Geopolymer with Hierarchically Meso‐/Macroporous Structures from Reactive Emulsion Templating

We present a simple synthetic route to hierarchically porous geopolymers using triglyceride oil for a reactive emulsion template. In the new synthetic method, highly alkaline geopolymer resin was first mixed with canola oil to form a homogeneous viscous emulsion which was then cured at 60°C to give a hard monolithic material. During the process, the oil in the alkaline emulsion undergoes a saponification reaction to be decomposed to water‐soluble soap and glycerol molecules which were then extracted with hot water to finally yield porous geopolymers. Nitrogen adsorption studies indicated the presence of mesopores, whereas the SEM studies revealed that the mesoporous geopolymer matrix are dotted with spherical macropores (10–50 μm) which are due to oil droplet template in the emulsion. Various synthetic parameters including the precursor compositions were examined to control the porosity. BET surface area and BJH pore volume of the materials were up to 124 m²/g and 0.7 cm³/g, respectively, and the total pore volumes up to 2.1 cm³/g from pycnometry.     

Evolution of the microstructure of unconsolidated geopolymers by thermoporometry

This paper studies the evolution of the pore size distribution of a fresh unconsolidated geopolymer paste between one day and a week, using thermoporometry. This was made possible by following a careful protocol for sample preparation and for analysis by differential scanning calorimetry. In contrast with nitrogen gas adsorption, this method quantifies directly the amount of water in pores. It also does not require heat and vacuum drying, thus maintaining the fragile pore structure of the unconsolidated paste. Moreover, it was found that, in a typical metakaolin-based sodium geopolymer with a 10 to 20 hours workability period, the porosity gradually refines during the first week while the mesoporous volume is cut in half. This is probably due to the fact that the geopolymer network was still actively condensing from the activation solution. Part of the pore water never froze and, from mass balance, this residual water was attributed to the water bound in the hydration shell of the sodium counter ions. Only a minor occurrence of covalently bound protons as silanol groups was observed. The results presented here usefully complement data obtained by conventional techniques at later ages on consolidated geopolymers. It supports the growing body of literature on the structural evolution of geopolymers with time.     

Geopolymer foams by gelcasting

Highly porous geopolymers, with homogeneous microstructure, open cells and porosity up to 80 vol%, were fabricated by gel-casting, a process commonly used to produce ceramic foams. Geopolymer foams were prepared by stirring an activated blend of metakaolin and fly ash with a mixture of potassium hydroxide and potassium silicate with Si/K=1.66. The cell size and size distribution of the geopolymer foams could be efficiently adjusted by the control of some parameters such as solid content, surfactant type and content and mixing speed. The influence of each parameter on the porosity and other characteristics of the geopolymer foams were investigated. The foams were evaluated only after heat treatment at 80 °C, which was conducted in order to complete the geopolymerization reactions. The produced components could be heat treated up to 1200 °C in air without melting, if desired.The characteristics (morphology, strength, chemical and thermal resistance) of the geopolymer foams suggest that they could be employed as low cost replacement for highly porous ceramics in applications such as catalysis supports, adsorption and separation, filtration of hot gases and refractory insulation of furnaces. In addition, these components could be considered sustainable, because they reach their final properties after processing at temperatures not exceeding 100 °C and part of the raw materials employed are industrial waste.     

Thermal energy storage performance of hierarchical porous kaolinite geopolymer based shape-stabilized composite phase change materials

Phase change materials (PCMs) are prospective energy materials that are widely applied in building energy conservation, waste heat recovery, infrared stealth technology and solar dynamic power system. The enhancement of heat transfer and leak-proof performance are critical to PCMs. Although geopolymers have been applied in thermal energy storage, meanwhile, hierarchically porous geopolymers have already shown superb performance in various functional applications, to the authors’ knowledge, no report concerning the application of hierarchical porous ones have been issued. This paper concerns the preparation of a shape-stabilized composite PCMs, consisting of hierarchically porous kaolinite-based geopolymer (PKG) embedding polyethylene glycol 4000 (PEG4000), which shows promising prospects in thermal energy storage. Optimized porous geopolymer matrices feature high porosity (>83%), combined with high specific surface area (4.7 m²/g) and thermal conductivity (TC, 1.324 W·m⁻¹·K⁻¹). Furthermore, the shape-stabilized composite PCMs show excellent thermal energy storage properties: loading rate of 80.93 wt%, latent heat of 168.80 J g⁻¹ and TC of ∼0.36 W·m⁻¹·K⁻¹ at 20–30 °C, which is 1.64 times of the TC of pure PEG4000. Finally, the photothermal conversion performances of the shape-stabilized composite PCMs were also simulated.     

