A photopolymerizable thermoplastic with tunable mechanical performance

Alim, Marvin D.; Childress, Kimberly K.; Baugh, Neil; Martinez, Alina M.; Davenport, A. T.; Fairbanks, Benjamin D.; McBride, Matthew K.; Worrell, Brady T.; Stansbury, Jeffrey W.; McLeod, Robert R.; Bowman, Christopher N.

doi:10.1039/c9mh01336a

Cited by 33 publications

(34 citation statements)

References 42 publications

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“…[ 5–9 ] Introducing alternative crosslinking chemistries to the VAM realm, as well as AM more broadly, is highly desirable as an alternative method to gain access to a wider range of mechanical, thermal, and optical performance. [ 10–14 ] Thiol‐ene‐based polymers are one class of materials that have drawn significant attention owing to their controllable, tunable mechanical properties. [ 15–17 ] This is generally attributed to more uniform molecular networks in thiol‐ene materials, resulting from the step‐growth mechanism of the polymerization reaction.…”

Section: Figurementioning

confidence: 99%

Highly Tunable Thiol‐Ene Photoresins for Volumetric Additive Manufacturing

et al. 2020

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Volumetric additive manufacturing (VAM) is an emerging approach to photo polymerbased 3D printing that produces complex 3D structures in a single step, rather than from layer-by-layer assembly. [1] This paradigm holds promise because it overcomes many of the drawbacks of layerbased fabrication, such as long build times and rough surfaces. VAM also augurs a broadening of the materials available for photopolymer 3D printing, having fewer constraints on viscosity and reactivity compared to layerwise printing. Indeed, though VAM has been demonstrated with extremely soft hydrogels, [2,3] it has relied until now almost exclusively on acrylate-based chemistry. [4] This is natural, because the oxygen inhibition of acrylate polymerization provides the threshold behavior required for VAM. However, acrylate chemistry is in general limiting due to the brittle and glassy properties of the resulting materials. Accordingly, extensive efforts have been made to identify and target specific soft, elastic acrylate formulations. [5-9] Introducing alternative crosslinking chemistries to the VAM realm, as well as AM more broadly, is highly desirable as an alternative method to gain access to a wider range of mechanical, thermal, and optical performance. [10-14] Thiol-ene-based polymers are one class of materials that have drawn significant attention owing to their controllable, tunable mechanical properties. [15-17] This is generally attributed to more uniform molecular networks in thiol-ene materials, resulting from the step-growth mechanism of the polymerization reaction. [18,19] Thiol-ene materials have already shown promise for applications including use in adhesives, electronics, and as biomaterials. [20,21] This work expands the versatility of volumetric AM by introducing a new class of VAM-compatible thiol-ene resins. We demonstrate the formulation of thiol-ene resins with the nonlinear threshold-type kinetics required for VAM and show bulk-equivalent performance in the resulting 3D printed parts, confirming the advantage of the layerless whole-part process. In our volumetric AM system, a 3D distribution of light energy is delivered to the resin vat by superimposing exposures from multiple angles, a method termed computed axial litho graphy (CAL) (Figure 1a). [2] The exposures are a sequence of projections calculated from 3D CAD models using algorithms from computed Volumetric additive manufacturing (VAM) forms complete 3D objects in a single photocuring operation without layering defects, enabling 3D printed polymer parts with mechanical properties similar to their bulk material counterparts. This study presents the first report of VAM-printed thiol-ene resins. With well-ordered molecular networks, thiol-ene chemistry accesses polymer materials with a wide range of mechanical properties, moving VAM beyond the limitations of commonly used acrylate formulations. Since free-radical thiol-ene polymerization is not inhibited by oxygen, the nonlinear threshold response required in VAM is introduced by incorporating 2,2,6,6-tetrameth...

