The application of α-hemihydrate gypsum (α-HH) is limited by several factors, such as a rapid hydration rate, short setting time, poor water resistance, and high cost. Especially because of the high production cost, although α-HH has excellent mechanical strength, it is rarely used in the field of building materials. In this study, based on the composition characteristics of new industrial solid waste (phosphate-rock acid-insoluble residue, PAIR) and to meet the needs of resource utilization, gypsum matrix composites were prepared by adding PAIR to α-HH to solve the problems of short setting time and poor water resistance of gypsum matrix composites and improve the comprehensive properties of α-HH products. The results show that when the different types of pores formed during the hydration of α-HH were filled with inert substances, such as silicon dioxide, insoluble phosphate, and calcium fluoride from PAIR, the proportion of mesopores in the composite products increased, whereas that of harmful macropores decreased. The compressive and flexural softening coefficients of the PAIR/α-HH system with 23% PAIR were the highest at 57.25 and 60.125%, respectively, and the water resistance of the system was improved; when the content of PAIR reaches 35%, the strength of the composite products decreased from 58.125 to 43.8MPa. The HPO42- in PAIR partially replaces the SO42- ion in the dihydrate gypsum (DH) lattice to form a Ca(SO4, HPO4)•2H2O double salt, leading to the production of eutectic phosphorus. Soluble F-, Al3+, Mg2+, and phosphorus-containing substances in PAIR form a variety of complex ions in PAIR/α-HH aqueous solution, which are adsorbed onto the surface of the new DH phase; the crystal morphology changed from thick, long columns to clusters, thin rods, and plates, inhibiting the nucleation and growth of DH and changing its crystal growth rate and crystallization behavior. Therefore, the setting time of gypsum is prolonged; when 35% PAIR was added, the induced nucleation period of the PAIR/α-HH system was prolonged from 40 to 265min, and the final setting time was from 12 to 360min. By mixing solid waste PAIR, while the setting time of α-HH is prolonged, its water resistance is improved, and its mechanical strength is not significantly reduced, reducing the cost. From the perspective of economy and environmental protection, this study is a way to α-HH is widely used in the field of building materials.
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