Characterisation and properties of geopolymer composite part 1: Role of mullite reinforcement

Geopolymer-mullite composite was prepared using fly ash and mullite powders with sodium silicate and sodium hydroxide as alkaline activators. Mullite was used as a replacement to fly ash in the 20–60 wt% range. Sodium silicate to sodium hydroxide (12 M) ratio was 1:1 while the liquid to solid ratio was 0.6:1. X-ray diffraction (XRD) analysis revealed that the set of geopolymer specimens without mullite replacement (control) showed the co-existence of amorphous and crystalline phases of quartz, magnesioferrite (Fe₂MgO₄), Lazurite (Na_8.56 (Al₆Si₆O₂₄) (SO₄)_1.56 S_0.44)) and calcium silicate hydrate. With an increasing amount of mullite replacement, calcium silicate hydrate and magnesioferrite diminished while the new phase of phillipsite (K, Na)₂(Si,Al)₈O₁₆·4H₂O) emerged. Microstructural analysis revealed Si-rich mullite needles possibly occurred by recrystallization of the original mullite. This suggestion was also confirmed by the change of the crystallite size as analysed using an X-ray diffraction technique. The ambient compressive strength was found to increase from 58 ± 21 MPa for the control geopolymer to 72–76 MPa, with a much smaller uncertainty, for the geopolymer-mullite composite. Modulus of rupture (MOR) was found to improve significantly from 0.7 ± 0.3 MPa to 3.7 ± 0.5 MPa in the 20% replacement and further to 7.8 ± 1.3 and 8.1 ± 1.1 MPa in the 40% and 60% replacement respectively. Improvement of fire resistance was observed in the 40–60% replacement thermal shock resistance property, however, was unchanged in these geopolymer-mullite composite.     

Preparation and thermal shock resistance of cordierite-spodumene composite ceramics for solar heat transmission pipeline

Cordierite-spodumene composite ceramics with 5, 10, 15 wt% spodumene used for solar heat transmission pipeline were in-situ prepared via pressureless sintering from kaolin, talc, γ-Al₂O₃ and spodumene. Effects of spodumene on densification, mechanical properties, thermal shock resistance, phase composition and microstructure of the composite ceramics were investigated. The results showed that spodumene used as flux material decreased the sintering temperature greatly by 40–80 °C, and improved densification and mechanical properties of the composite ceramics. Especially, sample A3 with 10 wt% spodumene additive sintered at 1380 °C exhibited the best bending strength and thermal shock resistance. The bending strengths of A3 before and after 30 thermal shock cycles (wind cooling from 1100 °C to room temperature) were 102.88 MPa and 96.29 MPa, respectively. XRD analysis indicated that the main phases of the samples before 30 thermal shock cycles were α-cordierite, α-quartz and MgAl₂O₄, and plenty of β-spodumene appeared after thermal shock. SEM micrographs illustrated that the submicron β-spodumene grains generated at the grain boundaries after thermal shock improved the thermal shock resistance. It is believed that the cordierite-spodumene composite ceramics can be a promising candidate material for heat transmission pipeline in the solar thermal power generation.     

Novel thermal insulating and lightweight composites from metakaolin geopolymer and polystyrene particles

In this work, new foamed thermal insulation geopolymer composite based on polystyrene particles (PP) and metakaolin was developed. Compressive strength, flexural strength, high temperature resistance and microstructure were evaluated. The experimental results show that compressivestrengthand flexural strength of the thermal insulation geopolymer composite decrease with increasing polystyrene particle content. However, it still exhibits considerable and sufficient strength. The dry density and thermal conductivityalso decrease as polystyrene particle content increases due to the contribution of polystyrene particles with low density. The floatation of the thermal insulation geopolymer composite on water surface indicates the relatively low density and a good quadratic function relationship can be found between thermal conductivity and dry density. Furthermore, the dense interfacial transition zone indicates the high compressive strength and flexural strength of thermal insulation geopolymer composites. The cumulative intrusion volume corresponding to the porosity decreases and the critical pore diametersshift to lower values with addition of polystyrene particles. Geopolymer composites gain strength after exposure around 400 °C, and it suffers dramatic strength loss after 800 °C temperature exposure especially for the 100% polystyrene particles addition specimen.     

