This review synthesizes recent advances in the characterization of eco-friendly cement composites, focusing on hydration kinetics, microstructural evolution, and mechanical durability. Advanced techniques—from isothermal calorimetry to nanoindentation—enable decoding of reaction pathways, mix optimization, and long-term performance prediction. The analysis covers supplementary cementitious materials (fly ash, slag, silica fume), geopolymers, bio-based additives (SNSs, biochar, CNCs, lignosulfonates), and microbially induced calcite precipitation (MICP). For each category, key mechanisms are identified, property effects quantified, and microstructural correlations established. SCMs achieve pore refinement and enhanced durability through long-term pozzolanic reactions. Geopolymers exhibit exceptional thermal stability (800–1000 °C) and acid resistance. Fly ash-based geopolymers exhibit chloride diffusion coefficients 1–2 orders of magnitude lower than ordinary Portland cement (OPC), though slag-based systems show more moderate improvements due to their different pore structure and higher calcium content. Bio-based additives enable accelerated hydration (SNSs), internal curing and CO2 sequestration (biochar), pore refinement (CNCs), workability enhancement (lignosulfonates), and autonomous crack healing (MICP). Multi-scale characterization is essential for establishing robust structure–property relationships. The review concludes that properly optimized eco-friendly cement composites offer viable pathways toward sustainable construction with reduced carbon footprint, enhanced durability, and extended service life. This review is novel in its systematic comparison of hydration kinetics, microstructural evolution, and mechanical performance across three distinct classes of eco-friendly additives (SCMs, geopolymers, and bio-based materials), with particular emphasis on the complementarity of advanced characterization techniques—an aspect that has received limited attention in previous reviews.
Barbir et al. (2026) studied this question.