Direct ink writing of porous SiC ceramics with geopolymer as binder

We herein report a novel strategy for direct ink writing of porous SiC parts by using geopolymers (GP) as binders and sintering SiC/GP composites at high temperatures via carbothermal reduction. The effects of treatment temperatures on the microstructure, pore size distribution and compressive strength of SiC/GP composites were systematically investigated. The total porosity of porous SiC carriers was as high as 76.4 vol% after being sintered at 1800 °C and exhibited a much broader pore size distribution (pore volumes) between 39 nm and 13.951 µm (~1.68 mL/g) accompanied by an interconnected hierarchical porous structure. After loading lamellar graphene oxide into the porous SiC carrier to form GO/SiC adsorbents, they exhibited fast and near-unity removal of methylene blue, and the adsorption efficiency still exceeded 82.0% after multiple times usage. These results prove that it is possible to remove hazardous materials from wastewater using reusable porous SiC ceramics as reusable adsorbent carriers.     

Porous alkali-activated material from hypergolic coal gangue by microwave foaming for methylene blue removal

Overall, 100% hypergolic coal gangue (HCG)-based geopolymer foams were produced by a novel saponification-microwave foaming combined route. Microwave foaming with and without expired vegetable oil was first used to produce CG-based geopolymer foams. Macropores were mainly generated by microwave foaming, and mesopores were mainly obtained by the addition of expired soybean oil that underwent a saponification reaction. The effects of the oil content on the density, porosity, pore morphology, compression strength, and methylene blue adsorption properties were studied. High total porosity (85.9–89.0 vol%) and acceptable compression strength (0.46–1.1 MPa) HCG-based geopolymer foams were produced. Foams with 12.59 wt% oil exhibited the best adsorption properties, with an adsorption capacity up to 9.4 mg/g and high removal efficiency of about 95.3%. These solid-waste-based porous components are promising monolithic adsorbents for wastewater treatment.     

Fast microwave syntheses of fly ash based porous geopolymers in the presence of high alkali concentration

Microwave synthesis of porous fly ash geopolymers was achieved using a household microwave oven. Fly ash paste containing SiO₂ and Al₂O₃ component was mixed with sodium silicate (Na₂SiO₃) solutions at different concentrations of sodium hydroxide (NaOH) of 2, 5, 10, and 15 M, which were used as NaOH activators of geopolymerization. The mass ratio of Na₂SiO₃/NaOH was fixed at 2.5 with SiO₂/Al₂O₃ at 2.69. After the fly ash and alkali activators were mixed for 1 min until homogeneous, the geopolymer paste was cured for 1 min using household microwave oven at different output powers of 200, 500, 700, and 850 W. Porous geopolymers were formed immediately. Micro X-ray CT and SEM results showed that the porous structure of the geopolymers was developed at higher NaOH concentrations when using 850 W power of the microwave oven. These results derive from the immediate increase of the temperature in the geopolymer paste at higher NaOH concentrations, meaning that aluminosilicate bonds formed easily in the geopolymers within 1 min.     

Mechanical properties and microstructure evaluation of fly ash - Slag geopolymer foaming materials

The existing fly ash-slag foaming geopolymer materials generally have the shortcomings of low fly ash content and low porosity. It is urgent to develop geopolymer foaming materials with high fly ash content and high porosity. Using fly ash and slag as the main raw materials, geopolymer foaming materials were prepared by alkali activation. The effects of activator content and sodium silicate modulus on the macroscopic mechanical properties, pore structures and microstructures of geopolymer foaming materials were studied. The experimental results showed that when the activator content was 21% (wt.) and the modulus of sodium silicate was 1, the specimen exhibited the best performance. The compressive strength of the specimen reached 2.18 MPa at 28 d, the porosity was 63.07%, and the average pore sizes of macroscopic pores were 920 μm. Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES) and Scanning Electron Microscopy and Energy Dispersive Spectrometer (SEM-EDS) analysis showed that when the content of activator was 21% and the modulus of sodium silicate was 1, the reaction grade of the system was the highest, reached 55.12%, meanwhile the main product Sodium silicate hydrate (N-A-S-H) gel produced the largest amount. The fractal dimension calculations showed that the spatial complexity of a specimen with large pores was greater than that of a specimen with small pores. This study can provide a basis for the design of geopolymer foaming materials with high proportion of fly ash and high porosity.     

