Microphase Separation 3D Printing of Binary Inorganic Polymer Precursors to Prepare Nanostructured Carbon‐Ceramic Multimaterials

Advanced Materials Technologies, Journal Year: 2024, Volume and Issue: 9(13)

Published: April 18, 2024

Abstract Traditionally, combining carbon and ceramic materials has been challenging due to their different chemical physical properties. Despite the development of numerous methodologies for synthesis, these techniques frequently necessitate intricate, multi‐stage protocols specialized equipment. This study introduces a novel approach fabricating nanostructured carbon‐ceramic multimaterials through polymerization‐induced microphase separation 3D printing. By inorganic precursors, polycarbosilane, acrylonitrile (AN) within photocurable resin, heterogeneous composed PAN‐preceramic sacrificial polymer phases are printed. Upon pyrolysis, domains transformed into matrix while thermally decomposed yield nanoscale voids. The utilization synchrotron X‐ray spectroscopy microscopy revealed that phase compositions microstructure resulting multi‐materials significantly influenced by initial composition resins. co‐existence single printed material brought together combination properties from both phases, such as low thermal conductivity ceramics relatively high electrical carbon, along with exceptional resistance. insights microstructure, atomic configuration, property relationships have broad implications multi‐phase hybrid materials.

Language: Английский

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Unleashing the potential of 3D printing soft materials

Device, Journal Year: 2023, Volume and Issue: 1(3), P. 100067 - 100067

Published: Sept. 1, 2023

Language: Английский

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Xolography for the Production of Polymeric Multimaterials

Advanced Materials Technologies, Journal Year: 2024, Volume and Issue: 9(15)

Published: April 1, 2024

Abstract Three‐dimensional (3D) printed multimaterials have quickly grown in interest as researchers aim to mimic the material chemistry and geometric complexity of natural materials. While some exceptional multimaterial 3D printing systems been developed, there is still a shortfall scope production these More recently, introduction xolography single‐step, auxiliary‐free additive manufacturing approach has enabled rapid materials with geometries inaccessible via other techniques. However, previous required resins high transparency for effective formation, formation not demonstrated. In this work, reversible deactivation radical polymerization used resin composition, viscosity, processing parameters are explored develop new capable application visible light‐mediated xolography. After optimization, non‐transparent containing thiocarbonylthio species applied manufacture geometrically complex, The resulting polymer network can be functionalized embedded moieties impart functionality Finally, unique capabilities demonstrated featuring chemically disparate domains 3D‐spatial control. This two‐step overprinting operationally simple provides avenue polymeric printing.

Language: Английский

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Tuning the Mechanical Properties of 3D‐printed Objects by the RAFT Process: From Chain‐Growth to Step‐Growth

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(10)

Published: Jan. 17, 2024

Photoinduced 3D printing based on the reversible addition-fragmentation chain transfer (RAFT) process has emerged as a robust method for creating diverse functional materials. However, achieving precise control over mechanical properties of these printed objects remains critical challenge practical application. Here, we demonstrated RAFT step-growth polymerization bifunctional xanthate and vinyl acetate. Additionally, photoinduced through with tetrafunctional By adjusting molar ratio components in resins, finely tuned mechanism from to chain-growth. This adjustment resulted remarkable range tunable Young's moduli, ranging 7.6 MPa 997.1 MPa. Moreover, post-functionalization polymer welding varying opens up promising way produce tailor-made materials specific properties.

Language: Английский

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Customized Nanostructured Ceramics via Microphase Separation 3D Printing

Advanced Science, Journal Year: 2023, Volume and Issue: 10(32)

Published: Sept. 26, 2023

To date, the restricted capability to fabricate ceramics with independently tailored nano- and macroscopic features has hindered their implementation in a wide range of crucial technological areas, including aeronautics, defense, microelectronics. In this study, novel approach that combines self- digital assembly create polymer-derived highly controlled structures spanning from macroscale is introduced. Polymerization-induced microphase separation resin during light processing generates materials nanoscale morphologies, distinct phases consisting either preceramic precursor or sacrificial polymer. By precisely controlling molecular weight polymer, domain size resulting material can be finely tuned. Pyrolysis printed objects yields complex geometries porosity, which display excellent thermal oxidation resistance, morphology-dependent conduction properties. This method offers valuable platform for simplified fabrication nanostructured shapes.

Language: Английский

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Fluorescence-readout as a powerful macromolecular characterisation tool

Chemical Science, Journal Year: 2023, Volume and Issue: 14(45), P. 12815 - 12849

Published: Jan. 1, 2023

We discuss the current state-of-the-art in exploiting fluorescence-based techniques for analysing polymer systems and soft matter materials, as well provide an outlook on future opportunities challenges.

