矿物掺合料早期水化活性的测试和分析

本文采用环境扫描电子显微镜(ESEM)和热重-差热(TG-DTA)分析仪对磨细矿渣微粉、高钙粉煤灰、低钙粉煤灰的早期水化活性进行了系统测试和分析.理论和试验结果分析表明,掺合料取代水泥时,浆体早期抗压强度的提高取决于掺合料自身参与水化反应的速度和水化产物的数量.水化产物在掺合料颗粒表面沉积的速度和浆体中硅酸盐、铝酸盐水化产物的非蒸发水量随掺合料活性的提高而提高.掺合料活性按磨细矿渣微粉、高钙粉煤灰、低钙粉煤灰的顺序降低,将磨细矿渣微粉或高钙粉煤灰与低钙粉煤灰复合,可以克服低钙粉煤灰大掺量取代水泥时混凝土早期强度降低的缺陷,这是提高低钙粉煤灰在高强高性能混凝土中掺量的一个有效措施.     

钢渣胶凝活性与体积稳定性优化研究现状

随着粗钢产量的逐年递增，我国钢渣累积存放量也不断上升，将钢渣用作辅助胶凝材料是提高钢渣综合利用率、降低水泥混凝土行业碳排放的有效措施。然而，钢渣存在的胶凝组分含量少且活性低、膨胀组分含量较高等问题限制了其在水泥和混凝土中的应用。目前，用于改善钢渣胶凝活性与体积稳定性的方法主要有机械粉磨、高温活化、碱活化、酸活化、有机物活化及碳化活化等。机械粉磨主要通过物理方式破坏钢渣晶体结构、减小颗粒粒径，但其能耗较高且仅对早期强度有利。高温活化主要包括高温养护和高温调质/重构：高温养护通过改变钢渣水化所处的外界环境促进水化，但较高温度会使钙矾石分解并引入孔洞；高温调质/重构工艺直接改变了钢渣的矿物组成，但存在能耗高和匀质性差的问题。碱活化可以促进离子溶出并消耗氢氧化钙，但存在碱骨料反应和泛碱等问题。酸活化也可以促进离子溶出，增大钢渣比表面积，但过量酸会消耗钢渣中活性组分。有机物活化中，醇胺可以通过络合作用促进离子溶出，但不同分子结构的醇胺作用机理仍不明确。碳化活化通过钙镁矿物与CO₂反应形成碳酸盐填充孔隙，但CO₂向试块内部的扩散阻力使内外碳化程度不均匀。...     

碱对粉煤灰的活化和微观结构的影响

用Ｘ－射线、ＳＥＭ研究了粉煤灰在不同碱度环境下的活化机制、水化产物和微观结构。研究表明：粉煤灰硅酸盐水泥在常温下养护，粉煤灰的反应能力较低，这是因为在Ｃａ（ＯＨ）２存在条件下的活化很慢，只有提高养护温度或在复合碱和硫酸盐存在条件下才有利于结构的解体和水化产物的稳定。     

高铁、高钙类粉煤灰高值化的醋酸分离规律研究

采用低腐蚀、低能耗、高选择性的醋酸分离法高值化利用粉煤灰中的铁、钙等,制得产物醋酸铁、醋酸钙等醋酸盐,产物通过IR分析、原子吸收光谱分析、XRD分析和SEM分析,表征了官能团结构和晶相特征。采用原子吸收法研究了反应温度和反应时间对粉煤灰中铁、钙的醋酸反应活性的影响规律,结果表明,CaO和Fe2O3的醋酸反应活性不同,Fe2O3的反应活性高于CaO,粉煤灰与醋酸的最佳反应温度为室温(20～25℃),较佳反应时间为2～3h,可使Fe2O3和CaO都获得较高的醋酸反应活性,粉煤灰中铁利用率为94.18%,钙、镁、钾利用率为94.99%。     

粉煤灰在饱和Ca（OH）2溶液中的溶出行为

对在饱和Ca(OH)2溶液中养护至不同龄期的粉煤灰进行测试,对粉煤灰中氧化硅、氧化铝等成分的溶解速率、粉煤灰颗粒表面的微观形貌以及反应产物进行了分析,同时,对SO42-在钙矾石AFt晶体的形成过程中的影响也进行了探讨。结果表明:在饱和Ca(OH)2溶液体系中,粉煤灰中活性SiO2和Al2O3的溶出速率要比粉煤灰水泥浆体中的火山灰反应快;经饱和Ca(OH)2溶液处理后,粉煤灰颗粒表面主要有4种形貌———碱刻蚀现象、结构致密层、疏松的沉积层、颗粒表面形成钙矾石晶体;SO42-的浓度影响钙矾石的成核结晶。     

