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TitleReactive Decaborane Initiates Low-Temperature Polymer Decomposition and Drives Ceramic Formation
Date2026
AbstractBoron carbide (B4C) is a ceramic of considerable interest due to its high hardness, melting point, excellent thermal stability, low density, and chemical inertness. Decaborane-functionalized preceramic polymers (PCPs) prepared from ring-opening metathesis polymerization (ROMP) are excellent single-source precursors of B4C, but the mechanistic details for the decomposition and ceramic conversion during pyrolysis have been overlooked, preventing advances in redesigning preceramic polymers that have high char yields and desirable chemical compositions. Herein, we reveal new insights into the role of decaborane during the polymer-to-ceramic transition of poly(cyclooctenyldecaborane) (PCD) to boron carbide. ROMP of the cyclooctenyldecaborane monomer enabled controllable molecular weight and produced a series of polymers with molecular weights up to 35 kg/mol and dispersities (D) in the range of 1.3-1.6. Thermogravimetric analysis coupled with infrared spectroscopy and mass spectrometry (TGA-IR and TGA-MS, respectively) of PCD revealed the evolution of small hydrocarbon species following an initial release of hydrogen at low decomposition temperatures around 250 °C, which is in stark contrast to the decomposition profile of unfunctionalized poly(cyclooctadiene) (PCOD) that transitions into volatile hydrocarbon species at approximately 450 °C. ReaxFF molecular dynamics simulations accurately predicted that hydrogen release from decaborane initiated the polymer-to-ceramic conversion, followed by the exothermic formation of boron clusters, which promote the thermal decomposition of the hydrocarbon polymer backbone. These findings establish that decaborane actively directs the polymer-to-ceramic conversion rather than serving solely as a boron source, providing mechanistic insight that will enable the rational design of next-generation PCPs with enhanced ceramic yields and tunable compositions.
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Data DOIdoi:10.26208/b305-3855

Researchers
Stovall, B. J.
Penn State Department of Materials Science and Engineering
Ul Hosna, A.
Penn State Department of Mechanical Engineering
Carvalho, T. C.
Penn State Department of Materials Science and Engineering
Sabaratne, K.
Penn State Department of Chemistry
Halanayake, K. D.
Penn State Department of Chemistry
Dasgupta, N.
University of Southern California
Baradwaj, N.
University of Southern California
Reifsnyder Hickey, D.
Penn State Department of Materials Science and Engineering
Nakano, A.
University of Southern California
Vashishta, P.
University of Southern California
Maria, Jon-Paul
Penn State Department of Materials Science and Engineering
van Duin, A.
Penn State Department of Materials Science and Engineering
Hickey, R. J.
Penn State Department of Materials Science and Engineering

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References
Benjamin J. Stovall, Asma Ul Hosna, Tainara Coutinho de Carvalho, Kavindi Sabaratne, Kalana D. Halanayake, Nabankur Dasgupta, Nitish Baradwaj, Danielle Reifsnyder Hickey, Aiichiro Nakano, Priya Vashishta, Jon-Paul Maria, Adri C. T. van Duin, Robert J. Hickey; Reactive Decaborane Initiates Low-Temperature Polymer Decomposition and Drives Ceramic Formation. Chem. Mater. 2026; https://doi.org/10.1021/acs.chemmater.6c02312