Geopolymer concrete contains inorganic aluminosilicate polymer gels formed through the activation of industrial solid wastes. This study investigated the effects of fly ash (FA) and silica fume (SF) on the durability and microstructure of geopolymer concrete exposed to freeze–thaw cycles and single-side salt erosion. Five mixtures were prepared using Baioheng geopolymer cement, with FA replacement levels of 15% and 25% and SF replacement levels of 3% and 5%. Mechanical tests, freeze–thaw tests, single-side salt-freezing tests, SEM-EDS, XRD, and CT analysis were conducted to evaluate the relationship between macroscopic performance and inorganic polymer gel structure. The results showed that 25% FA reduced compressive strength and freeze–thaw resistance, mainly due to insufficient reaction products and increased defect connectivity. In contrast, 3% SF improved the 56 d compressive strength by 13.24%, maintained the relative dynamic elastic modulus at 86.64% after 100 freeze–thaw cycles, and limited the mass loss to 0.72%. SEM-EDS and XRD results indicated that appropriate SF addition increased the Si/Al ratio and promoted the formation of C-(A)-S-H/N-A-S-H-related gel products, leading to a denser inorganic polymer matrix. However, excessive SF weakened the improvement effect, possibly due to local heterogeneity and dispersion difficulty. These results indicate that controlling the composition and spatial distribution of inorganic aluminosilicate polymer gels is essential for improving the salt-frost durability of geopolymer concrete.

This study systematically investigated the durability of low-carbon concrete under severe service conditions using industrial solid wastes. The mechanical properties and carbonation resistance (including carbonation depth, compressive strength after carbonation, and splitting tensile strength after carbonation) were tested. Multi-scale characterization techniques, including XRD, SEM-EDS, and nanoindentation, were employed to investigate the microstructure. This approach revealed a synergistic mechanism linking microstructural evolution to the concrete’s macroscopic mechanical and durability performance. Results showed that incorporating 25% fly ash (FA) reduced compressive strength by 11.30% and 11.39% in CF-25 and BF-25 mixes, respectively, and increased carbonation depth by 58.46% in CF-25. In contrast, the addition of 5% silica fume (SF) produced different effects. It significantly enhanced the compressive strength of the CS-5 and BS-5 mixes by 18.92% and 9.94%, respectively. Furthermore, it improved the micromechanical properties of the interfacial transition zone (ITZ) and reduced its thickness. Micro-mechanistic analysis revealed that the low pozzolanic activity of FA at early ages led to insufficient hydration products, higher porosity, and a weaker ITZ. Conversely, SF, through its high pozzolanic reactivity and nano-filling effect, promoted a dense, highly polymerized gel structure and optimized pore size distribution. The distinct chemical characteristics of high-calcium and low-calcium cementitious systems further amplified the differential effects of these supplementary materials.