Recycling and the end of life assessment of fluoropolymers: recent developments, challenges and future trends

Améduri, Bruno; Hori, Hisao

doi:10.1039/d2cs00763k

Cited by 44 publications

(32 citation statements)

References 160 publications

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“…This observation implies that the nascent behavior is thoroughly maintained without compromising the most interesting electroactive properties (β and γ) after processing. This feature is particularly important to process such materials in a solid state (below their melting temperature) to avoid the possible degradation or release of hazardous gas, , where the nascent polymer without melting, as received from the reactor, can be molded into desired shapes while retaining the polymorph perceived during polymerization.…”

Section: Resultsmentioning

confidence: 99%

Tailoring Electroactive β- and γ-Phases via Synthesis in the Nascent Poly(vinylidene fluoride) Homopolymers

Patil,

Zhao,

Ameduri

et al. 2024

Macromolecules

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Poly(vinylidene fluoride) (PVDF) has received much attention for its electroactive properties arising from βand γ-crystallographic phases. Until now, investigation deals with postpolymerization processing methods to secure βand γpolymorphs, although a deeper understanding of the promotion of βand γ-phases during the polymerization of vinylidene fluoride (VDF) is scarcely reported. This study scrutinizes the polymerization conditions and demonstrates how polymerization temperatures, times, and molar masses of the "nascent PVDF powder" affect the formation of the crystalline phases (α, β, and γ). It is presented that specific molar masses produced at various polymerization temperatures strongly control PVDF polymorphs and play a pivotal role in electroactive phase formation. The molar masses ranging from 100,000 to 350,000 g•mol −1 and polymerization temperatures ≤60 °C result in βand γ-phases, while the molar mass ≥450,000 g•mol −1 at 70 °C polymerization temperature promotes αand β-phases of PVDF. Additionally, PVDF chain defects also influence the electroactive phase formations; the lower the chain defects, the higher the β-phase content in PVDF. The polymorphs of PVDF homopolymers are identified by complementary spectroscopy and diffraction techniques, whereas the morphological changes influenced by the polymerization conditions are followed by electron microscopy. The morphological variation, from facet to spherical morphology, is correlated with the polymerization conditions. Finally, the preliminary results on the processing method demonstrate that the nascent PVDF homopolymers can be processed in the solid state, below their melting temperature, without influencing the polymorph perceived during polymerization. The nascent polymer having the β-polymorph retains its crystallographic and conformational structure prior to melting. The transformation from α to β and γ PVDF is accomplished through solid-state processing (compression-rolling-stretching) below the melting temperature of the nascent PVDF homopolymers. Compared to melt and solution processing, the solid-state processing is of advantage as it circumvents the work required against entropy to secure the oriented chains and the use of carcinogenic solvents. Moreover, environmentally friendly solid-state processing avoids the decomposition of the sample above the melting point that often causes the release of the hazardous gases in fluorinated polymers.

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Section: Resultsmentioning

confidence: 99%

Tailoring Electroactive β- and γ-Phases via Synthesis in the Nascent Poly(vinylidene fluoride) Homopolymers

Patil,

Zhao,

Ameduri

et al. 2024

Macromolecules

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“…In terms of durability, PVDF polymer is highly durable as it can be reused and processed for up to five times, which is very important in advanced applications and in the scope of sustainability. 141 A life cycle assessment (LCA) has been carried out to assess the environmental impact of PVDF, in which an acceptable value for the global warming potential (GWP) has been obtained (55.8 kg CO 2 equiv•kg −1 PVDF) due to the large demand for chlorine during its production. 142 With regard to processing and to increase sustainability, it has been demonstrated the suitability of replacing the conventional solvents with green solvents, including cyclic carbonate solvents 143 and acetyl tributyl citrate (ATBC), 144 among others.…”

Section: Sustainability and Circular Economy Considerationsmentioning

confidence: 99%

“…Thermal degradation process such as thermolysis is used to reuse and recycle PVDF. 141 Also, the decomposition of PVDF and its copolymers can be obtained by mineralization processes in subcritical water with the addition of KMnO 4 as oxidizing agent. 145 One of the possible ways is mechanical recycling through remelting through extrusion.…”