Fabrication of highly porous mullite microspheres via oil-drop molding accompanied by freeze casting

Porous mullite microspheres with a highly open porosity and average diameter of more than 800 µm were fabricated via an oil-drop molding method accompanied by a freeze casting process. After sintering, a highly porous structure was formed due to interlocking whisker-shaped mullite grains and formation of interconnected skeletons during the freeze-casting process. Additionally, it was found that a high porosity and large pore size in the microspheres green bodies are favorable for the synthesis of mullite whiskers with high aspect ratio.     

Geopolymer foams obtained by the saponification/peroxide/gelcasting combined route using different soap foam precursors

This work investigates the influence of eight different vegetable and animal sources of fatty acids as soap foam precursors in the processing of highly porous geopolymers. Four sources rich in saturated chains (coconut and babassu oils, palm stearin and beef tallow), two sources rich in monounsaturated chains (olive and castor oils) and two sources rich in polyunsaturated chains (sunflower oil and soybean biodiesel) were selected. For all soap precursors, bodies treated at 300°C possessed a very high total porosity (84‐88 vol%), open porosity (79‐85 vol%) and relatively high specific surface area (35.1‐63.5 m²/g), but rather low compressive strength (0.2‐0.4 MPa). The increase in the thermal treatment temperature caused a slight decrease in porosity but a substantial increase in compressive strength and decrease in specific surface area due to sintering and formation of crystalline phases. The Darcian permeability coefficients of all bodies (0.6‐10.6×10^?10 m²) were typical of gelcasted foams, aerosol filters and fibrous mats. The morphology of pores could be well‐associated to the features of lathers produced by the respective soap precursors.     

Open cell geopolymer foams by a novel saponification/peroxide/gelcasting combined route

Using a novel saponification/peroxide/gelcasting combined route it was possible to produce geopolymer foams with a total porosity of ∼85 vol%, open porosity as high as ∼70 vol%, average cell size (D50) of 318 μm, and possessing a specific surface area of 50 m²/g. The in situ formation of surfactants by the saponification reaction of oil in the geopolymer alkaline environment led to increased total and open porosity in comparison to alternative methods for the fabrication of geopolymer foams.     

Structural and chemical properties of thermally treated geopolymer samples

This article presents the results of the compositional, structural and morphological study of geopolymers synthesized from metakaolin and an alkali activator. The study involved the investigation of the structural and chemical properties of the geopolymer, in addition to thermally treated geopolymers up to 600 and 900 °C. The precursor of the geopolymer, and the geopolymer samples before and after the thermal treatment, were investigated by Fourier transformation infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and SEM analysis. The corrected average value of the ratio of silicon and aluminum in the geopolymer samples (Si_GP:Al) is about 1.46, which suggests that the obtained geopolymer samples represent a mixture of roughly equal amounts of sialate and sialate-siloxo units. Annealing the geopolymer samples at 600 °C decreases the amount of Si-ONa bonds and induces the cross-linking of polymer changes. At the same time, other sodium containing alumino-silicate phases are created. The thermal treatment at 900 °C leads to a considerable reduction of oxygen and particularly sodium, followed by significant morphological changes i.e. formation of a complex porous structure. Additionally, a new semicrystaline phase appears. Both XRD and XPS results imply that this new phase may be nepheline and it is plausible that this phase begins to nucleate at temperatures below 900 °C.     

