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    Material properties of ureolytically induced calcium carbonate adhesives
    (Montana State University - Bozeman, College of Engineering, 2023) Anjum, Sobia; Chairperson, Graduate Committee: Robin Gerlach; This is a manuscript style paper that includes co-authored chapters.
    Polymers used in adhesive applications are often petrochemical-based and release volatile organic compounds (VOCs) during application. These VOCs can accumulate indoors to the detriment of human health. Biopolymers potentially offer a non-toxic and sustainable alternative to synthetic polymers but generally have limited physical stability and low mechanical performance. One of the methods of improving the stability and adhesive performance of biopolymers is the addition of a mineral phase to reinforce biopolymer adhesives. In this work, biomineral-reinforced biopolymer adhesives were produced by ureolytically induced precipitation of calcium carbonate in the presence of guar gum and soy protein. The microbially and enzymatically induced ureolysis was carried out by the ureolytic bacterium, Sporosarcina pasteurii, or by jack bean urease. The resulting adhesives were referred to as ureolytically induced calcium carbonate precipitation (UICP)-reinforced adhesives and specifically microbially and enzymatically induced calcium carbonate (MICP and EICP)- reinforced adhesives. The adhesive strength of these composite adhesives was optimized by varying calcium and cell (or enzyme) concentrations. The adhesive strength of biomineral reinforced guar gum and soy protein biopolymers was up to 2.5 and 6 times higher than the adhesive strength of the biopolymers alone, respectively. The durability of the MICP-reinforced adhesives was tested after varying immersions (24 h and 7 days), relative humidities (50 and 80% RH), and temperatures (-20, 100, and 300?C). The durability of the MICP-reinforced adhesives, upon immersion, was significantly improved compared to biopolymer alone, and maintained their adhesive strength at moderate humidities and from below-freezing to room temperatures after 7- day exposures. To determine the effect of biopolymers on the nanoscale material properties of biomineral aggregates, enzymatically induced calcium carbonate precipitation was induced in the presence of a standard protein, Bovine Serum Albumin (BSA). Nanoindentation and Atomic Force Microscopy show that the moduli of the mineral precipitates were significantly lowered in the presence of BSA. Atomic force microscopy also showed that BSA introduced structural variations and moduli gradation in biominerals. These results demonstrate that the presence of a protein additive, specifically BSA, can alter the nanoscale structure and material properties of calcium carbonate precipitates. Using an organic additive to manipulate microscale material properties of biominerals offers possibilities for advanced control at the microscale and enhanced toughness at the macroscale for engineering applications such as in construction, binder, and adhesive applications.
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