skip to main content


Title: High‐Speed 3D Printing of High‐Performance Thermosetting Polymers via Two‐Stage Curing
Abstract

Design and direct fabrication of high‐performance thermosets and composites via 3D printing are highly desirable in engineering applications. Most 3D printed thermosetting polymers to date suffer from poor mechanical properties and low printing speed. Here, a novel ink for high‐speed 3D printing of high‐performance epoxy thermosets via a two‐stage curing approach is presented. The ink containing photocurable resin and thermally curable epoxy resin is used for the digital light processing (DLP) 3D printing. After printing, the part is thermally cured at elevated temperature to yield an interpenetrating polymer network epoxy composite, whose mechanical properties are comparable to engineering epoxy. The printing speed is accelerated by the continuous liquid interface production assisted DLP 3D printing method, achieving a printing speed as high as 216 mm h−1. It is also demonstrated that 3D printing structural electronics can be achieved by combining the 3D printed epoxy composites with infilled silver ink in the hollow channels. The new 3D printing method via two‐stage curing combines the attributes of outstanding printing speed, high resolution, low volume shrinkage, and excellent mechanical properties, and provides a new avenue to fabricate 3D thermosetting composites with excellent mechanical properties and high efficiency toward high‐performance and functional applications.

 
more » « less
NSF-PAR ID:
10050535
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Macromolecular Rapid Communications
Volume:
39
Issue:
7
ISSN:
1022-1336
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. 3D printing allows for moldless fabrication of continuous fiber composites with high design freedom and low manufacturing cost per part, which makes it particularly well-suited for rapid prototyping and composite product development. Compared to thermal-curable resins, UV-curable resins enable the 3D printing of composites with high fiber content and faster manufacturing speeds. However, the printed composites exhibit low mechanical strength and weak interfacial bonding for high-performance engineering applications. In addition, they are typically not reprocessable or repairable; if they could be, it would dramatically benefit the rapid prototyping of composite products with improved durability, reliability, cost savings, and streamlined workflow. In this study, we demonstrate that the recently emerged two-stage UV-curable resin is an ideal material candidate to tackle these grand challenges in 3D printing of thermoset composites with continuous carbon fiber. The resin consists primarily of acrylate monomers and crosslinkers with exchangeable covalent bonds. During the printing process, composite filaments containing up to 30.9% carbon fiber can be rapidly deposited and solidified through UV irradiation. After printing, the printed composites are subjected to post-heating. Their mechanical stiffness, strength, and inter-filament bonding are significantly enhanced due to the bond exchange reactions within the thermoset matrix. Furthermore, the utilization of the two-stage curable resin enables the repair, reshaping, and recycling of 3D printed thermosetting composites. This study represents the first detailed study to explore the benefits of using two-stage UV curable resins for composite printing. The fundamental understanding could potentially be extended to other types of two-stage curable resins with different molecular mechanisms. 
    more » « less
  2. Levoglucosan is a renewable chemical obtained in high yields from pyrolysis of cellulosic biomass, which offers rich functionality for synthetic modification and crosslinking. Here, we report the facile and scalable synthesis of a family of biobased networks from triallyl levoglucosan and multifunctional thiols via UV-initiated thiol–ene click chemistry. The multifunctional thiols utilized in this study can also be sourced from renewable feedstocks, leading to overall high bio-based content of the synthesized levoglucosan networks. The thermomechanical and hydrolytic degradation properties of the resultant networks are tailored based on the type and stoichiometric ratio of thiol crosslinker employed. The Young's modulus and glass transition temperature of levoglucosan-based networks are tunable over the wide ranges of 3.3 MPa to 14.5 MPa and −19.4 °C to 6.9 °C, respectively. The levoglucosan-based thermosets exhibit excellent thermal stability with Td,10% > 305 °C for all networks. The suitability of these resin formulations for extrusion-based 3D printing was illustrated using a UV-assisted direct ink write (DIW) system creating 3D printed parts with excellent fidelity. Hydrolytic degradation of these 3D printed parts via ester hydrolysis demonstrated that levoglucosan-based resins are excellent candidates for sustainable rapid prototyping and mass production applications. Overall, this work displays the utility of levoglucosan as a renewable platform chemical that enables access to tailored thermosets important in applications ranging from 3D printing to biomaterials. 
    more » « less
  3. Abstract

