Ridi Francesca, Fratini Emiliano, Mannelli Francesca, Baglioni Piero
Department of Chemistry and Consorzio Interuniversitario per lo Sviluppo dei Sistemi a Grande Interfase (CSGI), University of Florence, Via della Lastruccia 3-Sesto Fiorentino, I-50019 Florence, Italy.
J Phys Chem B. 2005 Aug 4;109(30):14727-34. doi: 10.1021/jp050237n.
In the cement industry, the extrusion technique is used to produce flat shapes with improved resistance to compression. Extrusion is a plastic-forming process that consists of forcing a highly viscous plastic mixture through a shaped die. The material should be fluid enough to be mixed and to pass through the die, and on the other hand, the extruded specimen should be stiff enough to be handled without changing in shape or cracking. These characteristics are industrially obtained by adding cellulosic polymers to the mixture. The aim of this work is to understand the action mechanism of these additives on the major pure phases constituting a typical Portland cement: tricalcium silicate (C(3)S), dicalcium silicate (C(2)S), tricalcium aluminate (C(3)A), and tetracalcium iron-aluminate (C(4)AF). In particular, a methylhydroxyethyl cellulose (MHEC) was selected from the best-performing polymers for further study. The effect of this additive on the hydration kinetics (rate constants, activation energies, and diffusional constants) was evaluated by means of differential scanning calorimetry (DSC) while the hydration products were studied by using thermogravimetry-differential thermal analysis (TG-DTA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). MHEC addition in calcium silicate pastes produces an increase in the induction time without affecting the nucleation-and-growth period. A less dense CSH gel was deduced from the diffusional constants in the presence of MHEC. Moreover, CSH laminar features and poorly structured hydrates were noted during the first hours of hydration. In the case of the aluminous phases, the additive inhibits the growth of stable cubic hydrated phases (C(3)AH(6)), with the advantage of the metastable hexagonal phases being formed in the earliest minutes of hydration.
在水泥行业,挤压技术用于生产抗压性能更好的扁平形状产品。挤压是一种塑性成型工艺,包括将高粘性塑料混合物通过成型模具挤出。材料应具有足够的流动性以便混合并通过模具,另一方面,挤出的试样应具有足够的硬度,以便在不改变形状或不开裂的情况下进行处理。这些特性可通过在混合物中添加纤维素聚合物在工业上获得。这项工作的目的是了解这些添加剂对构成典型波特兰水泥的主要纯相的作用机制:硅酸三钙(C(3)S)、硅酸二钙(C(2)S)、铝酸三钙(C(3)A)和铁铝酸四钙(C(4)AF)。特别地,从性能最佳的聚合物中选择了一种甲基羟乙基纤维素(MHEC)进行进一步研究。通过差示扫描量热法(DSC)评估该添加剂对水化动力学(速率常数、活化能和扩散常数)的影响,同时使用热重-差示热分析(TG-DTA)、X射线衍射(XRD)和扫描电子显微镜(SEM)研究水化产物。在硅酸钙浆料中添加MHEC会使诱导时间增加,而不影响成核和生长阶段。根据MHEC存在时的扩散常数推断出CSH凝胶密度较低。此外,在水化的最初几个小时内观察到了CSH层状特征和结构不良的水化物。对于含铝相,该添加剂抑制稳定立方水化物相(C(3)AH(6))的生长,有利于在水化最早的几分钟内形成亚稳六方相。