Section: Sustainability and Circular Economy Considerationsmentioning

confidence: 99%

Section: Poly(vinylidene Fluoride): Main Properties and Polymorphismmentioning

confidence: 99%

“…To further reduce environmental impact, it is necessary to define more efficient processing and recycling routes, as this polymer starts to degrade at relatively low temperatures (>400 °C). Thermal degradation process such as thermolysis is used to reuse and recycle PVDF . Also, the decomposition of PVDF and its copolymers can be obtained by mineralization processes in subcritical water with the addition of KMnO 4 as oxidizing agent …”

Section: Poly(vinylidene Fluoride): Main Properties and Polymorphismmentioning

confidence: 99%

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Smart and Multifunctional Materials Based on Electroactive Poly(vinylidene fluoride): Recent Advances and Opportunities in Sensors, Actuators, Energy, Environmental, and Biomedical Applications

Costa,

Cardoso,

Martins

et al. 2023

Chem. Rev.

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From scientific and technological points of view, poly(vinylidene fluoride), PVDF, is one of the most exciting polymers due to its overall physicochemical characteristics. This polymer can crystalize into five crystalline phases and can be processed in the form of films, fibers, membranes, and specific microstructures, being the physical properties controllable over a wide range through appropriate chemical modifications. Moreover, PVDF-based materials are characterized by excellent chemical, mechanical, thermal, and radiation resistance, and for their outstanding electroactive properties, including high dielectric, piezoelectric, pyroelectric, and ferroelectric response, being the best among polymer systems and thus noteworthy for an increasing number of technologies. This review summarizes and critically discusses the latest advances in PVDF and its copolymers, composites, and blends, including their main characteristics and processability, together with their tailorability and implementation in areas including sensors, actuators, energy harvesting and storage devices, environmental membranes, microfluidic, tissue engineering, and antimicrobial applications. The main conclusions, challenges and future trends concerning materials and application areas are also presented.

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Selected Fluoropolymers (A Class of PFAS Polymers)

Dourson,

Lasee,

Onyema

2024

Patty's Toxicology

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This chapter is about a series of fluorinated polymers (fluoropolymers) which belong to a broad class of chemical substances referred to as per‐ and polyfluoroalkyl substances (PFAS). PFAS are a unique class of anthropogenic chemicals consisting of carbon and fluorine atoms joined by very strong bonds, resulting in high‐performance properties. The overall structure of these fluoropolymers is the covalent linkage of one or more monomers, at least one of which is generally short carbon chains with fluorine atoms substituting for hydrogen atoms. The resulting fluoropolymer is a much larger molecule with very different uses, kinetics, and potential toxicity than the constituent monomers. For example, fluoropolymers are generally not well‐absorbed, if at all, in biological systems, thus avoiding to a great degree of any untoward toxicity. Unlike the monomers, the resulting fluoropolymers are usually chemically stable, biologically inert and nonbioaccumulative, water and oil resistant, and useful for many industrial applications. Because the chemical structure of these fluoropolymers makes them generally biologically unreactive and chemically inert, the available epidemiology and toxicology literature is minimal. This chapter will review the literature on fluoropolymers but will also briefly discuss the toxicity of the constituent monomers. Afterward, a summary of estimates of potential human risk by various agencies will be described. For information and practical guidance on the use of terminology in regard to PFASs, readers are referred to the OECD PFAS Terminology report [OECD, Reconciling Terminology of the Universe of Per‐ and Polyfluoroalkyl Substances: Recommendations and Practical Guidance , OECD Series on Risk Management, No. 61, OECD Publishing, Paris, 2021. Available at https://www.oecd.org/chemicalsafety/portal‐perfluorinated‐chemicals/terminology‐per‐and‐polyfluoroalkyl‐substances.pdf . Accessed October 10, 2023).

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Recycling and the end of life assessment of fluoropolymers: recent developments, challenges and future trends

Abstract: Herein, we present the state of the art technology on the recycling, reuse, thermal decomposition, and the life cycle assessment of fluoropolymers (FPs, ranging from PTFE and PVDF to various fluorinated copolymers based on VDF and TFE).

Cited by 44 publications

References 160 publications

Tailoring Electroactive β- and γ-Phases via Synthesis in the Nascent Poly(vinylidene fluoride) Homopolymers

Tailoring Electroactive β- and γ-Phases via Synthesis in the Nascent Poly(vinylidene fluoride) Homopolymers

Smart and Multifunctional Materials Based on Electroactive Poly(vinylidene fluoride): Recent Advances and Opportunities in Sensors, Actuators, Energy, Environmental, and Biomedical Applications

Selected Fluoropolymers (A Class of PFAS Polymers)

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