废玻璃粉的火山灰活性

研究中位粒径为15.63、14.93、9.54μm的3种废玻璃粉,分别以相同的质量分数取代10%、20%、30%的水泥制成的胶砂试件7、14、21、28、35、120 d的抗压强度比(活性指数),测定不同龄期废玻璃粉石灰溶液与粉煤灰石灰溶液pH。结果表明:取代率越大,废玻璃粉的活性指数越小;35 d以前的龄期,中位粒径为15.63、14.93μm的废玻璃粉组活性指数最大,35~120 d的后期,中位粒径为9.54μm的废玻璃粉组活性指数最大;废玻璃粉组活性指数前期随着龄期的延长呈减小趋势,后期增大,120 d时达90%以上,比粉煤灰组活性指数约小15%;废玻璃粉石灰溶液与粉煤灰石灰溶液前期pH均呈减小趋势,后期增大;废玻璃粉和粉煤灰的石灰溶液均生成大量CaO-SiO2-H2O凝胶,粉煤灰石灰溶液中还有钙矾石生成,说明废玻璃粉后期有很强的火山灰活性。     

碱对粉煤灰的活化和微观结构的影响

用X-射线、SEM研究了粉煤灰在不同碱度环境下的活化机制、水化产物和微观结构。研究表明:粉煤灰硅酸盐水泥在常温下养护,粉煤灰的反应能力较低,这是因为在Ca(OH)2存在条件下的活化很慢,只有提高养护温度或在复合碱和硫酸盐存在条件下才有利于结构的解体和水化产物的稳定。     

活化处理对竹纤维结构和性能的影响

为了提高竹纤维的反应活性,分别用碱液和超声波协同碱活化处理竹纤维。通过X-射线衍射分析(XRD)、热重分析(TG)和扫描电镜分析(SEM)研究了活化处理前后竹纤维的结构与热性能。通过竹纤维与高碘酸钠反应所得氧化竹纤维的醛基质量分数来分析活化处理对竹纤维反应活性的影响。结果表明:碱处理和超声波协同碱处理可降低竹纤维的结晶度和热稳定性,提高竹纤维的反应活性。     

硅酸盐水泥早期体积稳定性的调控研究

分别研究了利用硬石膏、粉煤灰制备的钙矾石型膨胀剂和硬石膏、石灰和粉煤灰三元组分制备的钙矾石-羟钙石复合膨胀刑对水泥体系膨胀性能的影响.利用XRD、TG-DSC-DTG和SEM等测试方法对水泥体系中的钙矾石和羟钙石进行了定性和定量分析,在微观上对钙矾石和羟钙石的形态进行了分析.结果表明,由硬石膏、粉煤灰制备的膨胀刺,膨胀主要发生在前7d,由硬石膏、石灰和粉煤灰制备的复合膨胀剂,膨胀效果较好,28d时仍有微膨胀.对硅酸盐水泥早期的体积稳定性进行调控,可以有效减小水泥体系早期开裂的几率.     

用于地聚合物的粉煤灰活性评价研究

由于粉煤灰的非均质性,很难直接预测粉煤灰的活性.本实验研究了不同粉煤灰在不同时间、温度和碱浓度条件下的浸出过程(先将粉煤灰在碱液中溶解,再将其残留物在酸溶液中解离).通过电感耦合等离子体发射光谱仪(ICP)和化学分析表明,温度、反应时间和碱浓度都会影响粉煤灰的溶解速率和浸出含量.粉煤灰中浸出的反应性n(Si)/n(Al)为2.3～2.7,粉煤灰中硅和铝的总浸出量与成型用其制备的地聚合物强度呈正相关.另外,可发现建立在硅酸盐水泥体系上的粉煤灰活性评价体系并不完全适用于地聚合物体系.通过XRD、FTIR和SEM分析可发现,粉煤灰由反应性材料和惰性材料组成,而活性物质在地聚合过程中迅速溶解,酸完全解离在地聚合过程中生成的凝胶,浸出过程更能准确表征粉煤灰中反应性物质的含量.碱溶解?酸解离法可定量估算粉煤灰的反应物含量和反应性n(Si)/n(Al),并简单预测用于地聚合物体系的粉煤灰的潜在反应活性,还可指导粉煤灰地聚合物的配比设计.     

