With the premise of investigating mechanical properties, the thermal conductivity of autoclaved aerated concrete (AAC) is a key index of self-insulation block walls for building energy conservation. This study focused on the effect of pore structures on the mechanical performance and thermal conductivity of AAC with the comparison of AAC base materials. Different kinds of AAC and their base materials were prepared and experimentally investigated. While maintaining a consistent mix proportion of the AAC base material, the pore structure of AAC was changed by the dosage of aluminum power/paste, foam stabilizer, and varying the stirring time of aluminum paste. The steam curing systems of AAC and the base material were determined based on SEM (Scanning Electronic Microscopy) and XRD (X-ray Diffraction) tests. With almost the same apparent density, the pore size decreased with the increasing content of foam stabilizer, and the mixing time of aluminum paste and foam stabilizer has a great influence on pore size. The thermal conductivity test and compressive test results indicated that that pore size had an effect on the thermal conductivity, but it had little effect on the compressive strength, and the thermal conductivity of sand aeration AAC was 8.3% higher than that of fly ash aeration AAC; the compressive strength was 10.4% higher, too. With almost the same apparent density, the regression mathematical model indicates that the thermal conductivity of AAC increased gradually with the increase of pore size, but it had little effect on the compressive strength. From the test results of basic mechanical properties, the mechanical model of cubic compressive strength, elastic modulus, axial compressive strength, and splitting tensile strength was obtained. The proposed stress–strain relationship model could well describe the relationship of AAC and the base material at the rising section of the curve.

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