Microstructural characterisation of alkali-activated PFA matrices for waste immobilisation

A variety of natural and industrial waste product materials rich in SiO₂ and Al₂O₃ may be activated with alkalis to produce cementitious systems which when cured under mild temperature conditions, set and harden to give a very compact paste. When fly ash is the activated material, fast setting and rapid strength development have been reported. In addition to their application in construction, they may have a role in the immobilisation of toxic waste.

Alkali-activated fly ash matrices containing arsenic were studied by a combination of scanning and transmission electron microscopy along with energy-dispersive X-ray analysis of argon-milled sections. Little arsenic was incorporated in the matrix of hydration product but it was apparently associated with iron derived from the hydration of the fly ash. There was no association of As with added Fe₂O₃.     

粉煤灰对氯氧镁水泥早期性能的影响

为了研究粉煤灰对氯氧镁水泥的改性作用以及拓展氯氧镁水泥在青海等地的应用,将粉煤灰掺入氯氧镁水泥中,分析了粉煤灰对氯氧镁水泥的凝结时间、强度、耐水性和耐硫酸盐的影响.结果表明:掺入粉煤灰会延长氯氧铁水泥的凝结时间,粉煤灰的掺量与初终凝时间呈线性相关;掺入20％粉煤灰能提高氯氧镁水泥的28天强度和耐水性;硫酸盐环境能够改善氯氧镁水泥的耐水性,虽然大掺量(40％)的氯氧铁水泥浸泡硫酸盐后强度降低幅度较大,但浸硫酸盐后氯氧镁水泥的剩余抗压强度依然是对照组普通硅酸盐水泥强度的1.5倍,适宜将其应用于干旱、少雨、硫酸盐侵蚀比较严重的西藏、青海等西部环境中.     

Strategies of using fly ash and their effect on properties of cement mortar

Abstract

Three different ways of using fly ash, namely, partial replacement of cement, or sand, or both cement and sand in the cement mortar, were studied in this investigation. The replacement varied from 10 percent to 60 percent by weight. The effects of design parameters such as water‐cement ratio and curing temperature on the replacements were studied. In this paper, strategies of using fly ash in concrete construction were also proposed in order to conserve resources.     

MSWIFA制阿利尼特水泥基材料的耐久性

以城市垃圾焚烧飞灰(MSWIFA)为主要原料,在实验室成功烧制了阿利尼特水泥,研究了阿利尼特水泥基材料的抗压强度和耐久性。结果表明:利用MSWIFA烧制的阿利尼特水泥熟料,掺加3%～5%石膏,水泥的抗压强度达到甚至超过对照水泥PC32.5R;阿利尼特水泥基材料的抗碳化、抗渗和抗硫酸盐侵蚀性能优良,干缩率比对照水泥略大;尽管阿利尼特水泥水化过程中溶出的氯离子含量不高,但是有可能加速钢筋锈蚀,因此,不建议将其用于钢筋混凝土中。     

Discrete element numerical simulation of fly ash triboelectrostatic separation in a nonlinear electric field

Fly ash is solid waste produced by thermal power generation, and its carbon content is a key factor affecting its recycling. Due to the large difference in fly ash quality and insufficient tribocharging, the parallel plate electric field with constant electric field strength cannot meet the practical needs of efficient decarbonization of fly ash particles with wide charge range or small charge to mass ratio (CMR). Therefore, a nonlinear electric field structure is proposed. The separation process of fly ash particles in the nonlinear electric field is explored through the establishment of geometric model and the application of CFD-DEM coupled calculation method, and the main influencing factors of fly ash electrostatic dry separation are studied. The results show that the nonlinear electric field structure is feasible to achieve high efficiency decarbonization of fly ash. With the increase of air flow velocity, the loss on ignition of positive electrode first increases and then decreases. The loss on ignition (LOI) of positive electrode products is directly proportional to the voltage and the CMR of the input, but inversely proportional to the feed quantity. Air flow velocity of 20 m/s, voltage of 30 kV, charge-mass ratio of 1.1–1.2 nC/g and feed quantity of 5000/s are suitable conditions for efficient decarbonization of fly ash. Compared with parallel plates, hyperbolic nonlinear electric field has higher decarbonization efficiency and lower energy consumption in experiment.     

