Slag-fly ash and slag-metakaolin binders: Part II—Properties of precursors and NMR study of poorly ordered phases

Sodium silicate-activated slag-fly ash binders (SFB) and slag-metakaolin binders (SMKB) are room-temperature hardening binders that have excellent mechanical properties and a significantly lower carbon footprint than ordinary Portland cement (OPC). The aim of this study was to use nuclear magnetic resonance (NMR) spectroscopy to study the nanostructure of poorly ordered phases in SFB by varying slag/fly ash ratio, curing time, and curing temperature. Fly ash was completely substituted with metakaolin and the effect of this substitution on the poorly ordered phases was studied. It was observed that the proportion of geopolymer was generally higher in SMKB when compared to SFB. Although C–N–A–S–H and geopolymer coexisted in SFB and SMKB, C–N–A–S–H was the major product phase formed. The mean chain length (MCL) and the structure of C–N–A–S–H gel were estimated as a function of time, temperature, and slag/fly ash ratio. The MCL was found to have a negative correlation with slag/fly ash ratio and Ca/(Si+Al) ratio, but positive correlation with curing temperature. The average Si/Al atom ratios for geopolymers were also estimated. Lastly, the increased proportion of five-coordinated aluminum (Al(V)) in metakaolin resulted in the decreased unreacted metakaolin in the hardened binder but did not increase the geopolymer content.     

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.     

Comparative performance of geopolymers made with metakaolin and fly ash after exposure to elevated temperatures

This paper presents the results of a study on the effect of elevated temperatures on geopolymers manufactured using metakaolin and fly ash of various mixture proportions. Both types of geopolymers (metakaolin and fly ash) were synthesized with sodium silicate and potassium hydroxide solutions.

The strength of the fly ash-based geopolymer increased after exposure to elevated temperatures (800 °C). However, the strength of the corresponding metakaolin-based geopolymer decreased after similar exposure. Both types of geopolymers were subjected to thermogravimetric, scanning electron microscopy and mercury intrusion porosimetry tests. The paper concludes that the fly ash-based geopolymers have large numbers of small pores which facilitate the escape of moisture when heated, thus causing minimal damage to the geopolymer matrix. On the other hand, metakaolin geopolymers do not possess such pore distribution structures. The strength increase in fly ash geopolymers is also partly attributed to the sintering reactions of un-reacted fly ash particles.     

富镁镍渣-粉煤灰基地质聚合物的制备与性能表征

以工业固体废弃物富镁镍渣和粉煤灰为原料,以水玻璃和NaOH为碱激发剂,制备了一系列富镁镍渣-粉煤灰基地质聚合物。研究了不同粉煤灰掺量对地质聚合物力学性能的影响,并测定地质聚合物的线性收缩和碱溶出,通过XRD、IR、DTA等手段对产物进行表征。结果表明:富镁镍渣-粉煤灰基地质聚合物的强度随粉煤灰的掺入先升高后降低,当掺量为30%(质量分数)时,地质聚合物的抗压强度可达最高值22.15 MPa,较镍渣基地质聚合物强度提高42.2%;XRD分析表明富镁镍渣中MgO以镁橄榄石相存在,而非游离态,故地质聚合物具有良好的体积安定性。     

Role of slag in microstructural development and hardening of fly ash-slag geopolymer

This paper presents the microstructural development and hardening rate of fly ash-slag geopolymers. The solid precursors are treated with a potassium hydroxide-silicate activator of modulus 1.25. Ultrasonic wave reflection and Proctor penetration methods are used to determine the rate of hardening. Microstructural development is investigated using SEM-EDS, and the reaction rate is monitored using semi-adiabatic calorimetry. Both UWR and Proctor penetration methods capture changes in the hardening rate due to changes in the reaction mechanism. An increase in the rate of hardening is observed with the addition of slag. It is concluded that the calcium that dissolves from slag significantly influences both early and late age properties, and the availability of free calcium ions seems to prolong fly ash dissolution and enhance geopolymer gel formation. It is proposed that the hardening process is initiated by the precipitation of C-A-S-H and that rapid hardening continues due to accelerated geopolymerization.     

Waste stabilization/solidification of an electric arc furnace dust using fly ash-based geopolymers

The stabilization/solidification (S/S) of a carbon steel electric arc furnace (EAF) dust containing hazardous metals such as Pb, Cd, Cr or Zn using geopolymerization technology is described in this paper. Different reagents such as sodium hydroxide, potassium hydroxide, sodium silicate, potassium silicate, kaolinite, metakaolinite and blast furnace slag have been used. Mixtures of EAF waste with these geopolymeric materials and class F fly ash have been processed for studying the potential of geopolymers as waste immobilizing agents. Compressive strength tests and leaching tests for determining the efficiency of heavy metal immobilisation have been carried out. Comparison of fly ash-based geopolymer systems with classic Portland cement stabilization methods has also been accomplished. Compressive strength values far better than those achieved by hydraulic S/S methods were easily obtained by geopolymer solids at 28 days. Regarding leachability, the geopolymer S/S solids also manifested in general a better behaviour, showing very promising results.     

