{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,17]],"date-time":"2026-09-17T20:58:52Z","timestamp":1789678732692,"version":"4.0.1"},"reference-count":34,"publisher":"MDPI AG","issue":"11","license":[{"start":{"date-parts":[[2025,5,23]],"date-time":"2025-05-23T00:00:00Z","timestamp":1747958400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Polymers"],"abstract":"<jats:p>To tackle the degradation of sealing performance in nitrile butadiene rubber (NBR) seals due to material aging during long-term service, this study integrates experimental and molecular simulation methods to elucidate the aging mechanism. Experimental results reveal that the contents of C=C and C=O functional groups significantly decrease during aging, accompanied by enhanced hydrophobicity and increased crosslink density of NBR, indicating that crosslinking reactions dominate the aging process with the participation of C=C and C=O groups. Quantum mechanics (QM) and molecular dynamics (MD) simulations further demonstrate that \u03b1-H, C=C, and C\u2261N groups are preferentially oxidized due to their low bond energies. The oxidation of NBR generates unstable epoxy intermediates, which undergo chain scission to form ketones, aldehydes, and ultimately crosslinked structures. Using a multi-dimensional evaluation system based on bond dissociation energy (BDE), solubility parameter (\u0394\u03b4), and migration coefficient (MSD), four antioxidants (4010NA, 4010, MC, and BHT) were screened. BHT emerges as the optimal choice, exhibiting superior free radical scavenging ability (BDE = 346.3 kJ\/mol), good matrix compatibility (\u0394\u03b4 = 2.95), and anti-migration properties. The MD-based screening method established herein provides a theoretical basis for designing antioxidant systems in high-performance rubber materials, facilitating the development of advanced rubber products.<\/jats:p>","DOI":"10.3390\/polym17111446","type":"journal-article","created":{"date-parts":[[2025,5,23]],"date-time":"2025-05-23T06:35:09Z","timestamp":1747982109000},"page":"1446","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":12,"title":["A Study on the Aging Mechanism and Anti-Aging Properties of Nitrile Butadiene Rubber: Experimental Characterization and Molecular Simulation"],"prefix":"10.3390","volume":"17","author":[{"given":"Min","family":"Zhu","sequence":"first","affiliation":[{"name":"Naval University of Engineering, Wuhan 430033, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hanyuan","family":"Huang","sequence":"additional","affiliation":[{"name":"Naval University of Engineering, Wuhan 430033, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Haiyan","family":"Li","sequence":"additional","affiliation":[{"name":"Naval University of Engineering, Wuhan 430033, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gui","family":"Huang","sequence":"additional","affiliation":[{"name":"Naval University of Engineering, Wuhan 430033, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jingjing","family":"Lan","sequence":"additional","affiliation":[{"name":"Naval University of Engineering, Wuhan 430033, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jing","family":"Fu","sequence":"additional","affiliation":[{"name":"Naval University of Engineering, Wuhan 430033, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Juqin","family":"Fan","sequence":"additional","affiliation":[{"name":"Naval University of Engineering, Wuhan 430033, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yujun","family":"Liu","sequence":"additional","affiliation":[{"name":"Naval University of Engineering, Wuhan 430033, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhiwu","family":"Ke","sequence":"additional","affiliation":[{"name":"China State Shipbuilding Corporation, Limited (CSSC) 719th Research Institute, Wuhan 430205, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiaojie","family":"Guo","sequence":"additional","affiliation":[{"name":"China State Shipbuilding Corporation, Limited (CSSC) 719th Research Institute, Wuhan 430205, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hongkuan","family":"Zhou","sequence":"additional","affiliation":[{"name":"China State Shipbuilding Corporation, Limited (CSSC) 719th Research Institute, Wuhan 430205, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yan","family":"Li","sequence":"additional","affiliation":[{"name":"Naval University of Engineering, Wuhan 430033, China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2025,5,23]]},"reference":[{"key":"ref_1","first-page":"608","article-title":"Hygrothermal aging characteristics and mechanism of nitrile rubber for transformer sealing","volume":"49","author":"Gao","year":"2023","journal-title":"High Volt. Eng."},{"key":"ref_2","first-page":"133","article-title":"Effects of heterogeneous aging in compressed HNBR and EPDM O-ring seals","volume":"134","author":"Jaunich","year":"2016","journal-title":"Polym. Degrad. Stab."