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

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

Fine limestone additions to regulate setting in high volume fly ash mixtures

High volume fly ash (HVFA) concrete mixtures are being considered more frequently due to their cost and sustainability advantages. While the long term performance of these HVFA concretes typically meets or exceeds that of conventional concretes, their early age performance is often characterized by excessive retardation of the hydration reactions, delayed setting times, and low strengths. Extending an HVFA mixture to a ternary blend that incorporates a fine limestone powder may provide a viable solution to these deficiencies, particularly the hydration retardation and setting issues. In this paper, a nano-limestone powder and two other limestone fillers of increasing median particle size (4.4 μm and 16.4 μm) are investigated for their propensity to accelerate early age reactions and reduce setting times in a Class C fly ash/cement blend. The fineness of the limestone has measurable effects on its efficacy in accelerating hydration and decreasing setting times. Companion specimens prepared with a fine silica powder suggest that the fine limestone may act favorably through both a physical and a chemical mechanism. Isothermal calorimetry and Vicat needle penetration measurements on pastes are accompanied by strength measurements on mortars, to verify that the limestone powder substitutions are not negatively impacting strength development. A linear relationship with a reasonable correlation is found to exist between 1 d and 7 d compressive strengths of mortars and their accompanying cumulative heat release values as determined using isothermal calorimetry.     

粉煤灰对氧化镁水泥膨胀的影响机理——探讨粉煤灰对膨胀源所处环境的结构和力学性能的影响

在外掺轻烧氧化镁的水泥净浆中掺入粉煤灰,通过膨胀率变化分析粉煤灰对氧化镁膨胀的影响及其机理。粉煤灰在早期促进了氧化镁膨胀,到后期却抑制了膨胀,而且随着粉煤灰掺量的增加上述作用增强。为了更好地分析膨胀机理,结合膨胀场理论和KELVIN粘弹性模型深入讨论了粉煤灰对膨胀源所处环境的影响,并从水泥石的结构和力学性能揭示了粉煤灰对氧化镁膨胀的影响机制。     

Fluid transport in high volume fly ash mixtures with and without internal curing

The transport of fluid and ions in concrete mixtures is central to many aspects of concrete deterioration. As a result, transport properties are frequently measured as an indication of the durability that a concrete mixture may be expected to have. This paper is the second in a series investigating the performance of high volume fly ash (HVFA) mixtures with low water-to-cementitious ratios (w/cm) that are internally cured. While the first paper focused on strength and shrinkage, this paper presents the evaluation of the transport properties of these mixtures. Specifically, the paper presents results from: rapid chloride migration (RCM), rapid chloride penetration test (RCPT), apparent chloride diffusion coefficient, surface electrical resistivity, and water absorption. The test matrix consisted of mortar samples with two levels of class C fly ash replacement (40% and 60% by volume) with and without internal curing provided with pre-wetted lightweight fine aggregates (LWA). These mixtures are compared to plain ordinary portland cement (OPC) mortars. The results indicate that HVFA mixtures with and without internal curing provide benefits in terms of reduced transport coefficients compared to the OPC mixtures.     

减水剂在水泥与粉煤灰表面的吸附行为研究

为了揭示水泥与粉煤灰对减水剂的竞争吸附规律,采用分光光度法研究了SMF、FDN和ASP三种减水剂在此两种颗粒表面的吸附行为.结果表明,三种减水剂在胶凝颗粒表面的吸附均符合Langmuir等温吸附方程,属单分子层吸附.吸附量顺序均为:SMF>FDN>ASP.20℃时,SMF、FDN、ASP减水剂在水泥表面的饱和吸附量分别为12.95、11.35、3.83mg/g,而在粉煤灰表面的饱和吸附量则分别为3.15、2.86、1.10mg/g,表明水泥对减水剂的吸附强于粉煤灰对减水剂的吸附.减水剂在胶凝颗粒表面的吸附动力学也遵循Lang-muir吸附速率方程,SMF、FDN在水泥表面的平均吸附速率大于在粉煤灰颗粒表面的平均吸附速率,而ASP在两种胶凝颗粒表面的吸附速率较为接近.研究表明SMF、FDN将优先吸附在水泥颗粒表面,而ASP在水泥和粉煤灰表面的吸附选择性不高.     

粉煤灰在水泥基材料中吸波性能的探索

为了研究粉煤灰在水泥基材料中的吸收电磁波性能,将Ⅲ级粉煤灰掺入水泥净浆中,制成厚度为15～30mm的试样,分别进行吸波性能测试.结果显示,粉煤灰在16GHz附近有一个14.5dB的吸收峰;掺入粉煤灰的水泥净浆,在低频率区1～4GHz范围内,有6～10dB的吸收峰;在高频率区4～18GHz内,一般只有4～6dB的吸收峰.掺量为30%、厚度为30mm的试样在17GHz附近有一个8.5dB的吸收峰.     

