the effect of different proportions of GGBFS and activator content on the workability and strength properties of fly ash based geopolymer concrete. In this study, GGBFS was added as 0%, 10% and 20% of the total binder with variable activator content (40% and 35%) and sodium silicate to sodium hydroxide ratio (1.5–2.5). Significant increase in strength and some decrease in the workability were observed in geopolymer concretes with higher GGBFS and lower sodium silicate to sodium hydroxide ratio in the mixtures. Similar to OPC concrete, development of tensile strength correlated well with the compressive strength of ambient-cured geopolymer concrete. The predictions of tensile strength from compressive strength of ambient-cured geopolymer concrete using the ACI 318 and AS 3600 codes tend to be similar to that for OPC concrete. The predictions are more conservative for heat-cured geopolymer concrete than for ambient-cured geopolymer concrete.     

Properties of geopolymer with seeded fly ash and rice husk bark ash

In the present work, compressive strength of inorganic polymers (geopolymers) produced of seeded fly ash and rice husk bark ash has been investigated. Different specimens made from a mixture of fly ash and rice husk bark ash in fine and coarse form were subjected to compressive strength tests at 7 and 28 days of curing. The curing regime was different: one set of the specimens were cured at room temperature until reaching to 7 and 28 days and the other sets were oven cured for 36 h at the range of 40-90 °C and then cured at room temperature until 7 and 28 days. The results indicate that in both 7 and 28 days regimes, the highest strengths are related to the specimens by SiO₂/Al₂O₃ ratio equals 2.99 cured at 80 °C. For these specimens, those contained finer fly ash particles show more compressive strength. Thermogravimetric analysis and Fourier transform infrared spectroscopy both also are in agreement with the obtained results from compressive strength tests. In addition, SEM micrographs of the specimens show that the finer the particle size of the utilized ashes, the denser the microstructure which confirms the results obtained by the strength tests.     

Characterisation of class F fly ash geopolymer pastes immersed in acid and alkaline solutions

Acid and alkaline resistance of class F fly ash based geopolymer pastes has been investigated. As prepared geopolymers showed high solubility in both strong alkali and acid solutions. Calcination of the fly ash based geopolymers at 600 °C resulted in a decrease of amorphous component from 63.4 to 61.6 wt.%. However, the solubility of the Al, Si and Fe ions in 14 M NaOH and 18% HCl after 5 days immersion decreased from 1.3 to 16-fold in comparison to as prepared geopolymer samples. Calcination of the geopolymers also resulted in a 30% reduction in compressive strength. Acid and alkali resistance of the geopolymers investigated strongly depends on mineralogical composition change of the calcined geopolymer. Partial crystallisation of non-reacted fly ash particles in the geopolymer decreases its solubility in acid and alkali solutions.     

Compressive strength and microstructure of fly ash based geopolymer blended with silica fume under thermal cycle

This work aims to reveal the effects of silica fume on properties of fly ash based geopolymer under thermal cycles. Geopolymer specimens were prepared by alkali activation of fly ash, which was partially replaced by silica fume at levels ranging from 0% to 30% with an interval of 10%, by mass. Microstructure, residual strength and mass loss of fly ash based geopolymer blended with silica fume before and after exposed to 7, 28 and 56 heat-cooling thermal cycles at different target temperatures of 200 °C, 400 °C and 800 °C were assessed and compared. The experimental results reveal that silica fume addition enhances strength development in geopolymer. Under thermal cycles, the compressive strength of geopolymer decreases, and the compressive strength loss, as well as the mass loss, increases with increasing target temperature. The strength loss is the same regardless of silica fume content after thermal cycles. Microstructure analysis uncovers that pore structure of geopolymer degrades after thermal cycles. The pores of geopolymer are refined by the addition of silica fume. The incorporation of silica fume optimizes the microstructure and improves the thermal resistance of geopolymer. Silica fume increases the strength of the geopolymer and even though the strength loss is the same, the strength after heat cycle exposure is still good.     

