Krivoborodov Yurii R, Samchenko Svetlana V, Korshunov Andrey V, Kozlova Irina V, Alpacky Dmitrii G
Department of Building Materials, Moscow State University of Civil Engineering, 26, Yaroslavskoye Shosse, 129337 Moscow, Russia.
Materials (Basel). 2023 Nov 8;16(22):7078. doi: 10.3390/ma16227078.
Tricalcium silicate (CS) as a binder material has a decisive influence on the processes of hardening and strength gain of cements and concretes. One of the promising directions is the introduction of dispersed additives into cement mixtures, which allow micro-level control of the composition of hydration products and change the dynamics of the structure formation of cement stone. In this paper, the effect of a microdisperse ettringite additive on the kinetics of the hydration and hardening process of tricalcium silicate was studied. It was shown that ettringite crystals selectively adsorb Ca and OH ions from a saturated solution of calcium hydroxide, which contributes to the formation of hydrosilicate nuclei on their surface during cement hydration. Hydration of CS in the presence of ettringite proceeds more intensively; the addition of ettringite contributes to an increase in the content of calcium hydrosilicates in hydration products at the initial stage of the process. Addition of 10 wt.% ettringite to CS reduces the induction period of the beginning of the main phase of heat release by around two times and increases the amount of heat released on the 1st day of hydration by 15% compared to the control sample. According to electron microscopy data, it was found that during the first hours of hydration of modified CS, a significant number of nuclei of fibrous particles of calcium hydrosilicates with sizes of 0.2-2 microns were formed on the surface of ettringite crystals. According to the results of kinetic modeling of the setting process of cement pastes using the Avrami-Erofeyev model, it was shown that in the presence of the addition of microcrystals of ettringite, the setting rate is characterized by a slowdown in nucleation, whereas for a sample without an additive, this process proceeds with an acceleration of the formation of solid-phase nuclei. Based on the comparison of kinetic results and mechanical measurements, it is concluded that needle crystals of ettringite during CS hydration and cement stone hardening are preformed centers for the growth of hydrosilicate nuclei, and they also act as a reinforcing filler, increasing the bending strength of modified samples. The results of the work can be used in practice in the development of methods for controlling the processes of hydration and hardening of cements, as well as for controllable structure formation of cement stone which is important in particular for 3D printing of building products and constructions.
硅酸三钙(CS)作为一种胶凝材料,对水泥和混凝土的硬化及强度增长过程具有决定性影响。一个有前景的方向是在水泥混合物中引入分散添加剂,这能够在微观层面控制水化产物的组成,并改变水泥石结构形成的动力学。本文研究了微分散钙矾石添加剂对硅酸三钙水化和硬化过程动力学的影响。结果表明,钙矾石晶体从氢氧化钙饱和溶液中选择性吸附Ca和OH离子,这有助于在水泥水化过程中在其表面形成水合硅酸盐核。在钙矾石存在的情况下,CS的水化进行得更剧烈;添加钙矾石有助于在过程初始阶段提高水化产物中水合硅酸钙的含量。与对照样品相比,向CS中添加10 wt.%的钙矾石可使主要放热阶段开始的诱导期缩短约两倍,并使水化第1天释放的热量增加15%。根据电子显微镜数据,发现在改性CS水化的最初几个小时内,在钙矾石晶体表面形成了大量尺寸为0.2 - 2微米的水合硅酸钙纤维状颗粒核。根据使用阿夫拉米 - 埃罗菲耶夫模型对水泥浆体凝结过程进行动力学建模的结果表明,在添加钙矾石微晶的情况下,凝结速率的特征是成核减缓,而对于无添加剂的样品,该过程随着固相核形成的加速而进行。基于动力学结果和力学测量的比较,得出结论:在CS水化和水泥石硬化过程中,钙矾石针状晶体是水合硅酸盐核生长的预制中心,并且它们还作为增强填料,提高改性样品的抗弯强度。该工作结果可实际应用于开发控制水泥水化和硬化过程的方法,以及用于水泥石的可控结构形成,这对于建筑产品和结构的3D打印尤为重要。