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Section: Figurementioning

confidence: 99%

Highly Tunable Thiol‐Ene Photoresins for Volumetric Additive Manufacturing

et al. 2020

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“…Additive manufacturing or three-dimensional (3D) printing is becoming a revolutionary technique in a wide variety of applications, including electronics, soft robots, and biomedical engineering. − Digital light processing (DLP) 3D printing has attracted particular attention due to its high printing efficiency and high resolution. − Dual- or multifunctional photoactive monomers are always used to meet the quick liquid-to-solid transition during DLP printing, leading to the production of massive thermosetting polymers. ,− Once these printed thermosets are damaged, they cannot be healed or recycled because of their covalently cross-linked networks. Therefore, they are always discarded at the end of their life, resulting in vast materials waste and serious environmental problems. , Thus, developing self-healing or recycling polymers for DLP printing can not only effectively prolong the service life of these 3D objects but also provide an appealing solution to deal with the above issues.…”

Section: Introductionmentioning

confidence: 99%

Digital Light Processing 3D Printing of Healable and Recyclable Polymers with Tailorable Mechanical Properties

Zhu

Hou

Xiang

et al. 2021

ACS Appl. Mater. Interfaces

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Three-dimensional (3D) printing is becoming a revolutionary technique across various fields. Especially, digital light processing (DLP) 3D printing shows advantages of high resolution and high efficiency. However, multifunctional monomers are commonly used to meet the rapid liquid-to-solid transformation during DLP printing, and the extensive production of unreprocessable thermosets will lead to resource waste and environmental problems. Here, we report a family of dynamic polymers with highly tailorable mechanical properties for DLP printing. The dynamic polymers cross-linked by ionic bonding and hydrogen bonding endow printed objects with excellent self-healing and recycling ability. The mechanical properties of printed objects can be easily tailored from soft elastomers to rigid plastics to satisfy practical applications. Taking advantage of the dynamic cross-linking, various assembling categories, including 2D to 3D, small to large 3D structures, and same to different materials assembly, and functional devices with a self-healing capacity can be realized. This study not only helps to address environmental issues caused by traditional DLP-printed thermosets but also realizes the on-demand fabrication of complex structures.

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“…To address the above‐mentioned problems, thermoplastics and dynamically crosslinked thermosets have been successfully developed for DLP printing. [ 19,25,26 ] The obtained 3D objects can be reprocessed by melting or by processing in solution. However, reprinting these materials by the same DLP has not been reported.…”

Section: Introductionmentioning

confidence: 99%

Reprintable Polymers for Digital Light Processing 3D Printing

Zhu

Hou

et al. 2020

Adv Funct Materials

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3D printing is becoming a disruptive technology and shows great potential for various practical applications. Specially, digital light processing (DLP) 3D printing demonstrates advantages in high resolution and high efficiency. However, extensive production of infusible and insoluble thermosets in DLP printing causes serious resource waste and environmental problems after its disposal. Herein, a reprintable linear polymer is reported for repeatable DLP printing. Taking advantage of the dissolution of linear polymer in its monomer, printed objects can be recycled into liquid resin and reprinted via the same DLP. Polymerization kinetics and printing resolution of recycled resins and mechanical properties of reprinted polymers retain identical as the original. The thermoplastic nature of linear polymer endows 3D objects with welding and reshaping property. Recyclable composites are also successfully fabricated, and sustainable usage of high‐value fillers comes true. This strategy helps to address environmental issues arising from unprocessable thermosets and may contribute to an efficient materials recycling.

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A photopolymerizable thermoplastic with tunable mechanical performance

Abstract: Semicrystalline polymeric materials possessing extraordinary mechanical properties were rapidly fabricated using light from low viscosity liquids at room temperature.

Cited by 33 publications

References 42 publications

Highly Tunable Thiol‐Ene Photoresins for Volumetric Additive Manufacturing

Highly Tunable Thiol‐Ene Photoresins for Volumetric Additive Manufacturing

Digital Light Processing 3D Printing of Healable and Recyclable Polymers with Tailorable Mechanical Properties

Reprintable Polymers for Digital Light Processing 3D Printing

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