Use of OPC to improve setting and early strength properties of low calcium fly ash geopolymer concrete cured at room temperature

Most previous works on fly ash based geopolymer concrete focused on concretes subjected to heat curing. Development of geopolymer concrete that can set and harden at normal temperature will widen its application beyond precast concrete. This paper has focused on a study of fly ash based geopolymer concrete suitable for ambient curing condition. A small proportion of ordinary Portland cement (OPC) was added with low calcium fly ash to accelerate the curing of geopolymer concrete instead of using elevated heat. Samples were cured in room environment (about 23 °C and RH 65 ± 10%) until tested. Inclusion of OPC as little as 5% of total binder reduced the setting time to acceptable ranges and caused slight decrease of workability. The early-age compressive strength improved significantly with higher strength at the age of 28 days. Geopolymer microstructure showed considerable portion of calcium-rich aluminosilicate gel resulting from the addition of OPC.     

Compressive stress-strain model for low-calcium fly ash-based geopolymer and heat-cured Portland cement concrete

This research focuses on elucidating the present knowledge gaps in geopolymer concrete's engineering properties, specifically its stress-strain behaviour. Geopolymer concrete (GPC) is an emerging alternative to ordinary Portland cement concrete (OPCC), and is produced via a polycondensation reaction between aluminosilicate source materials and an alkaline solution. As a relatively new material, many engineering properties of geopolymer concrete are still undetermined. In this paper, the compressive strength, modulus of elasticity and stress-strain behaviour of ambient and heat-cured GPC and OPCC have been studied experimentally. A total of 195 geopolymer concrete cylinders and 210 Portland cement concrete cylinders were tested for the above mentioned characteristics. Based on the experimental results, constitutive models describing the complete stress–strain behaviour in uniaxial compression have been developed for the low-calcium fly ash-based geopolymer concrete and the heat-cured Portland cement concrete.     

Analysis of geopolymer concrete columns

Ordinary portland cement (OPC) has been traditionally used as the binding agent in concrete. However, it is also necessary to search for alternative low-emission binding agents for concrete to reduce the environmental impact caused by manufacturing of cement. Geopolymer, also known as inorganic polymer, is one such material that uses by-product material such as fly ash instead of cement. Recent research has shown that fly ash-based geopolymer concrete has suitable properties for its use as a construction material. Since the strength development mechanism of geopolymer is different from that of OPC binder, it is necessary to obtain a suitable constitutive model for geopolymer concrete to predict the load–deflection behaviour and strength of geopolymer concrete structural members. This article has investigated the suitability of using an existing stress–strain model originally proposed by Popovics for OPC concrete. It is found that the equation of Popovics can be used for geopolymer concrete with minor modification to the expression for the curve fitting factor, to better fit with the post-peak parts of the experimental stress–strain curves. The slightly modified set of stress–strain equations was then used in a non-linear analysis for reinforced concrete columns. A good correlation is achieved between the predicted and measured ultimate loads, load–deflection curves and deflected shapes for 12 slender test columns.     

Efflorescence control in geopolymer binders based on natural pozzolan

This paper addresses methods to reduce efflorescence in a geopolymer binder based on a pumice-type natural pozzolanic material from Taftan, Iran. Geopolymer pastes samples are analyzed for compressive strength and efflorescence formation after curing at 95% humidity for 28 days. To reduce the extent of efflorescence, Al-rich mineral admixtures such as metakaolin, ground granulated blast-furnace slag, and three types of calcium aluminate cements are incorporated into the dry binder at a range of concentrations. Hydrothermal curing at elevated temperatures also shows a positive effect in efflorescence reduction. Calcium aluminate cements show the greatest effect in efflorescence reduction, which is attributed to their dissolution in alkaline media releasing high amounts of alumina into the aluminosilicate geopolymer gel. These results confirm that it is possible to develop a more reliable geopolymer binder with improved properties either by adding a suitable amount of active alumina to precursors such as natural pozzolan, or by manipulating the curing conditions to enhance alumina release from less-reactive precursor phases.     

Assessing the suitability of three Australian fly ashes as an aluminosilicate source for geopolymers in high temperature applications

Fly ash characteristics cannot be assumed to be constant between power stations as they are highly dependent on the coal source and burning conditions. It is critical to understand the characteristics of fly ash in order to produce geopolymers suitable for high temperature applications. We report on the characterisation of fly ash from three Australian power stations in terms of elemental composition, phase composition, particle size, density and morphology. Geopolymers were synthesised from each of the fly ashes using sodium silicate and sodium aluminate solutions to achieve a range of Si:Al compositional ratios. Mechanical properties of geopolymer binders are presented and the effect of the source fly ash characteristics on the hardened product is discussed, as well as implications for high temperature applications. It was found that the twenty eight day strength of geopolymers is largely dependent on the sub 20 μm size fraction of the fly ash. Strength loss after high temperature exposure was found to be dependent on the concentration of iron in the fly ash precursor and the Si:Al ratio of the geopolymer mixture.     