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"59","DOI":"10.1016\/j.polymertesting.2016.06.010","article-title":"Investigation of aging behavior and mechanism of nitrile-butadiene rubber (NBR) in the accelerated thermal aging environment","volume":"54","author":"Liu","year":"2016","journal-title":"Polym. Test."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"628","DOI":"10.1007\/s11668-018-0451-3","article-title":"Failure Analysis of Nitrile Rubber O-Rings Static Sealing for Packaging Barrel","volume":"18","author":"Wei","year":"2018","journal-title":"J. Fail. Anal. Prev."},{"key":"ref_5","first-page":"47156","article-title":"Stress\u2013thermal oxidative aging behavior of hydrogenated nitrile rubber seals","volume":"136","author":"Lou","year":"2018","journal-title":"J. Appl. Polym. Sci."},{"key":"ref_6","first-page":"89","article-title":"Infrared spectroscopy study on aging mechanism and life prediction of butyl rubber","volume":"43","author":"Zheng","year":"2013","journal-title":"Aerosp. Mater. Technol."},{"key":"ref_7","first-page":"762","article-title":"Aging behavior and mechanism of nitrile rubber under multi-factor coupling","volume":"52","author":"Li","year":"2021","journal-title":"Acta Polym. Sin."},{"key":"ref_8","doi-asserted-by":"crossref","unstructured":"Zhang, F., Yang, R., and Lu, D. (2023). Investigation of polymer aging mechanisms using molecular simulations: A review. Polymers, 15.","DOI":"10.3390\/polym15081928"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"21318","DOI":"10.1039\/D0RA03425H","article-title":"Insight into the anti-aging mechanisms of natural phenolic antioxidants in natural rubber composites using a screening strategy based on molecular simulation","volume":"10","author":"Lu","year":"2020","journal-title":"RSC Adv."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"110595","DOI":"10.1016\/j.compscitech.2024.110595","article-title":"Multiscale simulation study on radiation aging of EPDM and preparation of radiation-resistant materials","volume":"252","author":"Wang","year":"2024","journal-title":"Compos. Sci. Technol."},{"key":"ref_11","first-page":"57","article-title":"Research progress on additives for radiation-resistant rubber aging","volume":"36","author":"Zhu","year":"2024","journal-title":"J. Nav. Univ. Eng."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"117865","DOI":"10.1016\/j.molliq.2021.117865","article-title":"Insights into interfacial behaviours of surfactant and polymer: A molecular dynamics simulation","volume":"346","author":"Zhou","year":"2022","journal-title":"J. Mol. Liq."},{"key":"ref_13","doi-asserted-by":"crossref","unstructured":"Yang, J., and Lou, W. (2022). Molecule dynamics simulation of the effect of oxidative aging on properties of nitrile rubber. Polymers, 14.","DOI":"10.3390\/polym14020226"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"15","DOI":"10.1016\/j.polymdegradstab.2016.02.028","article-title":"DFT studies of the effectiveness of p-phenylenediamine antioxidants through their Cu(II) coordination ability","volume":"128","author":"Puskarova","year":"2016","journal-title":"Polym. Degrad. Stab."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"110223","DOI":"10.1016\/j.polymdegradstab.2022.110223","article-title":"Recent progress in the rubber antioxidants: A review","volume":"207","author":"Zhao","year":"2023","journal-title":"Polym. Degrad. Stab."},{"key":"ref_16","doi-asserted-by":"crossref","unstructured":"Song, M., Yue, X., Chang, C., Cao, F., Yu, G., and Wang, X. (2022). Investigation of the compatibility and damping performance of graphene oxide grafted antioxidant\/nitrile-butadiene rubber composite: Insights from experiment and molecular simulation. Polymers, 14.","DOI":"10.3390\/polym14040736"},{"key":"ref_17","unstructured":"(2018). National Technical Committee for Standardization of Rubber and Rubber Products (SAC\/TC 35). Determination Method for Constant Compression Permanent Deformation of Vulcanized Rubber. (Standard No. GB\/T 1683-2018)."},{"key":"ref_18","doi-asserted-by":"crossref","unstructured":"Zhu, M., Ma, D., Zhou, Y., Huang, H., Shao, Z., Wu, F., and Li, B. (2024). The change of sealing property in the aging process of NBR sealing equipment based on finite element analysis. Coatings, 14.","DOI":"10.3390\/coatings14091178"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"49526","DOI":"10.1002\/app.49526","article-title":"Promoting the dispersibility of silica and interfacial strength of rubber\/silica composites prepared by latex compounding","volume":"137","author":"Sun","year":"2020","journal-title":"J. Appl. Polym. Sci."