Improving compressive strength of fly ash-based geopolymer composites by basalt fibers addition

In this study, ASTM Class C fly ash used as an alumino-silicate source was activated by metal alkali and cured at low temperature. Basalt fibers which have excellent physical and mechanical properties were added to fly ash-based geopolymers for 10–30% solid content to act as a reinforced material, and its influence on the compressive strength of geopolymer composites has been investigated. XRD study of synthesized geopolymers showed an amorphous phase of geopolymeric gel in the 2θ region of 23°–38° including calcium-silicate-hydrate (C-S-H) phase, some crystalline phases of magnesioferrite, and un-reacted quartz. The microstructure investigation illustrated fly ash particles and basalt fibers were embedded in a dense alumino-silicate matrix, though there was some un-reacted phase occurred. The compressive strength of fly ash-based geopolymer matrix without basalt fibers added samples aged 28 days was 35 MPa which significantly increased 37% when the 10 wt%. basalt fibers were added. However, the addition of basalt fibers from 15 to 30 wt% has not shown a major improvement in compressive strength. In addition, it was found that the compressive strength was strong relevant to the Ca/Si ratio and the C-S-H phase in the geopolymer matrix as high compressive strength was found in the samples with high Ca/Si ratio. It is suggested that basalt fibers are one of the potential candidates as reinforcements for geopolymer composites development.     

Investigating the effect of andalusite on mechanical strength and thermal shock resistance of cordierite-spodumene composite ceramics

For increasing working stability of cordierite-spodumene composite ceramics for solar heat transmission pipeline, andalusite was utilized as modified additive to improve mechanical strength and thermal shock resistance of the composite ceramics. The effects of andalusite on densification, mechanical strength, thermal stability, phase composition and microstructure were studied. The experiment results showed that andalusite significantly influenced bending strength and thermal shock resistance of the composite ceramics. Especially, specimen B1 with 5 wt% andalusite sintered at 1400 °C achieved the best performances. The linear shrinkage, water absorption, apparent porosity, bulk density and bending strength were 5.62%, 0.02%, 0.06%, 2.19 g cm^?3 and 104.94 MPa, respectively. After 30 thermal shock cycles (wind cooling from 1100 °C to room temperature), the residual strength of the specimen increased to 110.65 MPa, accompanying with ?5.44% strength loss rate. The XRD and SEM analysis illustrated that mullite grains with short rod-like shape could prevent crack growth of inter-granular fracture to enhance bending strength of the specimens. Furthermore, the generation of β-spodumene grains with low thermal expansion coefficient after thermal shock improved thermal shock resistance of the composite ceramics. It is considered that the cordierite-spodumene composite ceramics with high densification, good mechanical strength and excellent thermal stability can be a potential material for high temperature thermal transmission pipeline in solar thermal power generation.     

Development of a High Strength Geopolymer by Novel Solar Curing

Geopolymer is a popular construction material derived from different sources of aluminosilicates known for its environmental benefits and excellent durability in harsh conditions. However, the curing of fly-ash based geopolymer normally requires a thermal treatment that increases the manufacturing cost and carbon footprint. This paper explored a new economical and environmentally-friendly alternative, i.e. solar curing, that harnesses solar radiation to achieve accelerated geopolymerization process. Geopolymer mortars coated in two different greyscales namely solar curing black (SCB) and 40% black (grey, SCG) were prepared to study the effect of solar radiation absorption ability on the strength of the specimens, along with ambient cured specimens (ATC) for comparison. Mechanical properties such as workability, compressive strength, stress-strain relationship from 1 day to 28 days were tested. The SCB specimens that can easily reach 65 °C under the sun showed a substantial improvement of the compressive strength especially at the early age, i.e. 49.2 MPa at 1-day compared with 25.5 MPa for the ATC ones. At 28-day, SCB reached 92 MPa in compressive strength which is 17.8% (13.9 MPa) higher than that of ATC. SCG showed a moderate enhancement in strength. Through in-depth physical and chemical characterizations, the structure and morphology of geopolymers were identified through X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDS). It was found that geopolymer cured by solar radiation had more calcium aluminate silicate content hence leading to a higher mechanical strength. Furthermore, a titration study that determines the conversion rate of the activators inside geopolymers suggested a faster geopolymerization process in the solar cured specimens.     

Fabrication and properties of thermal insulating material using hollow glass microspheres bonded by aluminum–chrome–phosphate and tetraethyl orthosilicate

Thermal insulation material made by hollow glass microspheres (HGM) with different content of aluminum–chrome–phosphate solution (ACP) and tetraethyl orthosilicate (TEOS) as binders was formed, dried and sintered at 250 °C, 450 °C or 650 °C for 2 h. Properties such as density, compressive strength, thermal conductivity and microstructure of the specimens were determined. It is found that TEOS improved the distribution of ACP and increased the compressive strength of the specimens. HGM bonded by appropriate amount of ACP and TEOS achieved preferable value of density, compressive strength and thermal conductivity which were significant for thermal insulation materials. The compressive strength of specimens sintered at 450 °C and 650 °C was higher than that of the specimens sintered at 250 °C.     