    Photopolymerization is a ubiquitous, indispensable technique widely applied in applications from coatings, inks, and adhesives to thermosetting restorative materials for medical implants, and the fabrication of complex macroscale, microscale, and nanoscale 3D architectures via additive manufacturing. However, due to the brittleness inherent in the dominant acrylate‐based photopolymerized networks, a significant need exists for higher performance resin/oligomer formulations to create tough, defect‐free, mechanically ductile, thermally and chemically resistant, high modulus network polymers with rapid photocuring kinetics. This study presents densely cross‐linked triazole‐based glassy photopolymers capable of achieving preeminent toughness of ≈70 MJ m−3and 200% strain at ambient temperature, comparable to conventional tough thermoplastics. Formed either via photoinitiated copper(I)‐catalyzed cycloaddition of monomers containing azide and alkyne groups (CuAAC) or via photoinitiated thiol‐ene reactions from monomers containing triazole rings, these triazole‐containing thermosets completely recover their original dimensions and mechanical behavior after repeated deformations of 50% strain in the glassy state over multiple thermal recovery–strain cycles.

     
    more » « less
  4. null (Ed.)
    3D printing is an essential tool for rapid prototyping in a variety of sectors such as automotive and public health. The 3D printing market is booming, and it is projected that it will continue to thrive in the coming years. Unfortunately, this rapid growth has led to an alarming increase in the amount of 3D printed plastic waste. 3D printing processes such as stereolithography (SLA) and digital light projection (DLP) in particular generally produce petroleum-based thermosets that are further worsening the plastic pollution problem. To mitigate this 3D printed plastic waste, sustainable alternatives to current 3D printing materials must be developed. The present review provides a comprehensive overview of the sustainable advances in SLA/DLP 3D printing to date and offers a perspective on future directions to improve sustainability in this field. The entire life cycle of 3D printed parts has been assessed by considering the feedstock selection and the end-of-use of the material. The feedstock selection section details how renewable feedstocks (from lignocellulosic biomass, oils, and animal products) or waste feedstocks ( e.g. , waste cooking oil) have been used to develop SLA/DLP resins. The end-of-use section describes how materials can be reprocessed ( e.g. thermoplastic materials or covalent adaptable networks) or degraded (through enzymatic or acid/base hydrolysis of sensitive linkages) after end-of-use. In addition, studies that have employed green chemistry principles in their resin synthesis and/or have shown their sustainable 3D printed parts to have mechanical properties comparable to commercial materials have been highlighted. This review also investigates how aspects of sustainability such as recycling for feedstock/end-of-use or biodegradation of 3D printed parts in natural environments can be incorporated as future research directions in SLA/DLP. 
    more » « less
  5. null (Ed.)
    3D woven composites are well known for their high strength, dimensional stability, delamination, and impact resistance. They are often used in aerospace, energy, and automotive industries where material parts can experience harsh service conditions including substantial variations in temperature. This may lead to significant thermal deformations and thermally-induced stresses in the material. Additionally, 3D woven composites are often produced using resin transfer molding (RTM) technique which involves curing the epoxy resin at elevated temperatures leading to accumulation of the processing-induced residual stress. Thus, understanding of effective thermal behavior of 3D woven composites is essential for their successful design and service. In this paper, the effective thermal properties of 3D woven carbon-epoxy composite materials are estimated using mesoscale finite element models previously developed for evaluation of the manufacturing-induced residual stresses. We determine effective coefficients of thermal expansion (CTEs) of the composites in terms of the known thermal and mechanical properties of epoxy resin and carbon fibers. We investigate how temperature sensitivity of the thermal and mechanical properties of the epoxy influences the overall thermal properties of the composite. The simulations are performed for different composite reinforcement morphologies including ply-to-ply and orthogonal. It is shown that even linear dependence of epoxy’s stiffness and CTE on temperature results in a nonlinear dependence on temperature of the overall composite’s CTE. 
    more » « less