粉煤灰地聚物反应体系下的反应影响因素分析

以粉煤灰基地质聚合物为研究对象,研究了粉煤灰在地聚物反应体系下的反应影响因素。主要研究内容有:反应时间、反应温度和反应碱浓度对反应过程及宏观强度的影响及相关反应机理。结果表明:在反应中后期,粉煤灰反应速率明显下降而此时地聚物的宏观性能反而呈现最大值。以75℃为例,反应时间从24h延长到672h的过程中,反应程度仅从20.8%增加到了32.4%,平均反应速率仅为0.0179%/h,而此时样品的抗压强度则从1.31MPa增加到了7.98 MPa;在地聚物反应体系下,反应产物为无定形的硅铝胶凝体,该物质的致密程度与地聚物宏观性能直接相关;温度的升高可有效提高粉煤灰的反应速率及地聚物的宏观性能,促进无定形胶凝体的形成和硬化。反应24h,75℃下的反应程度和抗压强度可以达到20.8%和1.31 MPa,而同期35℃下的反应程度只能达到7.8%且尚未形成宏观强度;碱浓度的变化不仅可影响反应速率和宏观性能,还可改变粉煤灰在地聚物反应体系下的最终反应程度,在反应温度为75℃和50℃时,10 mol/L体系下672h的反应程度比5 mol/L体系分别高了90%和28.6%。     

Microscopy and microanalysis of inorganic polymer cements. 1: remnant fly ash particles

Accurate and precise electron microscopic analysis of the remnant solid precursor (fly ash and blast furnace slag) particles embedded in an inorganic polymer cement (or “fly ash geopolymer”) provides critical information regarding the process of gel binder formation. Differential solubility of phases in the fly ash is seen to be important, with insoluble mullite crystals becoming exposed by the retreat of the surrounding glassy phases. High-iron particles appear to remain largely unreacted, and the use of sectioned and polished specimens provides a view of the inside of these particles, which can show a wide variety of phase separation morphologies and degrees of intermixing of high iron and other phases. Calcium appears to be active in the process of alkali activation of ash/slag blends, although the competitive and/or synergistic effects of ash and slag particles during the reaction process remain to be understood in detail.     

Reaction kinetics of fly ash geopolymerization: Role of particle size controlled by using ball mill

Fly ash is milled for 0, 30 and 90?min and used to study the role of particle size on the kinetics of geopolymer formation. The increase in particle fineness is very prominent in the initial milling stage, and then slows down due to agglomeration effect of finer fraction. The fly ash geopolymerization kinetics and its mechanism is determined using heat of reaction data measured by isothermal conduction calorimeter. The improvement in reaction rate with milling is correlated with the median particle size of the fly ash. The apparent activation energy decreases with size reduction because finer fractions are more prone to alkali activation. Although the kinetics changes with particle fineness, but no alternation is detected in the reaction mechanism, governed by nucleation and growth. The apparent activation energy evaluated by rate method is showing three major steps of geopolymerization such as dissolution, gel formation and restructuring.     

Microscopy and microanalysis of inorganic polymer cements. 2: the gel binder

By scanning electron microscopy and microanalysis of fly ash-based and mixed fly ash-slag inorganic polymer cement (i.e., “fly ash geopolymer”) binders, a more detailed understanding of the gel structure and its formation mechanism have been developed. The binder is predominantly an aluminosilicate gel charge balanced by alkali metal cations, although it appears that calcium supplied by slag particles becomes relatively well dispersed throughout the gel. The gel itself is comprised of colloidal-sized, globular units closely bonded together at their surfaces. The microstructure of the binder resulting from hydroxide activation of fly ash is much less uniform than that which forms in a corresponding silicate-activated system; this can be rationalized in terms of a newly developed explanation for the differences in reaction mechanisms between these two systems. In hydroxide activation, the newly formed gel phase nucleates and grows outwards from the ash particle surfaces, whereas the high silica concentration in a silicate-activated system enables a more homogeneous gelation process to take place throughout the inter-particle volume.     

Relationships between composition,structure and strength of inorganic polymers

This article is the second in a two-part series and discusses inorganic polymers derived from fly ash. Part 1 [1] concerns inorganic polymers derived from a metakaolin precursor. For this study, 15 fly ash-derived inorganic polymers were produced with various compositions. The effect of the concentration of each of the four component oxides (Na₂O, SiO₂, Al₂O₃ and H₂O) and two alkali cations (Na and K) on the microstructure and compressive strengths were assessed. Similar to metakaolin-derived inorganic polymers, it was observed that high-strength fly ash inorganic polymers were related to low porosity and a dense, fine-grained microstructure. Such structures were characteristic of formulations with high silica mole fractions (SiO₂/Al₂O₃ ∼ 3.9) and low water contents, as well as those with high alkali and low alumina contents. For the latter, not only was a characteristic slower strength development with increasing alkali content observed, but there was also a limit of alkali concentration (Na₂O/Al₂O₃ ∼1) beyond which the strength deteriorated. Furthermore, SEM micrographs disclose that the fly ash precursor dissolves more readily in the sodium-based system compared to the potassium equivalent. The interrelation between microstructures of the respective formulations and their strength development are discussed. It is observed that the charge-balancing role of the alkali cations in the fly ash formulations may be dominant compared to initial alkali dissolution reaction of the aluminosilicate fly ash particles, which is partly responsible for initial strength development.     