Alkali-activation potential of biomass-coal co-fired fly ash

Co-fired fly ash, derived from the co-combustion of coal and biomass, is examined as a potential precursor for geopolymers. Compared to a coal fly ash, two co-fired fly ashes have a lower vitreous content and higher carbon content, primarily due to differing combustion processing variables. As a result, binders produced with these co-fired fly ashes have reduced reaction potential. Nevertheless, compressive strengths are generally highest for all ashes activated with solutions with a molar ratio of SiO₂/(Na₂O + K₂O) = 1, and these mixes reach the highest extent of reaction among those studied. Activation with sodium hydroxide solution forms zeolitic phases for all ashes. The thermal and dilatometric behavior of the coal and co-fired fly ash geopolymers is similar between equivalent mix designs. These results indicate that co-fired fly ashes can be viably used to form alkali-activated geopolymers, which is a new beneficial end-use for these emerging waste materials.     

Coal fly ash-slag-based geopolymers: Microstructure and metal leaching

This study deals with the use of fly ash as a starting material for geopolymeric matrices. The leachable concentrations of geopolymers were compared with those of the starting fly ash to evaluate the retention of potentially harmful elements within the geopolymer matrix. Geopolymer matrices give rise to a leaching scenario characterised by a highly alkaline environment, which inhibits the leaching of heavy metals but may enhance the mobilization of certain oxyanionic species. Thus, fly ash-based geopolymers were found to immobilise a number of trace pollutants such as Be, Bi, Cd, Co, Cr, Cu, Nb, Ni, Pb, Sn, Th, U, Y, Zr and rare earth elements. However, the leachable levels of elements occurring in their oxyanionic form such as As, B, Mo, Se, V and W were increased after geopolymerization. This suggests that an optimal dosage, synthesis and curing conditions are essential in order to obtain a long-term stable final product that ensures an efficient physical encapsulation.     

Effect of NaOH concentration on properties and microstructure of a novel reactive ultra-fine fly ash geopolymer

This study used reactive ultra-fine fly ash (RUFA) as the primary raw materials in the preparation of a novel RUFA geopolymer. Note that the solution to binder weight ratio was maintained at the same level by varying the concentration of the NaOH solution. Extensive analysis was conducted to characterize the flowability and mechanical properties. X-ray diffraction (XRD), Scanning Electron Microscope-Energy Dispersive Spectrometer (SEM-EDS), Fourier transform infrared spectroscopy (FT-IR), mercury intrusion porosimetry (MIP), thermogravimetric (TG), and zeta potential analyses were used to examine the microstructure of RUFA geopolymers. Increasing the concentration of NaOH also led to an increase in compressive strength. A high NaOH concentration of 12 mol/L resulted in compressive strength of 97.6 MPa at 28 days. Finally, increasing the concentration of NaOH increased the formation of the primary reaction geopolymerization product, N-A-S-H gel, resulting in a denser microstructure with lower porosity.     

Influence of curing conditions on properties of high calcium fly ash geopolymer containing Portland cement as additive

This paper investigated the mechanical properties and microstructure of high calcium fly ash geopolymer containing ordinary Portland cement (OPC) as additive with different curing conditions. Fly ash (FA) was replaced with OPC at dosages of 0%, 5%, 10%, and 15% by weight of binders. Setting time and microstructure of geopolymer pastes, and flow, compressive strength, porosity and water absorption of geopolymer mortars were studied. Three curing methods viz., vapour-proof membrane curing, wet curing and temperature curing were used. The results showed that the use of OPC as additive improved the properties of high calcium fly ash geopolymer. The strength increased due to the formation of additional C–S–H and C–A–S–H gel. Curing methods also significantly affected the properties of geopolymers with OPC. Vapour-proof membrane curing and water curing resulted in additional OPC hydration and led to higher compressive strength. The temperature curing resulted in a high early compressive strength development.