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.     

室温碱激发低钙粉煤灰地质聚合物配比试验研究

为得到室温下粉煤灰与碱激发剂质量比、水玻璃与氢氧化钠溶液质量比和氢氧化钠溶液摩尔浓度对粉煤灰地质聚合物力学性能的影响,以低钙粉煤灰为原料,制备了地质聚合物胶凝材料。采用正交试验方法,分析粉煤灰地质聚合物抗压强度,探讨碱激发剂配比对粉煤灰地质聚合物力学性能的影响,结合SEM、XRD和FTIR对试样进行表征,并对该材料的应力-应变曲线进行了研究。结果表明:粉煤灰地质聚合物的抗压强度随着激发剂掺量的减少而增大,水玻璃在激发剂中的比值与粉煤灰地质聚合物的抗压强度呈现正相关,其中粉煤灰与碱激发剂质量比为1.8,水玻璃与氢氧化钠溶液质量比为2.5且氢氧化钠溶液的浓度为10 mol/L时,120 d龄期的抗压强度可达51.98 MPa。对应力-应变曲线分析得出,在一定程度上,激发剂的掺入量对粉煤灰地质聚合物的破坏应变和弹性模量有较大影响。SEM、XRD和FTIR分析表明随着养护时间增长,胶凝材料体系内结构更致密,生成了更多的硅铝酸盐凝胶。     

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.     

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.     

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.     

Suitability of Sarawak and Gladstone fly ash to produce geopolymers: A physical,chemical, mechanical,mineralogical and microstructural analysis

Two types of fly ash sourced from Sarawak, Malaysia and Gladstone, Australia reflect differences in chemical compositions, mineral phase and particle size distributions. In this paper, the Sarawak fly ash was used to produce geopolymer in comparison to the well-developed Gladstone fly ash-based geopolymer. Characteristics of fly ash and mixtures proportions affecting compressive strength of the geopolymers were investigated. It is found that the variations of both fly ash types on particle size distributions, chemical compositions, morphology properties and amorphous phase correspond to the compressive strength. The results obtained show that after 7 days, geopolymer using Sarawak fly ash has lower compressive strength of about 55 MPa than geopolymer using Gladstone fly ash with strength of about 62 MPa. In comparison with Gladstone fly ash-based geopolymer, it showed that Sarawak fly ash-based geopolymer can be a potential construction material. Moreover, the production of Sarawak fly ash-based geopolymer aids to widen the application of Sarawak fly ash from being treated as industrial waste consequently discharging into the ash pond.     

矿聚物及其复合材料研究进展

系统介绍了周内外关于矿聚物的组织结构、性能及影响因素、制备工艺及特点、矿聚物的反应过程与聚合机理。评述了矿聚物的陶瓷化、先进矿聚物基复合材料、矿聚物及其复合材料的应用等方面的研究进展,指出了今后矿聚物及其复合材料的研究方向。     

粉煤灰地聚合物力学性能影响因素研究综述

粉煤灰地聚合物是以粉煤灰为硅铝质原料制备的,具有强度高、耐高温、耐腐蚀、有效固封金属离子等优点。但它固有的脆性以及需高温养护才能快速获得高强度的特点限制了其运用范围,而以纤维作为增强材料不仅可以提高粉煤灰地聚合物的强度,还可以改善其延性和韧性。本文主要从粉煤灰原料特性、碱激发剂、养护制度和增强材料四方面入手,重点阐述了粉煤灰粒径和化学组成,碱激发剂的种类、用量和模数,升温养护时间和初期养护温度对抗压强度的影响,以及纤维对粉煤灰地聚合物抗压强度和弯曲性能的影响。最后,根据现有的研究成果,对四种影响因素分别是如何影响粉煤灰地聚合物力学性能进行总结。     

Fly Ash Porous Material using Geopolymerization Process for High Temperature Exposure

This paper presents the results of a study on the effect of temperature on geopolymers manufactured using pozzolanic materials (fly ash). In this paper, we report on our investigation of the performance of porous geopolymers made with fly ash after exposure to temperatures from 600 °C up to 1000 °C. The research methodology consisted of pozzolanic materials (fly ash) synthesized with a mixture of sodium hydroxide and sodium silicate solution as an alkaline activator. Foaming agent solution was added to geopolymer paste. The geopolymer paste samples were cured at 60 °C for one day and the geopolymers samples were sintered from 600 °C to 1000 °C to evaluate strength loss due to thermal damage. We also studied their phase formation and microstructure. The heated geopolymers samples were tested by compressive strength after three days. The results showed that the porous geopolymers exhibited strength increases after temperature exposure.     

