Dual-curable stereolithography resins for superior thermomechanical properties

Konuray, Osman; Donato, F. Di; Sangermano, Marco; Bonada, J.; Tercjak, Agnieszka; Fernández‐Francos, Xavier; Serra, À.; Ramis, Xavier

doi:10.3144/expresspolymlett.2020.72

Cited by 20 publications

(26 citation statements)

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“…At any rate, the curing process is either completed in the printer by photopolymerizing both monomers simultaneously, [ 6,8,11 ] or by using a two‐stage, sequential process. [ 12–15 ]…”

Section: Introductionmentioning

confidence: 99%

“…The reader is referred to our earlier work for specifics of this printer setup. [ 13,16 ] As with any 3D printing method that relies on photopolymerization, some problems must be considered, such as the occurrence of spatial conversion gradients (due to inhomogeneous irradiation). Although a UV post‐curing stage can partially mitigate this problem, curing schedules should be planned so as to avoid these spatial gradients along part dimensions and minimize deformation, cracking, or delamination.…”

Section: Introductionmentioning

confidence: 99%

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Epoxy Doped, Nano‐scale Phase‐separated Poly‐Acrylates with Potential in 3D Printing

Konuray

Altet

Bonada

et al. 2021

Macro Materials & Eng

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An efficient method to improve the mechanical performance of a commercially available photocure resin is described wherein the resin is modified with a mixture of a cycloaliphatic epoxy and an anhydride curing agent. Photocured samples are thermally treated in a subsequent step to cure the epoxy to obtain an interpenetrated polymer network (IPN) and also complete reaction of the acrylate monomers remaining from the photocure. The latter is accomplished by a thermal radical initiator added earlier into the formulation together with the epoxy‐anhydride. The thermal properties and microstructure of the resulting IPN are analyzed. Uniform and quantitative conversions are obtained, with glass transition temperatures comparable to conventional epoxies. The liquid, uncured samples containing different amounts of epoxy are stable at 30 °C for several weeks. In the fully cured epoxy‐rich materials, nano‐scale phase separation is observed by atomic force microscopy. This is corroborated by the existence of multiple relaxations determined by dynamic mechanical analysis analysis. Specimens from a formulation containing 50% by weight of epoxy‐anhydride are 3D printed in a customized masked image processing stereolithography, thermally treated, and are subjected to compression tests. Results show that Young's modulus increases by 900% over the neat resin.

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“…At any rate, the curing process is either completed in the printer by photopolymerizing both monomers simultaneously, [ 6,8,11 ] or by using a two‐stage, sequential process. [ 12–15 ]…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Epoxy Doped, Nano‐scale Phase‐separated Poly‐Acrylates with Potential in 3D Printing

Konuray

Altet

Bonada

et al. 2021

Macro Materials & Eng

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show abstract

“…However, it was also noted that, because traces of unreacted monomer might be still present in the sample, maximum properties could only be obtained if unreacted monomer was eventually removed from the material by soaking the sample in a suitable solvent after the 3D printing and a thermal treatment. Konuray et al [ 43 ] also reported that ultimate material properties could only be obtained if a thermal radical initiator was added in order to complete the reaction of acrylate monomers in dual-curing formulations for stereolithography.…”

Section: Sequential 3d Printing and Thermal Radical Polymerizationmentioning

confidence: 99%

“…Konuray et al [ 43 ] developed dual-curable formulations based on commercial acrylate resins for stereolithography modified with diepoxy monomer, with storage stability of up to 2 months at 32 °C, making it suitable for the preparation of stable one-pot formulations. Storage stability and control of the curing sequence were achieved by means of the use of (1) a radical photoinitiator for the 3D-printing stage and (2) a latent cationic initiator based on quaternary ammonium salts stabilized with a tertiary amine for the thermal cationic homopolymerization of the epoxy resin.…”

Section: Sequential Dual-curing Systems Combining Two Polymerizatimentioning

confidence: 99%

Enhancement of 3D-Printable Materials by Dual-Curing Procedures

et al. 2020

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Dual-curing thermosetting systems are recently being developed as an alternative to conventional curing systems due to their processing flexibility and the possibility of enhancing the properties of cured parts in single- or multi-stage processing scenarios. Most dual-curing systems currently employed in three-dimensional (3D) printing technologies are aimed at improving the quality and properties of the printed parts. However, further benefit can be obtained from control in the curing sequence, making it possible to obtain partially reacted 3D-printed parts with tailored structure and properties, and to complete the reaction by activation of a second polymerization reaction in a subsequent processing stage. This paves the way for a range of novel applications based on the controlled reactivity and functionality of this intermediate material and the final consolidation of the 3D-printed part after this second processing stage. In this review, different strategies and the latest developments based on the concept of dual-curing are analyzed, with a focus on the enhanced functionality and emerging applications of the processed materials.

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“…These parts are then removed from the build platform and placed in an oven to initiate thermal curing, allowing high‐performance materials to be used in these processes. [ 8‐11 ]…”

Section: Introductionmentioning

confidence: 99%

A model for modulus development of dual‐cure resin systems

Redmann

Osswald

2020

Polymer Engineering & Sci

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A phenomenological model for cure‐dependent modulus is described for materials undergoing a two‐stage curing reaction. These dual‐cure resin systems commonly use a thermally activated reaction in the second stage with temperatures exceeding the glass transition temperature of the intermediate product. This leads to a non‐linear development of the elastic modulus, with an observable softening effect and the potential for large structural deformations. In this study, the elastic modulus was measured at discrete levels of thermal conversion and processing temperatures. The results are used to determine the cure and temperature dependent‐modulus and create a model capable of following the modulus development throughout the entire thermal processing stage. Applications and a processing guideline are discussed.

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Dual-curable stereolithography resins for superior thermomechanical properties

Cited by 20 publications

References 0 publications

Epoxy Doped, Nano‐scale Phase‐separated Poly‐Acrylates with Potential in 3D Printing

Epoxy Doped, Nano‐scale Phase‐separated Poly‐Acrylates with Potential in 3D Printing

Enhancement of 3D-Printable Materials by Dual-Curing Procedures

A model for modulus development of dual‐cure resin systems

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