Nanostructure Control in 3D Printed Materials

Bobrin, Valentin A.; Lee, Kenneth; Zhang, Jin; Corrigan, Nathaniel; Boyer, Cyrille

doi:10.1002/adma.202107643

Cited by 59 publications

(81 citation statements)

References 59 publications

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“…Upon increasing the macroCTA wt % from 16.5 to 43.9 wt % for the R2‐180 resins, the q* value of the SAXS profiles increased from 0.28 nm −1 to 0.33 nm −1 (Figure 6C), revealing a slight decrease in the domain spacing ( d SAXS ) from 22 nm to 19 nm. The decrease in d SAXS is consistent with our previous study using linear (1‐arm) macroCTA, which was ascribed to reduction in average block copolymer size upon higher loading of macroCTA in a resin [24] . Similarly, SAXS profiles of materials 3D printed using R4‐180 resins also displayed the same trend, with d SAXS decreasing from 16 nm to 13 nm upon increasing macroCTA wt % from 16.5 to 43.9 wt % (SI, Figure S12).…”

Section: Resultssupporting

confidence: 91%

“…AFM measurements in PeakForce quantitative nanomechanics mode was used to investigate the nanostructure of 3D printed materials. It has been reported that soft PBA and hard PAA domains on 3D printed material surfaces can be distinguished due to elastic modulus differences [24] . Detailed parameters applied in the AFM study can be found in the SI, Characterization section.…”

Section: Resultsmentioning

confidence: 99%

“…Alternatively, Cavicchi and co‐workers, [21] Levkin and co‐workers, [22] and others, [23] have demonstrated that PIPS can be applied to 3D printing to provide nanostructured materials with advanced functions such as triple shape memory, [21] ultra‐hydrophobicity, [22a] hierarchical porosity, [22b] and electrical conductivity [23] . Recently, our group developed a photoinduced PIMS process to generate nanostructured materials via digital light projection (DLP) 3D printing, which allowed the rapid fabrication of nanostructured materials with enhanced toughness [24] . While these 3D printing processes provide geometrically complex materials in shorter times, there still remains a limitation in terms of final material morphologies (Figure 1B).…”

Section: Introductionmentioning

confidence: 99%

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Designing Nanostructured 3D Printed Materials by Controlling Macromolecular Architecture

et al. 2022

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Nanostructured polymeric materials play important roles in many advanced applications, however, controlling the morphologies of polymeric thermosets remains a challenge. This work uses multi-arm macro-CTAs to mediate polymerization-induced microphase separation (PIMS) and prepare nanostructured materials via photoinduced 3D printing. The characteristic length scale of microphase-separated domains is determined by the macroCTA arm length, while nanoscale morphologies are controlled by the macroCTA architecture. Specifically, using 2-and 4-arm macroCTAs provides materials with different morphologies compared to analogous monofunctional linear macroCTAs at similar compositions. The mechanical properties of these nanostructured thermosets can also be tuned while maintaining the desired morphologies. Using multi-arm macroCTAs can thus broaden the scope of accessible nanostructures for extended applications, including the fabrication of actuators and potential drug delivery devices.

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Section: Resultssupporting

confidence: 91%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Designing Nanostructured 3D Printed Materials by Controlling Macromolecular Architecture

et al. 2022

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“…Notably, our group recently developed a photoinduced 3D printing process using polymerization induced microphase separation (PIMS), to fabricate materials with nanostructured domains 21 . The PIMS process was originally developed by Seo and Hillmyer 22 , and relies on in-situ chain extension of a macromolecular chain transfer agent (macroCTA) to induce microphase separation between incompatible block segments; the microphase separation is then arrested via crosslinking which provides materials with nanoscale morphologies (Fig.…”

Section: Introductionmentioning

confidence: 99%

Nano- to macro-scale control of 3D printed materials via polymerization induced microphase separation

et al. 2022

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Although 3D printing allows the macroscopic structure of objects to be easily controlled, controlling the nanostructure of 3D printed materials has rarely been reported. Herein, we report an efficient and versatile process for fabricating 3D printed materials with controlled nanoscale structural features. This approach uses resins containing macromolecular chain transfer agents (macroCTAs) which microphase separate during the photoinduced 3D printing process to form nanostructured materials. By varying the chain length of the macroCTA, we demonstrate a high level of control over the microphase separation behavior, resulting in materials with controllable nanoscale sizes and morphologies. Importantly, the bulk mechanical properties of 3D printed objects are correlated with their morphologies; transitioning from discrete globular to interpenetrating domains results in a marked improvement in mechanical performance, which is ascribed to the increased interfacial interaction between soft and hard domains. Overall, the findings of this work enable the simplified production of materials with tightly controllable nanostructures for broad potential applications.

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“…[63] Furthermore, Boyer group demonstrated that RAFT 3D printing can be used for silica/polymer composite fabrication (Figure 5E) [64] as well as micro-to nanoscale structure control in 3D printed complex objects. [65] Recently, Jin and co-workers explored the possibility of RAFT 3D printing under red LED light (635 nm, 0.5 mW cm −2 ) by introducing ZnTPP to the resin, with a disk-shaped model printed. [66] Meanwhile, Zhu and co-workers attempted cationic RAFT polymerization toward NIR light 3D printing by using a commercially available iron catalyst, cyclopentadienyl iron dicarbonyl dimer (Fe 2 (Cp) 2 (CO) 4 ) as the photocatalyst.…”

Section: Raft Photoinitiating Systemmentioning

confidence: 99%

Recent Trends in Advanced Photoinitiators for Vat Photopolymerization 3D Printing

Bao

2022

Macromol. Rapid Commun.

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3D printing has revolutionized the way of manufacturing with a huge impact on various fields, in particular biomedicine. Vat photopolymerization‐based 3D printing techniques such as stereolithography (SLA) and digital light processing (DLP) attract considerable attention owing to their superior print resolution, relatively high speed, low cost, and flexibility in resin material design. As one key element of the SLA/DLP resin, photoinitiators or photoinitiating systems have experienced significant development in recent years, in parallel with the exploration of 3D printing (macro)monomers. The design of new photoinitiating systems cannot only offer faster 3D printing speed and enable low‐energy visible light fabrication, but also can bring new functions to the 3D printed products and even generate new printing methods in combination with advanced optics. This review evaluates recent trends in the development and application of advanced photoinitiators and photoinitiating systems for vat photopolymerization 3D printing, with a wide range of small molecules, polymers, and nanoassemblies involved. Personal perspectives on the current limitations and future directions are eventually provided.

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Nanostructure Control in 3D Printed Materials

Cited by 59 publications

References 59 publications

Designing Nanostructured 3D Printed Materials by Controlling Macromolecular Architecture

Designing Nanostructured 3D Printed Materials by Controlling Macromolecular Architecture

Nano- to macro-scale control of 3D printed materials via polymerization induced microphase separation

Recent Trends in Advanced Photoinitiators for Vat Photopolymerization 3D Printing

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