Formation of three-dimensional bicontinuous structures via molten salt dealloying studied in real-time by in situ synchrotron X-ray nano-tomography

Xiaoyang Liu, Arthur Ronne, Lin Chieh Yu, Yang Liu, Mingyuan Ge, Cheng Hung Lin, Bobby Layne, Phillip Halstenberg, Dmitry S. Maltsev, Alexander S. Ivanov, Stephen Antonelli, Sheng Dai, Wah Keat Lee, Shannon M. Mahurin, Anatoly I. Frenkel, James F. Wishart, Xianghui Xiao, Yu chen Karen Chen-Wiegart

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Abstract

Three-dimensional bicontinuous porous materials formed by dealloying contribute significantly to various applications including catalysis, sensor development and energy storage. This work studies a method of molten salt dealloying via real-time in situ synchrotron three-dimensional X-ray nano-tomography. Quantification of morphological parameters determined that long-range diffusion is the rate-determining step for the dealloying process. The subsequent coarsening rate was primarily surface diffusion controlled, with Rayleigh instability leading to ligament pinch-off and creating isolated bubbles in ligaments, while bulk diffusion leads to a slight densification. Chemical environments characterized by X-ray absorption near edge structure spectroscopic imaging show that molten salt dealloying prevents surface oxidation of the metal. In this work, gaining a fundamental mechanistic understanding of the molten salt dealloying process in forming porous structures provides a nontoxic, tunable dealloying technique and has important implications for molten salt corrosion processes, which is one of the major challenges in molten salt reactors and concentrated solar power plants.

Original languageEnglish
Article number3441
JournalNature Communications
Volume12
Issue number1
DOIs
StatePublished - Dec 1 2021

Funding

This work was supported as part of the Molten Salts in Extreme Environments (MSEE) Energy Frontier Research Center, funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. BNL, and ORNL are operated under DOE contracts DESC0012704, and DE-AC05-00OR22725, respectively. Work at Stony Brook University was supported by MSEE through a subcontract from BNL. This research used resources, the Full Field X-ray Imaging (FXI, 18-ID) beamline, and the Beamline for Materials Measurement (BMM, 6-BM) of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract DE-SC0012704. Partial support for A. Ronne was provided by an NSF NRT Award in Quantitative Analysis of Dynamic Structures (DGE 1922639) as a fellowship. The authors are grateful to Dr. Bruce Ravel (National Institute of Standards and Technology), scientist at BMM beamline, for his expertise and support of experiments. The authors acknowledged the inputs and support on heater design from Dr. Steve Hulbert (NSLS-II, BNL). Dr. Kazuhiro Iwamatsu is acknowledged for assistance during the sample preparation. Current and former Chen-Wiegart group members are acknowledged for operating the FXI and BMM beamtimes together: Chonghang Zhao, Qingkun Meng, Karol Dyro, Dean Yen, and Brian Conry.

FundersFunder number
MSEE
National Science FoundationDGE 1922639
National Science Foundation
U.S. Department of Energy
Office of Science
Basic Energy SciencesDE-AC05-00OR22725
Basic Energy Sciences
Brookhaven National LaboratoryDE-SC0012704, 6-BM, 18-ID
Brookhaven National Laboratory

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