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.     

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.     

Synthesis and thermal properties of inorganic polymers (geopolymers) for structural and refractory applications from volcanic ash

The volcanic ash occurring as an abundant and readily accessible natural resource in the Central African country of Cameroon was used to synthesize aluminosilicate geopolymers using sodium hydroxide as the sole alkaline activator. Both the curing conditions and the Na₂O/SiO₂ molar ratio were found to influence the development of compressive strength of the geopolymer cement paste, which achieved a maximum strength of 55 MPa at Na₂O/SiO₂ = 0.3. The formation of a mortar by the addition of 40 wt% sand to the optimized geopolymer cement composition reduced the compressive strength to 30 MPa, still within the useful range for construction applications. The geopolymers consist largely of X-ray amorphous material with a small content of crystalline phases. Scanning electron microscopy showed a homogenously distributed mixture of lath-shaped and agglomerated morphologies, with a homogeneous distribution of Si, Al and O in the geopolymer matrix. The geopolymers are relatively stable to heat, shrinking only slowly and retaining about 60% of their as synthesized compressive strength on heating to 900 °C. The FTIR spectra of both the as synthesized and heated geopolymers show two broad absorbance bands, between 820-1250 cm⁻¹ and 450-730 cm⁻¹ assigned to the internal vibrations of Si-O-Si, and Si-O-Al respectively. The compressive strengths and the thermal stability of these materials suggest their suitability for building applications and low-grade refractories.     

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.     

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.     

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。     

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。     

Thin fly ash/ ladle furnace slag geopolymer: Effect of elevated temperature exposure on flexural properties and morphological characteristics

The flexural properties and thermal performance of 10 mm-thin geopolymers made from fly ash and ladle furnace slag were evaluated before and after exposure to elevated temperatures (300 °C, 600 °C, 900 °C, 1100 °C and 1150 °C). Class F fly ash was mixed with liquid sodium silicate (Na₂SiO₃) and 12 M sodium hydroxide (NaOH) solution using aluminosilicate/activator ratio of 1:2.5 and Na₂SiO₃/NaOH ratio of 1:4 to synthesise thin fly ash (FA) geopolymers. 40 wt% of ladle furnace slag was partially replacing fly ash to produce fly ash/slag-based (FAS) geopolymers. Thermal treatment enhanced the flexural strength of thin geopolymers. In comparison to the unexposed specimen, the flexural strength of FA geopolymers at 1150 °C and FAS geopolymers 1100 °C was increased by 161.3% to 16.2 MPa and 208.9% to 24.1 MPa, respectively. A more uniform heating was achieved in thin geopolymers which favoured the phase transformation at high temperatures and contributed to the substantial increase in flexural strength. The joint effect of elevated temperature exposure and the incorporation of ladle furnace slag further improved the flexural strength of thin geopolymers. The calcium-rich slag refined the pore structure and increased the crystallinity of thin geopolymers which aided in high strength development.     

Effect of elevated temperatures on geopolymer paste, mortar and concrete

Geopolymers are generally believed to provide good fire resistance due to their ceramic-like properties. Previous experimental studies on geopolymer under elevated temperatures have mainly focused on metakaolin-based geopolymers. This paper presents the results of a study on the effect of elevated temperature on geopolymer paste, mortar and concrete made using fly ash as a precursor. The geopolymer was synthesized with sodium silicate and potassium hydroxide solutions. Various experimental parameters have been examined such as specimen sizing, aggregate sizing, aggregate type and superplasticizer type. The study identifies specimen size and aggregate size as the two main factors that govern geopolymer behavior at elevated temperatures (800 °C). Aggregate sizes larger than 10 mm resulted in good strength performances in both ambient and elevated temperatures. Strength loss in geopolymer concrete at elevated temperatures is attributed to the thermal mismatch between the geopolymer matrix and the aggregates.     

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.     