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"41287","DOI":"10.1021\/acsami.1c10765","article-title":"Gamma radiation chemistry of polydimethylsiloxane foam in radiation-thermal environments: Experiments and simulations","volume":"13","author":"Liu","year":"2021","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"108193","DOI":"10.1016\/j.compscitech.2020.108193","article-title":"Effect of multi-modified layered double hydroxide on aging resistance of nitrile-butadiene rubber","volume":"195","author":"Wan","year":"2020","journal-title":"Compos. Sci. Technol."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"109956","DOI":"10.1016\/j.compscitech.2023.109956","article-title":"Aminosilane modified graphene oxide for reinforcing nitrile butadiene rubber: Experiments and molecular dynamic simulations","volume":"235","author":"Yang","year":"2023","journal-title":"Compos. Sci. Technol."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"5216","DOI":"10.1021\/acs.est.2c08717","article-title":"Computational studies of rubber ozonation explain the effectiveness of 6PPD as an antidegradant and the mechanism of its quinone formation","volume":"57","author":"Rossomme","year":"2023","journal-title":"Environ. Sci. Technol."},{"key":"ref_24","first-page":"199","article-title":"Degradation of hydrogenated nitrile rubber (HNBR) O-rings exposed to simulated servo system conditions","volume":"140","author":"Lou","year":"2017","journal-title":"Polym. Degrad. Stab."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"110512","DOI":"10.1016\/j.polymdegradstab.2023.110512","article-title":"Investigation on the Thermo\u2014Oxidative Aging Resistance of Nitrile\u2014Butadiene Rubber\/Polyamide Elastomer Blend and the Swelling Behaviors in Fuels Predicted via Hansen Solubility Parameter Method","volume":"217","author":"Wang","year":"2023","journal-title":"Polym. Degrad. Stab."},{"key":"ref_26","doi-asserted-by":"crossref","unstructured":"Luo, R., Kang, D., Huang, C., Yan, T., Li, P., Ren, H., and Zhang, Z. (2023). Mechanical Properties, Radiation Resistance Performances, and Mechanism Insights of Nitrile Butadiene Rubber Irradiated with High\u2014Dose Gamma Rays. Polymers, 15.","DOI":"10.3390\/polym15183723"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"e54068","DOI":"10.1002\/app.54068","article-title":"Aging Characterization of Different Nitrile Butadiene Rubbers for Sealing in a Pneumatic System: Linking the Change of the Physicochemical State to the Mechanical Properties","volume":"140","author":"Redon","year":"2023","journal-title":"J. Appl. Polym. Sci."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"280","DOI":"10.1016\/j.compositesb.2016.03.039","article-title":"Enhanced Mechanical and Thermal Properties of Recycled ABS\/Nitrile Rubber\/Nanofil N15 Nanocomposites","volume":"93","author":"Nguyen","year":"2016","journal-title":"Compos. B Eng."},{"key":"ref_29","first-page":"107683","article-title":"Modal performance degradation of naturally aged NBR","volume":"114","author":"Ammineni","year":"2022","journal-title":"Polym. Test."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"106954","DOI":"10.1016\/j.polymertesting.2020.106954","article-title":"Tribological behaviour of acrylonitrile-butadiene rubber under thermal oxidation ageing","volume":"93","author":"Li","year":"2021","journal-title":"Polym. Test."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"2442","DOI":"10.1016\/j.carbon.2012.01.066","article-title":"Multi-walled carbon nanotubes acting as free radical scavengers in gamma-irradiated ultrahigh molecular weight polyethylene composites","volume":"50","author":"Castell","year":"2012","journal-title":"Carbon"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"109514","DOI":"10.1016\/j.polymdegradstab.2021.109514","article-title":"Study on the ozone aging mechanism of Natural Rubber","volume":"186","author":"Zheng","year":"2021","journal-title":"Polym. Degrad. Stab."},{"key":"ref_33","doi-asserted-by":"crossref","unstructured":"(2016). Ozonation of anilines: Kinetics, stoichiometry, product identification and elucidation of pathways. Water Res., 98, 147\u2013159.","DOI":"10.1016\/j.watres.2016.04.001"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"123523","DOI":"10.1016\/j.polymer.2021.123523","article-title":"Study on structures, dynamics and mechanical properties of styrene butadiene rubber (SBR)\/silica interfaces: A fully atomistic molecular dynamics","volume":"218","author":"Zhou","year":"2021","journal-title":"Polymer"}],"container-title":["Polymers"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2073-4360\/17\/11\/1446\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,9]],"date-time":"2025-10-09T17:39:01Z","timestamp":1760031541000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2073-4360\/17\/11\/1446"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,5,23]]},"references-count":34,"journal-issue":{"issue":"11","published-online":{"date-parts":[[2025,6]]}},"alternative-id":["polym17111446"],"URL":"https:\/\/doi.org\/10.3390\/polym17111446","relation":{},"ISSN":["2073-4360"],"issn-type":[{"value":"2073-4360","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,5,23]]}}}