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DOE OSTI · 2572397

Renewable Lactam Monomer for Tunable and Processable Polyamides

Häkkinen, Satu [Univ. of Minnesota, Minneapolis, MN (United States)]·Krajovic, Daniel M. [Univ. of Minnesota, Minneapolis, MN (United States)] (ORCID:0000000153111941)·Chamberlain, Kari M. [Univ. of Minnesota, Minneapolis, MN (United States)] (ORCID:0000000307436010)·Shippee, Joshua [Univ. of Minnesota, Minneapolis, MN (United States)]·Biswas, Arpan [Univ. of Minnesota, Minneapolis, MN (United States)]·Zhang, Honghu [Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)] (ORCID:0000000317847825)·Felsenthal, Lillian M. [Northwestern Univ., Evanston, IL (United States)] (ORCID:0009000478833130)·Dichtel, William R. [Northwestern Univ., Evanston, IL (United States)] (ORCID:0000000236356119)·Hillmyer, Marc A. [Univ. of Minnesota, Minneapolis, MN (United States)] (ORCID:0000000182553853)
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Abstract

Replacement of petroleum-derived monomers with renewable alternatives is an integral part of the sustainable polymer framework. Research in this area involves the search for bio-based or recycled starting materials for traditional polymers, as well as investigations into new materials accessible from renewable feedstocks. Focusing on the latter, we studied the properties of polyamides synthesized from γ-methyl-ε-caprolactam through anionic ring-opening polymerization by an activated monomer mechanism. Here, the amorphous homopolymer presents high stiffness (Young’s modulus, ≈3 GPa), strength (stress at break, ≈80 MPa) and toughness under dry (low humidity) conditions, high ductility (strain at break, ≈1100%) in humid environments, optical clarity, and excellent processability due to its non-crystallizable nature and solubility in common organic solvents. Copolymerization with ε-caprolactam allows tailoring the mechanical properties and crystallinity in the resultant copolymers and provides new opportunities for advanced manufacturing and other applications.

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36 MATERIALS SCIENCEAmidesCopolymersCrystallizationMonomersPolymers

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Häkkinen, Satu [Univ. of Minnesota, Minneapolis, MN (United States)], Krajovic, Daniel M. [Univ. of Minnesota, Minneapolis, MN (United States)] (ORCID:0000000153111941), Chamberlain, Kari M. [Univ. of Minnesota, Minneapolis, MN (United States)] (ORCID:0000000307436010), Shippee, Joshua [Univ. of Minnesota, Minneapolis, MN (United States)], Biswas, Arpan [Univ. of Minnesota, Minneapolis, MN (United States)], Zhang, Honghu [Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)] (ORCID:0000000317847825), Felsenthal, Lillian M. [Northwestern Univ., Evanston, IL (United States)] (ORCID:0009000478833130), Dichtel, William R. [Northwestern Univ., Evanston, IL (United States)] (ORCID:0000000236356119), Hillmyer, Marc A. [Univ. of Minnesota, Minneapolis, MN (United States)] (ORCID:0000000182553853). 2025-03-14. Renewable Lactam Monomer for Tunable and Processable Polyamides. https://doi.org/10.1021/acs.macromol.4c03199

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DOE OSTI2026

Cyclic moisture reactivation of calcium sorbents for long duration thermochemical energy storage

The transition to a flexible and reliable energy infrastructure, using electro-thermal energy generation technologies such as geothermal, concentrated solar power, and nuclear, usually demands simultaneous advancement of thermal energy storage (TES) to support on-demand electricity generation and industrial applications while mitigating the inherent intermittency of renewable energy sources and power outages from direct energy generation. Among TES technologies, thermochemical energy storage (TCES) based on calcium looping emerges as a compelling high-power energy storage candidate due to its high reaction enthalpy, compatibility with elevated operating temperatures, and abundance of low-cost materials. However, the long-term durability of calcium-based sorbents for TCES is hindered by surface sintering and particle aggregation, leading to performance degradation over repeated thermal cycles. This study explores a moisture hydration-based strategy to regenerate a degraded calcium sorbent and mitigate performance degradation for long duration TCES. The addition of moisture transforms calcium oxide into calcium hydroxide and produces intercalation water layers, associated with a regenerated surface area and reduced calcium oxide crystallite size. Both these effects are beneficial in restoring the sorbents' reactivity for carbonization. Additionally, an optimized hydration-assisted reactivation protocol balances the recovered energy storage capacity with heating penalty required for moisture removal from hydrated samples, resulting in an enhanced energy storage capacity up to 176% compared to benchmark sorbents that undergo cycling without reactivation after 60 cycles. In conclusion, these results highlight the potential of hydration-assisted reactivation to enhance the long-term performance of TCES, providing an effective pathway to advancing electro-thermal storage technologies.

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