Mechanism of quiescent nanoplastic formation from semicrystalline polymers

Nicholas F. Mendez, Vivek Sharma, Michele Valsecchi, Vighnesh Pai, Johnny K. Lee, Linda S. Schadler, Alejandro J. Müller, Shelby Watson-Sanders, Mark Dadmun, Guruswamy Kumaraswamy () and Sanat K. Kumar ()
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Nicholas F. Mendez: New York
Vivek Sharma: Indian Institute of Technology Bombay
Michele Valsecchi: New York
Vighnesh Pai: New York
Johnny K. Lee: New York
Linda S. Schadler: University of Vermont
Alejandro J. Müller: Paseo Manuel de Lardizabal 3
Shelby Watson-Sanders: University of Tennessee Knoxville
Mark Dadmun: University of Tennessee Knoxville
Guruswamy Kumaraswamy: Indian Institute of Technology Bombay
Sanat K. Kumar: New York

Nature Communications, 2025, vol. 16, issue 1, 1-11

Abstract: Abstract Polymers are known to spontaneously produce microplastics (sizes 1 μm – 3 mm) and nanoplastics (10 nm – 1 μm). Still, the mechanisms by which environmentally-triggered Å-level random bond breaking events lead to the formation of these relatively large fragments are unclear. Significantly, $$\approx$$ ≈ 70% of commercial polymers are semicrystalline, with a morphology comprised of alternating crystalline and amorphous layers, each tens of nanometers thick. It is well-accepted that chain scission events accumulate in the amorphous phase. We show that this leads to mechanical failure and the concurrent release of particulate nanoplastics comprised of polydisperse stacks of lamellae even under quiescent conditions. Noncrystalline analogs, which do not have a well-defined microstructure, do not form nanoplastics. While the amorphous phase of the semicrystalline nanoplastics continues to degrade, crystal fragments do not, and hence, they temporally persist in the environment. These results stress the critical role of polymer microstructure and fracture mechanics on particulate nanoplastic creation.

Date: 2025
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DOI: 10.1038/s41467-025-58233-3

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