Fibre-reinforced boroaluminosilicate geopolymers: A comparative study

This paper investigates the effect of fibres on the physical and mechanical behaviour of boroaluminosilicate geopolymers (BASG) compared to conventional aluminosilicate binders. The use of various types of fibres by the means of reinforcing geopolymers against flexural loads is very common. In this work, fly ash and ground granulated blast furnace slag (GGBS) are utilised as raw materials to generate geopolymer specimens. Different alkaline solutions comprising sodium hydroxide, sodium silicate, and borax are prepared to activate precursors. The sodium silicate solution is substituted with borax by 30?wt% and 70?wt% in order to produce fly ash and slag-based BASG respectively. Steel and polymer fibres are employed in the mixtures for reinforcement. Three-point bending and mini slump tests are conducted for assessing the flexural strength, elastic modulus, toughness, and flow of geopolymer specimens. A pair plotting interpretation is also used in order to illustrate the patterns. The obtained results indicate that the fly ash-based BASG mortar shows superior flexural strength to the GGBS-based BASG mortar. The flexural strength of fly ash-made aluminosilicate geopolymer declines from 7.3?MPa to 6.4?MPa with an increase in the content of steel fibres from 1% to 2%. Inversely, raising the percentage of steel fibres in the fly ash-based BASG mortar caused a slight growth in the flexural strength of specimens. The polypropylene fibres, when added sufficiently, play a significant role in improving the toughness of fly ash-based BASG and slag-based aluminosilicate mixtures, more than 0.8 and 0.7?J surge in the toughness respectively. In addition, the polypropylene and steel fibres perform well in improving the elastic modulus of slag-based BASG and fly ash-based aluminosilicate binders. While keeping the water to binder ratio constant, introducing the steel fibre increased the flow of fly ash-based geopolymers. Nonetheless, the polymer fibres declined the flow of mortars.     

The evolution of strength and crystalline phases for alkali-activated ground blast furnace slag and fly ash-based geopolymers

The increase in strength and evolution of crystalline phases in inorganic polymer cement, made by the alkali activation of slag, Class C and Class F fly ashes, was followed using compressive strength test and synchrotron X-ray diffraction. In order to increase the crystallinity of the product the reactions were carried out at 80 °C. We found that hydrotalcite formed in both the alkali-activated slag cements and the fly ash-based geopolymers. Hydroxycancrinite, one member of the ABC-6 family of zeolites, was found only in the fly ash geopolymers. Assuming that the predominantly amorphous geopolymer formed under ambient conditions relates to the crystalline phases found when the mixture is cured at high temperature, we propose that the structure of this zeolitic precursor formed in Na-based high alkaline environment can be regarded as a disordered form of the basic building unit of the ABC-6 group of zeolites which includes poly-types such as hydroxycancrinite, hydroxysodalite and chabazite-Na.     

Resistance of geopolymer materials to acid attack

This article presents an investigation into durability of geopolymer materials manufactured using a class F fly ash (FA) and alkaline activators when exposed to 5% solutions of acetic and sulfuric acids. The main parameters studied were the evolution of weight, compressive strength, products of degradation and microstructural changes. The degradation was studied using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The performance of geopolymer materials when exposed to acid solutions was superior to ordinary Portland cement (OPC) paste. However, significant degradation of strength was observed in some geopolymer materials prepared with sodium silicate and with a mixture of sodium hydroxide and potassium hydroxide as activators. The deterioration observed was connected to depolymerisation of the aluminosilicate polymers in acidic media and formation of zeolites, which in some cases lead to a significant loss of strength. The best performance was observed in the geopolymer material prepared with sodium hydroxide and cured at elevated temperature, which was attributed to a more stable cross-linked aluminosilicate polymer structure formed in this material.     

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.     

Synthesis of heat and ambient cured one-part geopolymer mixes with different grades of sodium silicate

The use of solid activators in the manufacture of geopolymer enhances its commercial viability as it aids the development of a one-part “just add water” geopolymer mixture, similar to the conventional Portland cement-based materials. This study is aimed to synthesize heat and ambient cured one-part geopolymer mixes. Appropriate combinations of low calcium (Class F) fly ash, slag and hydrated lime as the aluminosilicate source materials were activated by three different grades of sodium silicate and a combination of sodium silicate and sodium hydroxide powders. A conventional two-part geopolymer mix with the commonly used sodium hydroxide and sodium silicate solutions was also made for comparison. Effects of the type and amount of the solid activator, the amount of fly ash replacement with slag and hydrated lime and water content on short term mechanical properties of the heat cured one-part geopolymer mixtures including workability of the fresh mix, hardened density and compressive strength were evaluated. Subsequently, effects of ambient curing on the properties of the developed one-part geopolymer mixes were also investigated. Moderate to high compressive strength of over 37 MPa developed for the heat and ambient cured one-part geopolymer mixes. The 28-days compressive strengths of the ambient cured one-part geopolymer mixtures, regardless of the type of activator and geopolymer source materials, were comparable to those of the counterpart heat cured one-part geopolymer mixes. Such one-part geopolymer mixes could enhance the commercial viability and large-scale applications of the geopolymer in the construction industry.     