Durability of concrete incorporating high-volume of low-calcium (ASTM Class F) fly ash

Research on structural concrete incorporating high volumes of low-calcium (ASTM Class F) fly ash has been in progress at CANMET since 1985. In this type of concrete, the cement content is kept at about 150 kg/m³. The water-to-cementitious materials ratio is of the order of 0·30, and fly ash varies from 54 to 58% of the total cementitious material. A large dosage of a superplasticizer is used to achieve high workability.

This paper presents data on the durability of this new type of concrete. The durability aspects considered are: freezing and thawing cycling; resistance to chloride ion permeability; and the expansion of concrete specimens when highly reactive aggregates are used in the concrete.

The investigations performed at CANMET indicate that concrete incorporating high volumes of low-calcium fly ash has excellent durability with regard to frost action, has very low permeability to chloride ions and shows no adverse expansion when highly reactive aggregates are incorporated into the concrete.     

Shrinkage characteristics of alkali-activated fly ash/slag paste and mortar at early ages

The purpose of this study is to investigate the shrinkage characteristics of alkali-activated fly ash/slag (henceforth simply AFS) and the factors affecting it. A series of tests were conducted to determine the chemical shrinkage, autogenous shrinkage and drying shrinkage. The microstructures and reaction products were also characterized through XRD and SEM/EDS analyses. An increase in the slag content from 10% to 30% resulted in a denser matrix and showed a higher Ca/Si ratio of C–N–A–S–H in the microstructure. Higher sodium silicate and slag contents in a mixture caused more chemical, autogenous, and drying shrinkage, but led to a higher compressive strength. From the test results, it can be concluded that the autogenous shrinkage of AFS mortar occurs mainly due to self-desiccation in hardened state rather than volume contraction by chemical shrinkage in fresh state. The AFS paste showed higher drying shrinkage than ordinary Portland cement (OPC), which may be caused by the higher mesopore volume of the AFS paste compared to that of OPC paste.     

生态水泥中SiO2掺量对焚烧飞灰中重金属固溶特性的影响

按不同SiO2掺量(质量分数)进行垃圾焚烧飞灰的水泥固化试验,研究了SiO2掺量对熟料试样的重金属分布、浸出毒性的影响。结果表明,SiO2掺量低于16%时,提高掺量有利于增加熟料中Cr、Ni、Cu、As固溶率;但SiO2掺量超过16%后,重金属固溶率与其成反比。Cd、Pb、Zn的挥发率随SiO2掺量增加而减少,掺加SiO2能明显抑制Zn的挥发,但基本不影响Hg的挥发。SiO2掺量增加后熟料结构进一步致密化,重金属浸出量减少。     

含粉煤灰或矿渣水泥石的孔结构

本文对掺粉煤灰与掺矿渣的水泥石孔结构特征进行了比较,结果表明：与掺矿渣相比,掺粉煤灰时水泥石总孔隙率较大,但趋于小孔分布,增加的主要是孔径在5nm以下的孔,孔径大于5nm的孔反而较少。     

Alteration of a cement matrix subjected to biolixiviation test

This paper reports on the assessment of durability and long-term performance of a cement matrix subjected to heterotrophic microbial mediated degradation. In near surface disposal facilities for hazardous and radioactive wastes, microbial activities may likely, in a long-term perspective threaten the integrity of cement-solidified wastes. To investigate the detrimental impact of heterotrophic microorganisms on cement matrices, Aspergillus niger reputed as versatile and prevalent fungus in soil flora was selected as candidate. It was shown that this fungus has the potential of severely degrading ordinary Portland cement pastes through organic acids production. Cement pastes experienced chemical alterations such as substantial leaching of calcium, and mechanical degradation was evident as highlighted by the drastic decline in Young’s modulus. Their poor behaviour with respect to heterotrophic biodeterioration and susceptibility to failure were therefore demonstrated. Consequently, biolixiviation scenario should be seriously considered in order to ensure safe long-term disposal for cement-solidified wastes.

粉煤灰对双膨胀水泥膨胀性能的影响

本文研究粉煤灰对双膨胀水泥水化和膨胀性能的影响。结果表明 ,粉煤灰对双膨胀水泥早期和后期膨胀都有显著的抑制作用 ,对早期膨胀的抑制作用与形成钙矾石的化学环境改变以及钙矾石形成提前结束有关 ,对后期膨胀的抑制作用与其抑制水泥浆体中水镁石的形成一致。