Interplay of photopolymerization and phase separation kinetics and the resulting structure-property relationship of photocurable resins

Zakrzewski, Lauren; Kim, Yeongsik; Song, Younghan; Ryu, Chang Y.; Bae, Chulsung; Picu, Catalin R.

doi:10.1016/j.polymer.2023.126032

Cited by 3 publications

(7 citation statements)

References 62 publications

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“…A custom-built light transmission apparatus previously described and employed in our previous studies ,, is used to evaluate the extent of phase separation in the photocurable resins. Transmittance tests are performed using a film thickness, b , of 100 μm, which is controlled using Scotch tape placed on a glass slide as a spacer.…”

Section: Methodsmentioning

confidence: 99%

“…Various techniques have been developed to create heterogeneous polymeric materials including polymer blends, − block copolymer self-assembly, − the addition of elastomeric particles and of nanoparticles, − and polymerization-induced phase separation (PIPS). ,,− All of these methods have their own advantages and disadvantages, such as the cost and strict processing conditions. However, among them, PIPS offers unique opportunities such as the development of various microstructures, including droplet-like or interpenetrating subdomains, obtained by a simple variation of the chemical composition and/or light intensity used for photopolymerization.…”

Section: Introductionmentioning

confidence: 99%

“…While various solutions to improve the ductility and toughness of acrylic- and epoxy-based thermosets exist, including the use of elastomeric microbeads, copolymers, and nanoparticles, little attention has been given to a phase-separation-based approach for the same purpose. In our previous study, we explored the mechanical properties of several photocurable resins in which phase separation of polypropylene glycol (PPG) occurs. This work indicated that PPG works both as a plasticizer and as a phase-separating agent and that the plasticizing effect may be dominant.…”

Section: Introductionmentioning

confidence: 99%

“…PIPS begins with an initially homogeneous liquid photocurable mixture consisting of monomers, which polymerize into a thermosetting network, and a phase-separating agent, which phase-separates upon polymerization. ,,,− This process can be initiated through several reactive pathways such as anionic, cationic, thermal, or radical-light-initiated polymerization (photo-PIPS). Among these polymerization processes, photo-PIPS was selected for this work due to the ease of controlling the polymerization kinetics.…”

Section: Introductionmentioning

confidence: 99%

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Increasing Ductility and Toughness of Photocurable Thermosets with Microstructures Controlled by Phase Separation

Zakrzewski,

Purkaysta,

Bae

et al. 2024

ACS Appl. Polym. Mater.

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In this work, photopolymerization-induced phase separation (photo-PIPS) is implemented into a polymer network consisting of both acrylic and epoxy-based chemistries to allow for the development of an acrylic network through photopolymerization and for enhanced strength and stiffness to be obtained via thermal cross-linking of the epoxy-based chemistries. Two epoxy-based end-group terminated polydimethylsiloxane (PDMS) polymer additives [hydroxy-terminated PDMS (OH-PDMS) and diglycidyl ether-terminated PDMS (epoxy-PDMS)] are added to enable phase separation, creating a heterogeneous polymeric material. During thermal treatment applied after photopolymerization, these additives can cross link together, concurrently with the cross-linking of the epoxy-based monomers which are part of the network, therefore creating elastomeric, phase-separated subdomains. Mixtures of OH-PDMS and epoxy-PDMS of various molar ratios are used to alter the extent of phase separation and the amount of cross-linking that occurs within the subdomains. It is observed that OH-PDMS does not phase separate when present alone, while it separates in the presence of epoxy-PDMS. Cross-linking within the phase-separated domains containing both types of PDMS leads to enhanced ductility, with the optimal ductility and toughness enhancement being obtained for the PDMS stoichiometry (OH-PDMS:epoxy-PDMS 80:20 by mol %). This composition retains good creep resistance and has only a slightly smaller strength than the neat resin.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Increasing Ductility and Toughness of Photocurable Thermosets with Microstructures Controlled by Phase Separation

Zakrzewski,

Purkaysta,

Bae

et al. 2024

ACS Appl. Polym. Mater.

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Section: Characterization Toolboxmentioning

confidence: 99%

From Unregulated Networks to Designed Microstructures: Introducing Heterogeneity at Different Length Scales in Photopolymers for Additive Manufacturing

Ahmadi,

Ehrmann,

Koch

et al. 2024

Chem. Rev.

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Photopolymers have been optimized as protective and decorative coating materials for decades. However, with the rise of additive manufacturing technologies, vat photopolymerization has unlocked the use of photopolymers for three-dimensional objects with new material requirements. Thus, the originally highly cross-linked, amorphous architecture of photopolymers cannot match the expectations for modern materials anymore, revealing the largely unanswered question of how diverse properties can be achieved in photopolymers. Herein, we review how microstructural features in soft matter materials should be designed and implemented to obtain high performance materials. We then translate these findings into chemical design suggestions for enhanced printable photopolymers. Based on this analysis, we have found microstructural heterogenization to be the most powerful tool to tune photopolymer performance. By combining the chemical toolbox for photopolymerization and the analytical toolbox for microstructural characterization, we examine current strategies for physical heterogenization (fillers, inkjet printing) and chemical heterogenization (semicrystalline polymers, block copolymers, interpenetrating networks, photopolymerization induced phase separation) of photopolymers and put them into a material scientific context to develop a roadmap for improving and diversifying photopolymers' performance.

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Photopolymerization-induced phase separation kinetics explored by intermittent irradiation

Zakrzewski,

Ryu,

Bae

et al. 2024

Polymer

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Interplay of photopolymerization and phase separation kinetics and the resulting structure-property relationship of photocurable resins

Cited by 3 publications

References 62 publications

Increasing Ductility and Toughness of Photocurable Thermosets with Microstructures Controlled by Phase Separation

Increasing Ductility and Toughness of Photocurable Thermosets with Microstructures Controlled by Phase Separation

From Unregulated Networks to Designed Microstructures: Introducing Heterogeneity at Different Length Scales in Photopolymers for Additive Manufacturing

Photopolymerization-induced phase separation kinetics explored by intermittent irradiation

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