Assessment of recycling use of GFRP powder as replacement of fly ash in geopolymer paste and concrete at ambient and high temperatures

Environmental issues caused by glass fiber reinforced polymer (GFRP) waste have attracted much attention. The development of cost-effective recycling and reuse methods for GFRP composite wastes is therefore essential. In this study, the formulation of the GFRP waste powder replacement was set at 20–40 wt%. The geopolymer was formed by mixing GFRP powder, fly ash (FA), steel slag (SS) and ordinary Portland cement (OPC) with a sodium-based alkali activator. The effects of GFRP powder content, activator concentration, liquid to solid (L/S) ratio, and activator solution modulus on the physico-mechanical properties of geopolymer mixtures were identified. Based on the 28-day compressive strength, the optimal combination of the geopolymer mixture was determined to be 30 wt% GFRP powder content, an activator concentration of 85%, L/S of 0.65, and an activator solution modulus of 1.3. The ratios of compressive strength to flexural strength of the GFRP powder/FA-based geopolymers were considerably lower than those of the FA/steel slag-based geopolymers, which indicates that the incorporation of GFRP powder improved the geopolymer brittleness. The incorporation of 30% GFRP powder in geopolymer concrete to replace FA can enhance the compressive and flexural strengths of geopolymer concrete by 28%. After exposure to 600 °C, the flexural strength loss for geopolymer concretes containing 30 wt% GFRP powder was less than that of specimens without GFRP powder. After exposure to 900 °C, the compressive strength and flexural strength losses of geopolymer concretes containing 30 wt% GFRP powder were similar to those of specimens without GFRP powder. The developed GFRP powder/FA-based geopolymers exhibited comparable or superior physico-mechanical properties to those of the FA-based geopolymers, and thus offer a high application potential as building construction material.     

On the hydrogen production of geopolymer wasteforms under irradiation

The hydrogen gas (H₂) production of wasteforms is a major safety concern for encapsulating nuclear wastes. For geopolymers, the H₂ produced by radiolytic processes is a key factor because of the large amount of water present in their porous structure. Herein, the hydrogen production was measured under ⁶⁰Co gamma irradiation. The effect of water saturation and sample size were studied for pure geopolymers, or using zeolites as an example waste. To interpret results, a simple model was used, considering only hydrogen production, a potential recombination and its diffusion in the geopolymer matrix. When geopolymer monolithic samples were large and saturated by water, the hydrogen released was measured up to two orders of magnitude lower with a 40-cm long cylinder samples (1.9 × 10⁻¹⁰ mol/J) than a sample in powder form (2.2 × 10⁻⁸ mol/J). Knowing the diffusion constant of the matrix, the model was able to reproduce the evolution of the hydrogen release as a function of the water saturation level and predict accurately the evolution when sample size is increased up to 40 cm.     

Porous YbB6 Ceramics Prepared by In Situ Reaction between Yb2O3 and B4C Combined with Partial Sintering

Porous YbB₆ ceramic, a member of the ultrahigh‐temperature (UHT) family, is successfully prepared from Yb₂O₃ and B₄C powders by in situ synthesis combined with partial sintering method. Due to the fact that pores can be produced using the gases such as B₂O₃ and CO generated in reaction between Yb₂O₃ and B₄C, phase‐pure porous YbB₆ ceramics are obtained after sintering the Yb₂O₃/B₄C green bodies at 1750°C for 2 h in a flowing argon atmosphere under ambient pressure without addition of pore‐forming agent. Using this new and simple method, the porosity and volume shrinkage of porous YbB₆ ceramics are controllable by changing the green density. The prepared porous YbB₆ ceramic has homogeneous pore structure with very narrow pore diameter distribution. Furthermore, the porous YbB₆ possesses high compressive strength of ~21.34 MPa when the porosity is ~58.7% and the density is ~2.27 g/cm³. The combination of these favorable properties renders porous YbB₆ ceramic being a light‐weight structural and functional component for UHT applications.     

Synthesis and characteristics of fly ash and bottom ash based geopolymers–A comparative study

The research was carried out to develop geopolymers mortars and concrete from fly ash and bottom ash and compare the characteristics deriving from either of these products. The mortars were produced by mixing the ashes with sodium silicate and sodium hydroxide as activator solution. After curing and drying, the bulk density, apparent density and porosity, of geopolymer samples were evaluated. The microstructure, phase composition and thermal behavior of geopolymer samples were characterized by scanning electron microscopy, XRD and TGA-DTA analysis respectively. FTIR analysis revealed higher degree of reaction in bottom ash based geopolymer. Mechanical characterization shows, geopolymer processed from fly ash having a compressive strength 61.4 MPa and Young's modulus of 2.9 GPa, whereas bottom ash geopolymer shows a compressive strength up to 55.2 MPa and Young's modulus of 2.8 GPa. The mechanical characterization depicts that bottom ash geopolymers are almost equally viable as fly ash geopolymer. Thermal conductivity analysis reveals that fly ash geopolymer shows lower thermal conductivity of 0.58 W/mK compared to bottom ash geopolymer 0.85 W/mK.     