Microstructure,strength, and moisture stability of alkali activated glass powder-based binders

Thermally assisted alkali activation of silica-rich glass powder to produce sustainable binders is investigated. Glass powder activated using NaOH provides higher compressive strengths than NaOH activated fly ash binders at lower heat curing temperatures. Sodium silicate gel is the reaction product when glass powder alone is used as the source material, while a combination of sodium silicate and sodium aluminosilicate (N–A–S–H) gels form in activated glass powder–fly ash blends. The activated glass powder-containing binders are found to disintegrate and lose strength when exposed to moisture or an alkaline solution, with the pure glass powder binders suffering the highest strength loss. Structural changes to the reaction product on exposure to moisture are explained using microstructural and FTIR spectroscopic observations. Doping the systems with Al containing (metakaolin) and Ca containing (slag) source materials, while retaining glass powder as the major component (50% or more), result in the formation of moisture-stable reaction products thereby mitigating the strength loss to a large extent.     

Simulation of a temperature rise in concrete incorporating fly ash or slag

Granulated slag from metal industries and fly ash from the combustion of coal are among the industrial by-products and have been widely used as mineral admixtures in normal and high strength concrete. Due to the reaction between calcium hydroxide and fly ash or slag, compared with Portland cement, the hydration of concrete containing fly ash or slag is much more complex. In this paper, by considering the producing of calcium hydroxide in cement hydration and the consumption of it in the reaction of mineral admixtures, a numerical model is proposed to simulate the hydration of concrete containing fly ash or slag. The heat evolution rate of fly ash or slag blended concrete is determined from the contribution of both cement hydration and the reaction of mineral admixtures. Furthermore, a temperature rise in blended concrete is evaluated based on the degree of hydration of cement and mineral admixtures. The proposed model is verified with experimental data on the concrete with different water-to-cement ratios and mineral admixtures substitution ratios.     

Properties of alkali activated slag–fly ash blends with limestone addition

In this article, the effects of raw materials’ composition on fresh behavior, reaction kinetics, mechanical properties and microstructure of alkali activated slag–fly ash–limestone blends are investigated. The results indicate that, with the increasing content of fly ash and limestone, the slump flow increases. The setting times are shortened when increasing the slag content, while both fly ash and limestone show a negligible influence. The reaction process is slightly accelerated by the presence of limestone due to the extra provided nucleation sites, but the reaction process is mainly governed by the slag. The slag content exhibits a dominant role on strength in this ternary system, while for a constant slag content, the compressive strength increases with the increasing limestone content up to 30%. The microstructure analysis shows that the gel characteristics are independent of the limestone powder content. The presence of limestone in initially high Ca and Al conditions does not lead to the formation of additional crystalline phases, which is different from Portland cement systems. Both physically and chemically bound water contents are slightly increased when limestone powder is incorporated.     

Biostabilization assessment of MSW co-disposed with MSWI fly ash in anaerobic bioreactors

Municipal solid waste incinerator (MSWI) fly ash has been examined for possible use as landfill interim cover. For this aim, three anaerobic bioreactors, 1.2m high and 0.2m in diameter, were used to assess the co-digestion or co-disposal performance of MSW and MSWI fly ash. Two bioreactors contained ratios of 10 and 20 g fly ash per liter of MSW (or 0.2 and 0.4 g g(-1) VS, that is, 0.2 and 0.4 g fly ash per gram volatile solids (VS) of MSW). The remaining bioreactor was used as control, without fly ash addition. The results showed that gas production rate was enhanced by the appropriate addition of MSWI fly ash, with a rate of approximately 6.5l day(-1)kg(-1)VS at peak production in the ash-added bioreactors, compared to approximately 4l day(-1)kg(-1)VS in control. Conductivity, alkali metals and VS in leachate were higher in the fly ash-added bioreactors compared to control. The results show that MSW decomposition was maintained throughout at near-neutral pH and might be improved by release of alkali and trace metals from fly ash. Heavy metals exerted no inhibitory effect on MSW digestion in all three bioreactors. These phenomena indicate that proper amounts of MSWI fly ash, co-disposed or co-digested with MSW, could facilitate bacterial activity, digestion efficiency and gas production rates.