Synergistic Dual-Cure Reactions for the Fabrication of Thermosets by Chemical Heating
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Al(ReCu)2 crystallizes in the tetragonal P4/mbm space group. The structure is three-dimensional. Re is bonded in a 11-coordinate geometry to five equivalent Re, six equivalent Cu, and four equivalent Al atoms. There are one shorter (2.74 Å) and four longer (3.13 Å) Re–Re bond lengths. There are two shorter (2.58 Å) and four longer (2.64 Å) Re–Cu bond lengths. All Re–Al bond lengths are 2.95 Å. Cu is bonded in a 2-coordinate geometry to six equivalent Re and two equivalent Al atoms. Both Cu–Al bond lengths are 2.30 Å. Al is bonded in a square co-planar geometry to eight equivalent Re and four equivalent Cu atoms.
Thermoset composites are strong candidates for large-scale material extrusion additive manufacturing (AM). However, uncured thermoset composites become unstable as print height increases. Here, chemical initiation of vinyl ester immediately before deposition was used to suppress collapse and enable large-scale thermoset printing. Structural stability was assessed by printing thin walls at various layer times and monitoring thermal gradients with an infrared camera. Stable printing was observed at a layer time of 4.50 min, approximately half the gel time of the material (8 min). Self-weight collapse occurred at short layer time (0.68 min), whereas warpage occurred at long layer time (6.50 min). Here, a new behavior was discovered at intermediate layer time (2.25 min) where the heat generated by the reaction causes new, un-gelled layers to flow. Forced convection eliminates this behavior, stabilizing the 2.25-min layer time print. These findings motivated development of a less exothermic material system, which was used to print a large-scale mold and demonstrate the value of this understanding. By presenting these challenges of large-scale reactive thermoset AM for the first time, this work motivates focused studies of the complex interplay between rheological, thermal, and chemical behaviors to improve the feasibility of large-scale thermoset AM. Tensile properties of the printed material were also measured. Longitudinal and transverse elastic moduli are 3.79 and 2.95 GPa, respectively, and corresponding tensile strengths are 36.11 and 18.83 MPa. The glass transition temperature is 93.13 °C.
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K-struvite, the main hydrate of magnesium potassium phosphate (MKP) cements, dehydrates at ~50 °C, thus elevated temperatures at service conditions could affect cement properties and durability. In this study, properties and hydration of MKP cement without and with wollastonite were investigated at 20 and 50 °C. In hydrated pure MKP cement K-struvite decomposes progressively over time to MgKPO{sub 4}·H{sub 2}O at 50 °C, which leads to a strong reduction of solid volume and severe strength loss. The presence of wollastonite significantly slows down the decomposition rate of K-struvite, which is still observed after 393 days at 50 °C. K-struvite together with amorphous hydroxyapatite, M-(C)-S-H and CaK{sub 3}H(PO{sub 4}){sub 2} from the wollastonite reaction result in a cement with good short and long-term strength at both 20 and 50 °C.
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This paper evaluates the lifecycle economic and environmental benefits of implementing CO 2 utilization and storage within advanced engineered cementitious composite (ECC) railway ties. Using CO 2 -treated ECC ties can yield lifecycle benefits primarily due to enhanced material properties – increased lifespan in this case – instead of due to the stored CO 2 that would otherwise enter the atmosphere. Sequestration-based policies such as 45Q in the United States would therefore not incentivize deployment of ECC railway ties, despite their considerable CO 2 avoidance opportunities. To reach these conclusions, cradle-to-grave lifecycle models were developed for ECC ties and conventional concrete ties and evaluated under 1000 possible use-phase scenarios. The models incorporated premature tie failures – consistent with real-world observations – that were used to study a wide range of non-linear impacts arising from the random nature of tie failures and replacements. The results show that past studies that neglected premature failure of ties may have underestimated lifecycle greenhouse gas (GHG) emissions of concrete rail ties by nearly three times. Overall, servicing a track with ECC ties instead of concrete ties can reduce the lifecycle costs and GHG emissions by 12% and 21% respectively, based on median values of 1000 model run results. The expected benefits would be larger for entities like Amtrak that plan to expand concrete tie infrastructure despite significant challenges with premature concrete tie failures. Furthermore, the results of this study suggest that the lifespan of ECC ties needs to be at least 25% longer than concrete ties to achieve net lifecycle benefits. The possibility of this should be tested and confirmed under real-world conditions.
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Photopolymerization induced phase separation (PIPS) is utilized to develop materials in a single step that are hydrophobic on one face and hydrophilic on the other.