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.     

高炉矿渣-粉煤灰基地质聚合物固化铅离子及防辐射性能研究

研究利用高炉矿渣（BFS）、粉煤灰（FA）作为原材料制备地质聚合物。以氢氧化钠与水玻璃作为碱激发剂,在碱激发条件下制备地质聚合物固化二价铅离子（Pb²⁺）。研究Pb²⁺的掺量对固化体强度的影响,并通过浸出毒性实验、X射线衍射分析（XRD）、红外光谱分析（FT-IR）、扫描电镜（SEM）等表征分析、防辐射实验测试,探究其固化效果与固化机理。结果表明,高炉矿渣-粉煤灰基地质聚合物与Pb²⁺具有良好的相容性,且固化体在28 d最高抗压强度可以达到43 MPa,Pb²⁺的添加质量分数为1%时能提高其固化体的强度。浸出实验表明,固化体对质量分数为1% Pb²⁺的固化效率在97%以上。微观分析认为大部分重金属是以羟基配合离子的形式被物理封装在地质聚合物内部。防辐射实验测试表明,Pb²⁺的掺量与高炉矿渣-粉煤灰基地质聚合物的γ射线屏蔽效果成正相关,实验中Pb²⁺最优掺入质量分数为3%,线性吸收系数和半衰减层厚度最优值分别为0.222 0 cm^-1和2.309 5 cm。     

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。     

Mechanical and durable behaviour of alkaline cement mortars reinforced with polypropylene fibres

The development of new binders, alternative to traditional cements and concretes obtained by the alkaline activation of different industrial by-products (blast furnace slags and/or fly ashes), is an ongoing study and research topic of the scientific community.

The mechanical and durable behaviour of alkaline cement mortars reinforced with polypropylene fibres has been the object of the present investigation. Three different alkaline matrices were used: (a) granulated blast furnace slag activated with waterglass (Na₂SiO₃+NaOH) with a concentration of 4% Na₂O by mass of slag and cured at room temperature, (b) aluminosilicate fly ash activated with 8M NaOH and cured at 85 °C during the first 24 h and (c) 50% fly ash+50% slag activated with 8M NaOH solution at room temperature. In the mechanical tests (flexural and compressive strengths), two different dosages of fibres were used: 0.5% and 1% by mortar volume. Shrinkage tests according to ASTM C 806-87 standard with (1%) and without fibres were also carried out. The durability tests carried out were freeze/thaw and wet/dry cycles. In these tests, the dosage of fibre was 0.5% by mortar volume. The results obtained show that the nature of the matrix is the most important factor to strength development, more than fibre presence and content amount.     

Compressive strength of fly‐ash‐based geopolymer concrete at elevated temperatures

This paper presents the compressive strength of fly‐ash‐based geopolymer concretes at elevated temperatures of 200, 400, 600 and 800 °C. The source material used in the geopolymer concrete in this study is low‐calcium fly ash according to ASTM C618 class F classification and is activated by sodium silicate (Na₂SiO₃) and sodium hydroxide (NaOH) solutions. The effects of molarities of NaOH, coarse aggregate sizes, duration of steam curing and extra added water on the compressive strength of geopolymer concrete at elevated temperatures are also presented. The results show that the fly‐ash‐based geopolymer concretes exhibited steady loss of its original compressive strength at all elevated temperatures up to 400 °C regardless of molarities and coarse aggregate sizes. At 600 °C, all geopolymer concretes exhibited increase of compressive strength relative to 400 °C. However, it is lower than that measured at ambient temperature. Similar behaviour is also observed at 800 °C, where the compressive strength of all geopolymer concretes are lower than that at ambient temperature, with only exception of geopolymer concrete containing 10 m NaOH. The compressive strength in the latter increased at 600 and 800 °C. The geopolymer concretes containing higher molarity of NaOH solution (e.g. 13 and 16 m ) exhibit greater loss of compressive strength at 800 °C than that of 10 m NaOH. The geopolymer concrete containing smaller size coarse aggregate retains most of the original compressive strength of geopolymer concrete at elevated temperatures. The addition of extra water adversely affects the compressive strength of geopolymer concretes at all elevated temperatures. However, the extended steam curing improves the compressive strength at elevated temperatures. The Eurocode EN1994:2005 to predict the compressive strength of fly‐ash‐based geopolymer concretes at elevated temperatures agrees well with the measured values up to 400 °C. Copyright © 2014 John Wiley & Sons, Ltd.