Effect of Sm2O3 on microstructure,thermal shock resistance and thermal conductivity of cordierite-mullite-corundum composite ceramics for solar heat transmission pipeline

Cordierite-mullite-corundum composite ceramics for solar heat transmission pipeline were fabricated via pressureless sintering at a low sintering temperature with added Sm₂O₃. The effects of Sm₂O₃ on sintering behaviors, mechanical property, phase transformation, microstructure, thermal shock resistance and thermal conductivity of the composite ceramics were investigated. TEM analysis results demonstrated that Sm³⁺ located in glass and grain boundaries to facilitate the densification via the liquid-phase sintering mechanism and improve bending strength by grain refinement, respectively. Proper addition (3 wt%) of Sm₂O₃ could promote the crystallization of cordierite, and improve thermal shock resistance of the composite ceramics with an increasing rate of 16.70% for bending strength after 30 thermal shock cycles (air cooling from 1100 °C to RT). The composite ceramics possessed a superior thermal shock resistance, where a large amount of particles were formed to suppress crack initiation and propagation during thermal shock. Cordierite-mullite-corundum composite ceramics with proper Sm₂O₃ addition (3 wt%) had a lower thermal conductivity than that of composite ceramics without Sm₂O₃ addition by strengthening the scattering of phonon, which could reduce the heat loss during solar heat transmission process.     

Effect of transient creep on compressive strength of geopolymer concrete for elevated temperature exposure

The strength and transient creep of geopolymer and ordinary Portland cement (OPC)-based material (paste and concrete) were compared at elevated temperatures up to 550 °C. The strength properties were determined using an unstressed hot strength test and unstressed residual strength test for paste and concrete, respectively. At 550 °C, compared with the original strength, the strength of geopolymer was increased by 192% while the strength of OPC paste showed little change. However, after exposure to 550 °C, the residual strength percentage of both geopolymer and OPC concretes was similar. Transient creep data show that geopolymer had little change in transitional thermal creep (TTc) between 250 and 550 °C while OPC paste developed significant TTc in this temperature range. In comparison with OPC concrete, a higher strength loss of geopolymer concrete is thus believed to be due to the absence of TTc to accommodate nonuniform deformation during thermal exposure.     

Thermo-mechanical and high-temperature dielectric properties of cordierite-mullite-alumina ceramics

Heterogeneous ceramics made of cordierite (55–56 wt%), mullite (22–33 wt%) and alumina (23–11 wt%) were prepared by sintering non-standard raw materials containing corundum, talc, α-quartz, K-feldspar, kaolinite and mullite with small amounts of calcite, cristobalite and glass phases. The green specimens prepared by PVA assisted dry-pressing were sintered within the temperature range of 950–1500 °C for different dwelling times (2–8 h). The effects of sintering schedule on crystalline phase assemblage and thermomechanical properties were investigated. The sintered ceramics exhibited low coefficients of thermal expansion (CTE) (3.2–4.2×10⁻⁶ °C⁻¹), high flexural strength (90−120 MPa and high Young modulus (100 GPa). The specimens sintered at 1250 °C exhibited the best thermal shock resistance (∆T~350 °C). The thermal expansion coefficients and thermal shock resistance were studied using Schapery model, the modelling results implying the occurrence of non-negligible mechanical interactions between the phases in bulk. The dielectric properties characterized from room to high temperature (RT– HT, up to 600 °C) revealed: (i) noticeable effects of sintering schedule on dielectric constant (5–10) and dielectric loss factor (~0.02–0.04); (ii) stable dielectric properties until the failure of the electrode material. The thermomechanical properties coupled with desirable dielectric properties make the materials suitable for high density integrated circuitry or high temperature low-dielectric materials engineering.     

Production of nepheline/quartz ceramics from geopolymer mortars

This research has investigated the mechanical properties and microstructure of metakaolin derived geopolymer mortars containing 50% by weight of silica sand, after exposure to temperatures up to 1200 °C. The compressive strength, porosity and microstructure of the geopolymer mortar samples were not significantly affected by temperatures up to 800 °C. Nepheline (NaAlSiO₄) and carnegieite (NaAlSiO₄) form at 900 °C in the geopolymer phase and after exposure to 1000 °C the mortar samples were transformed into polycrystalline nepheline/quartz ceramics with relatively high compressive strength (～275 MPa) and high Vickers hardness (～350 HV). Between 1000 and 1200 °C the samples soften with gas evolution causing the formation of closed porosity that reduced sample density and limited the mechanical properties.     

