Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Stony Brook Univ., NY (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II); Univ. of Grenoble Alpes (France)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II); National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Stony Brook Univ., NY (United States)
Vapor-phase infiltration (VPI) of inorganic materials in polymers is increasingly becoming popular for synthesizing various functional hybrid materials. While AlOx infiltration using trimethylaluminum (TMA) has been extensively studied, the mechanism of diethylzinc (DEZ)-based ZnOx infiltration, especially one that is initiated by AlOx priming, has not received much attention because highly reactive hydroxyl groups generated by AlOx-priming are expected to dominate the initial binding of DEZ, thus enabling the overall ZnOx VPI. Here, we interrogate the ZnOx infiltration mechanism in AlOx-primed poly(methyl methacrylate) (PMMA) in comparison to the control AlOx-only infiltration by utilizing a suite of complementary characterizations, including quartz crystal microbalance mass gain measurement, transmission electron microscopy, infrared reflection–absorption spectroscopy (IRRAS), and synchrotron X-ray absorption spectroscopy (XAS). The multivalent TMA precursor and associated hyperbranched AlOx network can quickly saturate the AlOx infiltration by clogging the polymer-free volume near the top. On the contrary, the ZnOx infiltration using divalent DEZ precursor, once activated via AlOx-priming, can lead to accelerated ZnOx infiltration. With the help of IRRAS, XAS, and density functional theory (DFT) simulations, we uncover that the AlOx-priming enhances the reactivity of neighboring carbonyl groups toward DEZ and opens up simultaneous reaction pathways, leading to accelerated high-fidelity infiltration of ZnOx.
Tiwale, Nikhil, et al. "Alumina Priming-Mediated Enhanced Binding of Diethylzinc with Carbonyl Groups in Poly(Methyl Methacrylate) during Vapor-Phase Infiltration." Chemistry of Materials, vol. 38, no. 4, Feb. 2026. https://doi.org/10.1021/acs.chemmater.5c02584
Tiwale, Nikhil, Subramanian, Ashwanth, Sikder, Sayantani, et al., "Alumina Priming-Mediated Enhanced Binding of Diethylzinc with Carbonyl Groups in Poly(Methyl Methacrylate) during Vapor-Phase Infiltration," Chemistry of Materials 38, no. 4 (2026), https://doi.org/10.1021/acs.chemmater.5c02584
@article{osti_3020761,
author = {Tiwale, Nikhil and Subramanian, Ashwanth and Sikder, Sayantani and Qu, Xiaohui and Freychet, Guillaume and Gann, Eliot and Jaye, Cherno and Kisslinger, Kim and Boscoboinik, Jorge Anibal and Nam, Chang-Yong},
title = {Alumina Priming-Mediated Enhanced Binding of Diethylzinc with Carbonyl Groups in Poly(Methyl Methacrylate) during Vapor-Phase Infiltration},
annote = {Vapor-phase infiltration (VPI) of inorganic materials in polymers is increasingly becoming popular for synthesizing various functional hybrid materials. While AlOx infiltration using trimethylaluminum (TMA) has been extensively studied, the mechanism of diethylzinc (DEZ)-based ZnOx infiltration, especially one that is initiated by AlOx priming, has not received much attention because highly reactive hydroxyl groups generated by AlOx-priming are expected to dominate the initial binding of DEZ, thus enabling the overall ZnOx VPI. Here, we interrogate the ZnOx infiltration mechanism in AlOx-primed poly(methyl methacrylate) (PMMA) in comparison to the control AlOx-only infiltration by utilizing a suite of complementary characterizations, including quartz crystal microbalance mass gain measurement, transmission electron microscopy, infrared reflection–absorption spectroscopy (IRRAS), and synchrotron X-ray absorption spectroscopy (XAS). The multivalent TMA precursor and associated hyperbranched AlOx network can quickly saturate the AlOx infiltration by clogging the polymer-free volume near the top. On the contrary, the ZnOx infiltration using divalent DEZ precursor, once activated via AlOx-priming, can lead to accelerated ZnOx infiltration. With the help of IRRAS, XAS, and density functional theory (DFT) simulations, we uncover that the AlOx-priming enhances the reactivity of neighboring carbonyl groups toward DEZ and opens up simultaneous reaction pathways, leading to accelerated high-fidelity infiltration of ZnOx.},
doi = {10.1021/acs.chemmater.5c02584},
url = {https://www.osti.gov/biblio/3020761},
journal = {Chemistry of Materials},
issn = {ISSN 0897-4756},
number = {4},
volume = {38},
place = {United States},
publisher = {American Chemical Society (ACS)},
year = {2026},
month = {02}}