Hydration kinetics of C3A: effect of lithium, copper and sulfur-based mineralizers

IF 3 3区 工程技术 Q2 CHEMISTRY, ANALYTICAL Journal of Thermal Analysis and Calorimetry Pub Date : 2024-09-10 DOI:10.1007/s10973-024-13525-6
Eva Bartonickova, Petr Ptacek, Radoslav Novotny, Jakub Palovcik, Jiri Masilko, Jiri Svec, Martin Sedlacik, Jan Koplik, Theodor Stanek, Dusan Hemzal
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Abstract

Calcium aluminate phases have a particular effect on the early heat release during setting initiation and have a substantial influence on the further workability of ordinary Portland cement. The nature of the calcium aluminate hydration products and its kinetics strongly depends on sulfate content and humidity. The effect of mineralisers on melt formation and viscosity is well described for calcium silicate systems, but information is still lacking for calcium aluminates. Therefore, the synergistic effect on the crystal structure and hydration mechanism of the tricalcium aluminate phase of the addition of mineralizers, i.e. Li2O, CuO, SO3 to the raw meal is here investigated. Co-doped calcium aluminate structures were formed during high-temperature treatment. Thermal analysis (TG–DTA and heating microscopy) was used to describe the ongoing high-temperature reaction. Resulting phase composition was dependent on the concentration of the mineralizer. While phase pure system was prepared with low mineralizer concentrations, with increasing mineralizer content the secondary phases were formed. Raman spectroscopy and XPS analysis were used to investigate the cation substitution and to help describe the cations bonding in co-doped calcium aluminate system. Prepared powders have been hydrated in a controlled manner at different temperatures (288, 298, 308 K). The resulting calorimetric data have been used to investigate the hydration kinetics and determine the rate constant of hydration reaction. First-order reaction (FOR) model was here applied for the activation energy and frequency factor calculations. The metastable and stable calcium aluminate hydrates were formed according to initial phase composition. In phase pure systems with low S content, the formation of stable and metastable hydrates was depended on the reaction temperature. Conversely, in systems with secondary phases and higher S content, the hydration mechanism resembled that which appears in calcium sulfoaluminates.

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C3A 的水合动力学:锂、铜和硫基矿化剂的影响
铝酸钙相对凝结初期的热量释放有特殊的影响,并对普通硅酸盐水泥的进一步可加工性有重大影响。铝酸钙水化产物的性质及其动力学在很大程度上取决于硫酸盐含量和湿度。矿化剂对熔体形成和粘度的影响在硅酸钙体系中已有很好的描述,但在铝酸钙体系中仍缺乏相关信息。因此,本文研究了在生料中添加矿化剂(即 Li2O、CuO 和 SO3)对铝酸钙三相的晶体结构和水合机制的协同效应。在高温处理过程中形成了掺杂铝酸钙结构。热分析(TG-DTA 和加热显微镜)用于描述正在进行的高温反应。最终的相组成取决于矿化剂的浓度。低浓度矿化剂可制备出纯相体系,而随着矿化剂含量的增加,则会形成次生相。拉曼光谱和 XPS 分析用于研究阳离子置换,并帮助描述共掺杂铝酸钙体系中的阳离子键合。制备的粉末在不同温度(288、298、308 K)下以受控方式进行水合。所得热量数据用于研究水合动力学和确定水合反应的速率常数。一阶反应(FOR)模型被用于活化能和频率因子的计算。根据初始相组成的不同,形成了逸散和稳定的铝酸钙水合物。在 S 含量较低的纯相体系中,稳定和逸散水合物的形成取决于反应温度。相反,在具有次生相和 S 含量较高的体系中,水合机制类似于硫铝酸钙中出现的机制。
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来源期刊
CiteScore
8.50
自引率
9.10%
发文量
577
审稿时长
3.8 months
期刊介绍: Journal of Thermal Analysis and Calorimetry is a fully peer reviewed journal publishing high quality papers covering all aspects of thermal analysis, calorimetry, and experimental thermodynamics. The journal publishes regular and special issues in twelve issues every year. The following types of papers are published: Original Research Papers, Short Communications, Reviews, Modern Instruments, Events and Book reviews. The subjects covered are: thermogravimetry, derivative thermogravimetry, differential thermal analysis, thermodilatometry, differential scanning calorimetry of all types, non-scanning calorimetry of all types, thermometry, evolved gas analysis, thermomechanical analysis, emanation thermal analysis, thermal conductivity, multiple techniques, and miscellaneous thermal methods (including the combination of the thermal method with various instrumental techniques), theory and instrumentation for thermal analysis and calorimetry.
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