Repeated thermal shock behavior of ZrB2-SiC-graphite composite under prestress

The thermal shock resistance of ZrB₂-SiC-graphite composite under nominal prestress of 0, 20, 30, 40 or 50 MPa after subjected to 10 and 30 cycles of thermal shock was evaluated by measuring the residual flexural strength of the tested specimen. In each test the applied prestress kept constant and in each cycle the specimen center was heated to 2000 °C within 5 s through electrical resistance heating method and cooled down naturally to room temperature. A lot of broken SiO₂ bubbles in the tested specimens were observed with a SEM. For the specimen subjected to 10 cycles of thermal shock, the residual flexural strength does not show big change under different levels of prestress, although the thickness of oxide layer increases at larger prestress, which is presumably attributed to the effect of the oxide layer that heals the cracks and the pores and enhances the strength. For the specimen subjected to 30 cycles of thermal shock, the residual strength decreases, in general, with the increase of prestress level. The thermal shock fatigue under different levels of prestress was also tested, and it was found that the increase of prestress may speed the failure of the specimen, indicating that the level of prestress may fatally affect the failure of the material.     

Characterization of transparent glaze for single-crystalline anorthite porcelain

The objective of this work was to design a transparent glaze for matching single-crystalline anorthite porcelain. Excessive amounts of quartz were used in glaze to improve surface hardness. Technological properties including hardness and thermal shock resistance were investigated. X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies were also carried out to analyze the microstructure. The phases found in glaze were aluminosilicate glass, quartz and cristobalite crystals. The Vickers hardness of the transparent glaze was about 2.48 GPa, which was much higher than that of commercial soft glaze and was close to hard porcelain glaze due to forming dispersed crystal particles (quartz and cristobalite) in the glass matrix. Moreover, the thermal expansion coefficient of the glaze was slightly lower than that of porcelain body which was easy to produce compressive stress in glaze surface to increase the strength of porcelain. And no cracks were observed on glaze surface after heat exchange three times from 220 °C to 25 °C, presenting excellent thermal shock resistance.     

Effect of SiC content on electrical,thermal and ablative properties of pressureless sintered ZrB2-based ultrahigh temperature ceramic composites

The effects of SiC content (10–40 vol.%) on electrical, thermal and ablation properties of pressureless sintered ZrB₂-SiC composites showing interfacial segregation of W-rich phases have been studied. The electrical resistivity was measured by four-probe method, whereas thermal diffusivity and coefficient of thermal expansion (CTE) were determined using laser-flash method and thermo-mechanical analyzer, respectively. Whereas thermal conductivities calculated from experimentally obtained thermal diffusivity values are found to be the highest for the ZrB₂-20 SiC composite, both electrical conductivity and CTE decrease with increasing SiC content. The specimens were subjected to thermal shock by soaking at 800–1200 °C, followed by water-quenching. Further, some specimens were exposed to oxyacetylene flame (2200 °C) for 10 min. The damage was estimated from changes in mass, Young’s modulus, and hardness. The highest thermal shock and ablation resistance have been observed for the ZrB₂-20 SiC composite, as thermal properties and formation of protective oxide scale play key role.     

Improvement of high-temperature mechanical properties of heat treated Cf/geopolymer composites by Sol-SiO2 impregnation

Unidirectional carbon fiber reinforced geopolymer composite was prepared by ultrasonic-assisted slurry infiltration method and heat treated at 1100 °C. Then it was impregnated with Sol-SiO₂ to seal the cracks and pores formed during heat treatment. The ambient strength of composite after impregnation was enhanced by 35.6% due to the increase relative density from the starting 79% to 93.6%. Composites both before and after impregnation fractured in a non-brittle manner at both ambient and high temperatures. Over an elevated temperature range from 700 to 900 °C, the strength of the two composites showed anomalous gains and reached their maximum values at 900 °C, 322.1 and 425.1 MPa, respectively. These values were 19.8% and 16.8% higher than their ambient ones. When the temperature was further increased to 1100 °C, the impregnated composite showed superior high-temperature properties, which was attributed to the improved fiber integrity due to the Sol-SiO₂ sealing effect.     

