Manipulating Frontal Polymerization and Instabilities with Phase-Changing Microparticles

Gao, Yuan; Dearborn, Mason A.; Vyas, Sagar; Kumar, Aditya; Hemmer, Julie; Wang, Zhao; Wu, Qiong; Alshangiti, Omar; Moore, Jeffrey S.; Esser‐Kahn, Aaron P.; Geubelle, Philippe H.

doi:10.1021/acs.jpcb.1c03899

Cited by 15 publications

(16 citation statements)

References 41 publications

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“…Systems employing FROMP have heavily employed DCPD or norbornene derivatives as the monomer of choice (refs , , , , , , , , , , , − ). As stated previously, the heat released by polymerization (Δ H p ) dictates the feasibility toward frontal application; as a catalytic process, the total quantity of heat released in ROMP depends only on the monomer itself, assuming that the reaction reaches completion.…”

Section: Chemistries Of Existing Frontal Polymerization Systemsmentioning

confidence: 99%

“…Pattern formation in FROMP may also occur through localized disruption of thermal or mass transport. Recent work from Gao et al , demonstrated that the inclusion of poly(caprolactone) microparticles in COD or DCPD resins introduces bias into the introduces periodic features in the temperature and velocity profiles of the front. During polymerization, the microparticles undergo an endothermic solid to liquid phase change that redirects thermal energy away from the reaction front.…”

Section: Applications Of Frontal Polymerizationmentioning

confidence: 99%

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Frontal Polymerizations: From Chemical Perspectives to Macroscopic Properties and Applications

et al. 2023

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The synthesis and processing of most thermoplastics and thermoset polymeric materials rely on energy-inefficient and environmentally burdensome manufacturing methods. Frontal polymerization is an attractive, scalable alternative due to its exploitation of polymerization heat that is generally wasted and unutilized. The only external energy needed for frontal polymerization is an initial thermal (or photo) stimulus that locally ignites the reaction. The subsequent reaction exothermicity provides local heating; the transport of this thermal energy to neighboring monomers in either a liquid or gel-like state results in a self-perpetuating reaction zone that provides fully cured thermosets and thermoplastics. Propagation of this polymerization front continues through the unreacted monomer media until either all reactants are consumed or sufficient heat loss stalls further reaction. Several different polymerization mechanisms support frontal processes, including free-radical, cat-or anionic, amine-cure epoxides, and ring-opening metathesis polymerization. The choice of monomer, initiator/catalyst, and additives dictates how fast the polymer front traverses the reactant medium, as well as the maximum temperature achievable. Numerous applications of frontally generated materials exist, ranging from porous substrate reinforcement to fabrication of patterned composites. In this review, we examine in detail the physical and chemical phenomena that govern frontal polymerization, as well as outline the existing applications.

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Section: Chemistries Of Existing Frontal Polymerization Systemsmentioning

confidence: 99%

Section: Applications Of Frontal Polymerizationmentioning

confidence: 99%

Frontal Polymerizations: From Chemical Perspectives to Macroscopic Properties and Applications

et al. 2023

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“…The FP-based fabrication of thin layers with thickness down to ∼100 μm on a thermally insulating substrate has been achieved recently with reduced volatile organics emission and controllable initiation of curing, which further broadens the application of FP to the manufacturing of thin coatings. , Because the FP-based manufacturing of thin layers is characterized by a reduced availability of reaction heat, the thermal diffusion into the substrate plays a key role in this process . Therefore, leveraging the competition between the heat generated by the reaction and the thermal transport enables the tuning of key features that influence the efficiency and feasibility of FP, that is, the front shape, velocity, and temperature. , Moreover, thermochemical instabilities emerge at a critical reaction–thermal transport power balance, − potentially resulting in polymeric parts with complex geometries and heterogeneous properties . A recent numerical study has reported that the resin layer thickness controls the front dynamics and determines its existence subject to convective heat loss .…”

Section: Introductionmentioning

confidence: 99%

Frontal Polymerization of Thin Layers on a Thermally Insulating Substrate

Gao

Koett

Hemmer

et al. 2022

ACS Appl. Polym. Mater.

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Motivated by the use of frontal polymerization for the manufacturing of thin layers with thickness down to ∼100 μm, we numerically and experimentally investigate the interplay between the exothermic polymerization and the heat losses to the substrate. The results show how the reaction–diffusion power balance affects the velocity and temperature of the polymerization front. The lower thickness limit of the thin layer depends on the cure kinetics of the resin and the thermal properties of the substrate and is described by a scaling law. Concurrently, thin-layer frontal polymerization experiments confirm the effects of front–substrate interaction on the front propagation and the limiting thickness of the polymerized layer. The present study offers a fundamental understanding of the resin–substrate interplay in thin-layer frontal polymerization and provides a quantitative description of the limiting thickness of the layer in the fabrication of functional thin polymeric parts and resin coatings.

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“…Pattern formation in FROMP may also occur through localized disruption of thermal or mass transport. Recent work from Gao et al 153,154 demonstrated that the inclusion of poly(caprolactone) microparticles in COD or DCPD resins introduces bias into the introduces periodic features in the temperature and velocity profiles of the front. During polymerization, the microparticles undergo an endothermic solid to liquid phase change that redirects thermal energy away from the reaction front.…”

Section: Instability Driven Spontaneous Patterningmentioning

confidence: 99%

Frontal Polymerizations: From Chemical Perspectives to Macroscopic Properties and Applications

Suslick

Hemmer

Groce

et al. 2022

Preprint

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The synthesis and processing of thermoplastics and thermoset polymeric materials rely on energy-inefficient and environmentally burdensome manufacturing methods. Frontal polymerization has emerged as an attractive, scalable alternative due to its exploitation of the heat of polymerization, which generally is wasted as unutilized heat-loss. The only external energy needed for frontal polymerization is an initial thermal (or photo) stimulus that locally ignites the reaction. The subsequent reaction exothermicity provides local heating; the transport of this thermal energy to neighboring monomers in either a liquid or gel-like state results in a self-perpetuating reaction zone that provides fully-cured polymeric thermosets and thermoplastics. Propagation of this polymerization front continues through the unreacted monomer media until either all reactants are consumed or sufficient heat-loss stalls further reaction. Several different polymerization mechanisms support frontal processes, including free-radical, cat- or anionic, amine-cure epoxides, and ring-opening metathesis polymerization. The choice of monomer, initiator/catalyst, and additives dictates how fast the polymer front traverses the reactant medium, as well as the maximum temperature achievable. Frontal polymerization enables the preparation of moldable thermoplastics derived from linear polymers. When crosslinking is involved, polymeric networks (e.g., rigid thermosets) are obtainable through a related process best described as a frontal curing reaction. Numerous applications of frontally-generated polymers and thermosets exist, ranging from the reinforcement of porous substrates to the design of patterned composite materials. In this review, we examine in detail the physical and chemical phenomena that govern frontal polymerization, as well as outline the existing applications.

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Manipulating Frontal Polymerization and Instabilities with Phase-Changing Microparticles

Cited by 15 publications

References 41 publications

Frontal Polymerizations: From Chemical Perspectives to Macroscopic Properties and Applications

Frontal Polymerizations: From Chemical Perspectives to Macroscopic Properties and Applications

Frontal Polymerization of Thin Layers on a Thermally Insulating Substrate

Frontal Polymerizations: From Chemical Perspectives to Macroscopic Properties and Applications

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