Influence of water and aluminium powder content on the properties of waste-containing geopolymer foams

The production of low thermal conductivity geopolymers has attracted increasing attention over the past years due to their low cost and green processing technology. In this work, light and porous geopolymers were produced by the proper association of aluminium content and solid-to-liquid ratio. This allowed the production of very low thermal conductivity geopolymers (78.6 mW/m K) exhibiting homogeneous pore size distribution which suggests their use in thermal insulating applications. Moreover this study also reduced the existing knowledge gap concerning the fresh-state characterization of foamed geopolymer slurries. The influence of aluminium powder, curing temperature and solid-to-liquid ratio on the calorimetric response of biomass fly ash-containing geopolymer slurries was evaluated. The calorimetric response of geopolymer slurries shows that the time needed to reach the maximum temperature decreases when the aluminium powder rises, thus shortening the open time before in situ application. It was also found that the geopolymerization rate is governed by the curing temperature.     

Development of fly ash and iron ore tailing based porous geopolymer for removal of Cu(II) from wastewater

This work aims to verify the feasibility of utilizing iron ore tailing (IOT) in porous geopolymer and intends to broaden the application of porous geopolymer in heavy metal removal aspect. Porous geopolymer was prepared using fly ash as resource material, which was partially replaced by IOT at level of 30%, by weight, with H₂O₂ as foaming agent and removal efficiency, adsorption affecting factors, adsorption isotherms and thermodynamics of Cu²⁺ by the developed porous geopolymer were investigated.The experimental results uncover that the porous amorphous geopolymer was successful synthesized with total porosity of 74.6%. The transformation of fly ash and IOT into foaming geopolymer leads to the formation of porous structure encouraging Cu²⁺ sorption. Batch sorption tests were carried out and geopolymer dosage, Cu²⁺ initial concentration, pH, contact time and temperature were the main concern. Both Langmuir and Freundlich models could explain the adsorption of Cu²⁺ on the porous geopolymer due to the high fitting coefficients. The uptake capacity reaches the highest value of 113.41 mg/g at 40 °C with pH value of 6.0. The thermodynamic parameters ΔHº, ΔSº and ΔGº suggests the spontaneous nature of Cu²⁺ adsorption on porous geopolymer and the endothermic behavior of sorption process.     

Fe speciation in geopolymers with Si/Al molar ratio of ∼2

The speciation of Fe was studied in metakaolin-based geopolymers to which Fe was added as ferric nitrate solution or freshly precipitated ferric hydroxide. From Mössbauer and near-edge X-ray absorption spectroscopies, coupled with X-ray diffraction and electron microscopy, it was concluded that in as-cured geopolymers the Fe was present in octahedral sites, either as isolated ions in the geopolymer matrix or as oxyhydroxide aggregates which had not reacted with the starting geopolymer components. For material to which iron nitrate was added, heating to 900 °C allowed the formation of nepheline and a glass, both of which contained tetrahedrally coordinated, substituted Fe³⁺.     

Thermally Induced Microstructural Changes in Fly Ash Geopolymers: Experimental Results and Proposed Model

This study presents a proposed model for thermally induced microstructural changes in fly ash geopolymers. Two paste mixes with different as‐cured microstructures are evaluated for thermal resistance. One mix was a highly reacted, high‐strength geopolymer with a compact microstructure and the other mix had higher degree of unreacted fly ash resulting in a low strength, low‐density geopolymer. Changes in the microstructure and bulk properties for each formulation were assessed at 100°C temperature intervals up to 1000°C using SEM, Q‐XRD and physical testing. It was observed that the higher density and apparent lower permeability of the high‐strength geopolymer led to it being more vulnerable to dehydration damage. Dimensional and phase changes also caused further strength losses before sintering at higher temperatures promoted strength gains. The low‐strength geopolymer was not damaged by dehydration and was better able to accommodate volumetric changes; hence it exhibited an increase in strength after thermal exposure due to the sintering. From these results and others in the literature, a model has been proposed for thermally induced changes in fly ash geopolymers.