粉煤灰地聚物反应体系下的反应动力学研究

本文以实验数据为基础,利用“Jander”动力学方程,借助现代分析手段,对粉煤灰地聚物反应体系下的反应动力学进行了研究。主要研究内容有：液固比对粉煤灰在强碱体系下反应过程的影响;粉煤灰在地聚物体系下反应动力学阶段的划分;温度及碱浓度对动力学各反应阶段的影响以及地聚物宏观强度产生的机理等。研究结果表明：液固比的降低会造成反应速率的下降,固相产物形成所需的反应程度提前及反应产物形态的变化;地聚物反应过程以动力学方程模型中N＝2和N＞2以扩散反应阶段为主;温度的升高在提高各阶段反应速率的同时可降低反应时长。碱浓度的升高可有效提高各阶段的反应速率。粉煤灰主体与反应产物在化学成分上的明显差异与地聚物反应过程及其宏观强度的形成有密切关联。     

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.     

不同侵蚀环境下地质聚合物耐久性研究

地质聚合物作为新兴绿色无机胶凝材料,因独特的三维网络骨架结构而兼具矿物和高分子材料的特性。分别以固体废弃物粉煤灰和偏高岭土为原料,采用碱激发方式制备地质聚合物试块,考察养护28 d后试块在5%HCl、10%NaOH、5%MgCl₂+5%NaCl和5%H₂SO₄(均为质量分数)溶液中浸泡1~84 d的耐化学侵蚀能力。X射线衍射仪(XRD)、扫描电子显微镜(SEM)及试块质量、抗压强度测试表明,不同浸泡环境所引起地质聚合物胶凝材料的响应差异较大,粉煤灰基地质聚合物表现出较优异的耐低浓度硫酸、氢氧化钠、盐溶液侵蚀性能,微观结构及外观形貌稳定,试块质量和抗压强度稳定。偏高岭土基地质聚合物在盐溶液中性条件下结构和性能较稳定。在盐酸环境下两种地质聚合物被腐蚀明显,质量损失率大,抗压强度降低显著。对比研究表明,粉煤灰基地质聚合物的耐低浓度酸、碱溶液腐蚀性明显优于偏高岭土基地质聚合物。上述两类地质聚合物可潜在应用于海洋建筑领域。     

Fly ash-based geopolymers containing added silicate waste. A review

This review summarizes different types of industrial wastes such as biomass ash, red mud, recycled glass and heavy metals waste, in their application for geopolymer production. These wastes, which are currently abundant and urgent to dispose of, cannot be used alone in the geopolymer process because they do not provide a suitable SiO₂/Al₂O₃ molar ratio for this technology. For this reason, these by-products are commonly used in addition to other aluminosilicate sources such as fly ash or metakaolin. Important parameters which affect the properties and performance of fly ash based geopolymers with addition of a variety of wastes are discussed based on a comprehensive literature review.     

Development of an activated carbon-geopolymer composite for treatment of Pb(II) polluted water and soil

An activated carbon-geopolymer composite (ACGC) was prepared by using fly ash as raw materials via a simple geopolymerization process for treating the Pb(II) contaminant in wastewater and soil. The phase composition, microtopography, pore structure, and surface groups of the composites were studied by X-ray diffractometer, field emission scanning electron microscopy, X-ray photoelectron spectroscopy, N₂ adsorption-desorption isotherm, and Fourier transform infrared spectroscope. It was discovered that there was a synergistic effect between geopolymer matrix and activated carbon (AC), that is, addition of AC particles could increase the pores in geopolymer while strong alkalis condition provided by geopolymer enhanced the contents of oxygenic groups of AC. When the composite was used as the adsorbent, the sample containing 20 wt% AC (40ACGC) showed the maximum adsorption capacity (319.72 mg/g), and its adsorption isotherm fitted the Langmuir model well, suggesting the monolayer adsorption of Pb²⁺ on the 40ACGC. The kinetics of Pb²⁺ adsorption on the 40ACGC belonged to the pseudo-second-order model, indicating that Pb²⁺ adsorption on the composite followed chemical adsorption. In addition, the 40ACGC sample showed excellent stabilization performance for Pb²⁺ in soil. This work offered a new thinking to the application of geopolymers into remediation of heavy metal-polluted soil.