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This article is devoted to the study of the combined effect of siliceous fly ash (FA), silica fume (SF), and nanosilica (nS) on the cement matrix morphology and size of microcracks occurring in the Interfacial Transition Zone (ITZ) between the coarse aggregate and the cement paste of concrete composites based on ordinary Portland cement (OPC). The manuscript contains analyses of width of microcracks (Wc) occurring in the ITZ area of concretes based on quaternary blended cements and changes in ITZ morphology in the concretes in question. Experiments were planned for four types of concrete. Three of them were composites based on quaternary blended cements (QBC), while the fourth was reference concrete (REF). Based on the observations of the matrices of individual composites, it was found that the REF concrete was characterized by the most heterogeneous structure. However, substitution of part of the cement binder with active pozzolanic additives resulted in a more compact and homogenous structure of the cement matrix in each of the QBC series concretes. Moreover, when analyzing the average Wc values, it should be stated that the modification of the basic structure of the cement matrix present in the REF concrete resulted in a significant reduction of the analyzed parameter in all concretes of the QBC series. For QBC-1, QBC-2, and QBC-3, the Wc values were 0.70 μm, 0.59 μm, and 0.79 μm, respectively, indicating a decrease of 38%, almost 48%, and 30%, respectively, compared with the working condition of concrete without additives. On the basis of the above results, it can therefore be concluded that the proposed modification of the binder composition in the analyzed materials clearly leads to homogenization of the composite structure and limitation of initial internal damages in concrete.
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