Language: Английский

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Effect of Macromolecular Structure on Phase Separation Regime in 3D Printed Materials

Macromolecular Rapid Communications, Journal Year: 2023, Volume and Issue: 44(24)

Published: June 8, 2023

In this study, the fabrication of 3D-printed polymer materials with controlled phase separation using polymerization induced microphase (PIMS) via photoinduced 3D printing is demonstrated. While many parameters affecting nanostructuration in PIMS processes are extensively investigated, influence chain transfer agent (CTA) end group, i.e., Z-group, macromolecular (macroCTA) remains unclear as previous research has exclusively employed trithiocarbonate CTA group. Herein, effect macroCTAs containing four different Z-groups on formation nanostructure printed explored. The results show that lead to distinct network and behaviors between resins, influencing both process resulting material properties. Specifically, less reactive toward acrylic radical addition, such O-alkyl xanthate N-alkyl-N-aryl dithiocarbamate, result translucent brittle macrophase morphology. contrast, more S-alkyl 4-chloro-3,5-dimethylpyrazo dithiocarbamate produce transparent rigid nano-scale Findings study provide a novel approach manipulate properties materials, which can have important implications for science engineering.

Language: Английский

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Degradable 3D Printed Objects with Tunable Mechanical Properties via Photoinduced Free Radical Promoted Cationic RAFT Polymerization

ACS Applied Polymer Materials, Journal Year: 2024, Volume and Issue: 6(2), P. 1584 - 1591

Published: Jan. 17, 2024

The emergence and development of photopolymerization 3D printing based on controlled polymerization techniques have shown significant advantages in the fabrication "living" polymeric materials with various functionalities. However, it is crucial to consider degradation these printed objects for environmentally friendly development. Herein, mono-, bi-, trifunctional vinyl ether monomers degradable ester cores were synthesized used via photoinduced free radical promoted cationic reversible addition–fragmentation chain transfer polymerization. model conditions using studied detail. A fast speed (7.61–10.23 cm h–1) tunable mechanical properties (tensile strength ranging from 1.7 41.6 MPa Young's modulus 6.5 1.3 GPa) can be achieved by adjusting resins. Moreover, partial starting material (benzoic acids) could easily recovered after objects, offering a promising avenue advancing sustainable

Language: Английский

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Design and Synthesis of a New Indazole-Decorated RAFT Agent for Highly Efficient PET-RAFT Polymerization

Macromolecules, Journal Year: 2024, Volume and Issue: 57(9), P. 4421 - 4429

Published: April 15, 2024

While enabling precise control and well-defined molecular weights in polymer synthesis, photocatalyzed reversible deactivation radical polymerization (photo-RDRP) suffers from slow kinetics, limiting its broader application advanced manufacturing. Despite a decade of research on photocatalyst design, progress significantly improving the kinetics photo-RDRP remains insufficient. In contrast, role initiator is often overlooked, especially photoinduced electron/energy transfer addition–fragmentation chain (PET-RAFT) polymerization, where RAFT agent serves as both agent. this work, we first designed synthesized new with an indazole Z group (InZ) for highly efficient PET-RAFT under irradiation. This strongly electron-donating accelerates initiation by facilitating π* → σ* charge systems. Compared to commonly used trithiocarbonates utilization InZ improved rates 2.7-fold. Additionally, discovered (PC) i.e., zinc 5,10,15,20-tetra(naphthalen-2-yl)porphyrin (ZnTNP), through experimental screening various porphyrin derivates. ZnTNP/InZ system exhibits temporal weight course being compatible broad range acrylates acrylamides exhibiting good oxygen tolerance. Importantly, may inspire further development high-performance agents polymerization.

Language: Английский

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Nitroxide-Mediated Photopolymerization: When Surface Grafting on Cross-Linked Networks Goes up to Several Hundred Microns

ACS Applied Polymer Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 24, 2025

Chain extension with multiple blocks is one of the major advantages reversible deactivation radical polymerization (RDRP), and as such, it widely applied to synthesis (block)copolymers. Mainly exploited for linear branched structures, this characteristic less recognized in highly cross-linked networks by RDRP, possibly due limited thickness usually achieved, which generally sits below a few tens nanometers. In study, we demonstrated how, under optimized conditions, chain on possible up several hundred micrometers, obvious opportunities microfabrication structuring complex polymer surfaces. By using nitroxide-mediated photopolymerization (NMP2) patterning digital light processing (DLP) photolithography, successfully grew layers model glass substrates extended more than 300 μm simply depositing bare monomer top every polymerized layer. A systematic study irradiation UV–vis, Fourier transform infrared, profiling measurements revealed that surface grafting process was efficient when supporting underlayer not fully grown. We speculated its "incomplete polymerization" grants gel phase allowing easy diffusion both fresh reactive nitroxide ends. similar behavior, although much weaker, also observed reference, free-radical photopolymerized resins, relates slow activation unreacted photoinitiator. Thus, besides advantage NMP2 DLP illustrates how interlayer properties critically affect efficiency surface-(re)initiated polymerization, opening unique possibilities NMP2.

Language: Английский

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