Energetic silicones: synthesis and characterization of pentaoxadiazole-PDMS copolymers
Standing at the forefront of energetics research is the exploration of energetic binders.
Shear, Trevor A.↗
Engineering topics
Varni, Anthony J.
Publications and source records attributed to Varni, Anthony J..
Competing Kinetic Consequences of CO 2 on the Oxidative Degradation of Branched Poly(ethylenimine)
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Enhanced hydrogen bonding via epoxide-functionalization restricts mobility in poly(ethylenimine) for CO 2 capture
Combined modeling and experiments uncover the influence of epoxide-functionalization on hydrogen bonding and mobility within poly(ethylenimine) CO 2 sorbents, rationalizing the antidegradation benefits conferred by functionalization.
36 MATERIALS SCIENCE↗
Proposed synthesis of a linear poly-ethylenimine with hydroxyl pendants substituents at the adjacent carbon
The synthesis of a linear poly-ethylenimine with pendant hydroxyl groups bonded to backbone carbons adjacent to the backbone amine groups is investigated and compared to the conventional method of functionalizing branched poly-ethylenimine using epoxides for use in direct air capture of carbon dioxide. The addition of hydroxyl groups imparts stability against both oxidative degradation and the formation of urea by reducing the number of primary amines, while the novel method of bonding to the adjacent backbone carbon rather than directly to the amine is hypothesized to retain the higher capacity for carbon dioxide of secondary amines when compared to tertiary amines. We also expect that the hydroxyl substituents will impart stronger hydrogen bonding capabilities, resulting in stronger interactions between adjacent polymer chains and a subsequent decrease in mobility.
36 MATERIALS SCIENCE↗
Thermal modulation of reaction equilibria controls mass transfer in CO 2 -binding organic liquids
CO 2 BOLs are promising CCS solvents, whose mass transfer rates improve upon cooling. We show this unintuitive behavior is due to slow transport of reaction products from the gas–liquid interface, caused by shifts in reaction equilibria.
36 MATERIALS SCIENCE↗
Probing the Kinetic Origin of Varying Oxidative Stability of Ethyl- vs. Propyl-spaced Amines for Direct Air Capture
Amine-based adsorbents are promising for direct air capture of CO 2 , yet oxidative degradation remains a key unmitigated risk hindering wide-scale deployment. Borrowing wisdom from the basic auto-oxidation scheme, insights are gained into the underlying degradation mechanisms of polyamines by quantum chemical, advanced sampling simulations, adsorbent synthesis, and accelerated degradation experiments. The reaction kinetics of polyamines are contrasted with that of typical aliphatic polymers and they elucidate for the first time the critical role of aminoalkyl hydroperoxide decomposition in the oxidative degradation of amino-oligomers. The experimentally observed variation in oxidative stability of polyamines with different backbone structures is explained by the relationship between the local chemical structure and the free energy barrier of aminoalkyl hydroperoxide decomposition, suggesting that its energetics can be used as a descriptor to screen and design new polyamines with improved stability. In conclusion, the developed computational capability sheds light on radical-induced degradation chemistry of other organic functional materials.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