Fully reacted high strength geopolymer made with diatomite as a fumed silica alternative

Geopolymers are formed by mixing of aluminosilicate sources with alkaline meta-silicate solution at room temperature. In the current study, diatomite of Turkish origin was fully utilized as a fumed silica alternative for the preparation of geopolymer, having a typical formula of K₂O•Al₂O₃•4SiO₂•11H₂O. From XRD of this sample, a broad peak centered at 28° 2θ indicated the well-known formation of amorphous geopolymer, as well as a fully reacted microstructure of geopolymer as seen by scanning electron microscopy. Additionally, geopolymer having the same formula was made by using fumed silica, in order to compare with geopolymers prepared from diatomite. The Weibull modulus was calculated from four-point bending and compressive strength testing of both geopolymer composites. The use of diatomite as a fumed silica substitute in geopolymer production resulted in a very close flexure strength 9.2 (± 4.2 MPa) when compared to geopolymer made from fumed silica 10.2 (± 3.3 MPa). There was a significantly higher compressive strength 71 (± 13.9 MPa) and Weibull modulus (5.4), than comparable properties of geopolymer made from fumed silica, which had a compressive strength 54 (± 25.8 MPa) and Weibull modulus of 2.0. The discrepancy was attributed to some self-reinforcement of the geopolymer matrix due to unreacted diatomite.     

Improvement of the mechanical properties of SiC reticulated porous ceramics with optimized three-layered struts for porous media combustion

Silicon carbide reticulated porous ceramics (SiC RPCs) with three-layered struts were fabricated by polymer replica method, followed by infiltrating alumina slurries containing silicon (slurry-Si) and andalusite (slurry-An), respectively. The effects of composition of infiltration slurries on the strut structure, mechanical properties and thermal shock resistance of SiC RPCs were investigated. The results showed that the SiC RPCs infiltrated with slurry-Si and slurry-An exhibited better mechanical properties and thermal shock resistance in comparison with those of alumina slurry infiltration, even obtained the considerable strength at 1300 °C. In slurry-Si, silicon was oxidized into SiO₂ in the temperature range from 1300 °C to 1400 °C and it reacted with Al₂O₃ into mullite phase at 1450 °C. Meantime, the addition of silicon in slurry-Si could reduce SiC oxidation of SiC RPCs during firing process in contrast with alumina slurry. With regard to slurry-An, andalusite started to transform into mullite phase at 1300 °C and the secondary mullitization occurred at 1450 °C. The enhanced mechanical properties and thermal shock resistance of SiC RPCs infiltrated alumina slurries containing silicon and andalusite were attributed to the optimized microstructure and the triangular zone (inner layer of strut) with mullite bonded corundum via reaction sintering. In addition, the generation of residual compressive stress together with better interlocked needle-like mullite led to the crack-deflection in SiC skeleton, thus improving the thermal shock resistance of obtained SiC RPCs.     

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.     

Mullite-based refractory castable engineering for the petrochemical industry

Refractory castables used in fluid catalytic converter (FCC) risers should present suitable particle erosion and thermal shock resistances at temperatures below 900 °C. Considering that calcium aluminate cement (CAC)-bonded refractories usually start their densification above 1200 °C, the use of sintering additives to induce faster densification is a promising technological alternative. Therefore, this work addresses the evaluation of mullite-based castables containing a boron-based sintering additive and CAC and/or hydratable alumina as the binder sources. Hot elastic modulus, cyclical thermal shock, hot modulus of rupture and cold erosion resistance measurements were carried out to evaluate the compositions. According to the attained results, adding 1.5 wt% of the evaluated sintering additive to the designed castables led to a remarkable increase of the hot modulus of rupture (maximum of 40.4 MPa at 800 °C for the CAC-containing refractory) and high erosion resistance (1.5–2.9 cm³) after pre-firing at 800 °C for 5 h. Moreover, the combination of CAC and hydratable alumina gave rise to an improved refractory (M–2CAC–2HA–S) showing a transient liquid formation at an increased temperature, high thermal shock resistance (no E decay after 8 thermal cycles, ΔT=800 °C) and high mechanical strength at 800 °C and 1000 °C.     

Thermo-mechanical characterization of a silica-alumina refractory concrete based on calcined algerian kaolin

The aim of this work is to study the thermo-mechanical behaviour (bending and compressive tests, creep and thermal shock resistance) of a refractory concrete based on local kaolin grogs and aluminous cement. Strength tests revealed a behaviour that is almost linear elastic for temperatures up to 800 °C and visco-plastic at 900 °C. A crack bridging strengthening process was observed at 800 °C. The creep tests were carried out at different temperatures between 1000 and 1150 °C using stresses in the range (0.75–2.76 MPa). The stress exponent was about 1.255. Microscopic observations suggested an intergranular creep mechanism.A water quenching test was used for estimating the thermal shock resistance of the material. The tested samples supported 80 cycles of standardized cyclic thermal shock without failure. Ultrasonic measurements were applied in order to evaluate the of ultrasonic velocity changes after these thermal shock tests. Strength degradation of the samples was evaluated using two models based on ultrasonic velocity changes during test and compared with the experimental values.