Thermoset polymers and fiber-reinforced polymer composites possess the chemical, physical, and mechanical properties necessary for energy-efficient vehicles and structures, but their energy-inefficient manufacturing and the lack of end-of-life management strategies render these materials unsustainable. Here, we demonstrate end-of-life deconstruction and upcycling of high-performance poly(dicyclopentadiene) (pDCPD) thermosets with a concurrent reduction in the energy demand for curing via frontal copolymerization. Triggered material deconstruction is achieved through cleavage of cyclic silyl ethers and acetals incorporated into pDCPD thermosets. Both solution-state and bulk experiments reveal that seven- and eight-membered cyclic silyl ethers and eight-membered cyclic acetals are incorporated efficiently with norbornene-derived monomers, permitting deconstruction at low comonomer loadings. Frontal copolymerization of DCPD with these tailored cleavable comonomers enables energy-efficient manufacturing of sustainable, high-performance thermosets with glass transition temperatures of >100 °C and elastic moduli of >1 GPa. The polymers are fully deconstructed, yielding hydroxyl-terminated oligomers that are upcycled to polyurethane-containing thermosets having a higher glass transition temperatures than that of the original polymer upon reaction with diisocyanates. This approach is extended to frontally polymerized fiber-reinforced composites, where large-fiber volume fraction composites (Vf = 65%) containing a cleavable comonomer are deconstructed and the reclaimed fibers are used to regenerate composites via frontal polymerization that display properties nearly identical to those of the original. This work demonstrates that the use of cleavable monomers, in combination with frontal manufacturing, provides a promising strategy to address sustainability challenges for high-performance materials at multiple stages of their lifecycle.
more »
« less
SELECTIVE CLEAVAGE OF AMINE-LINKED EPOXY COMPOSITE MATRICES BY OXYGEN
This presentation will describe conditions for the use of oxygen as a reagent for the selective cleavage of thermoset composites.
Carbon fiber-reinforced polymer (CFRP) composites have a prominent role in aviation, sporting goods, marine, and other manufacturing sectors and are accumulating en masse as waste, both at end-of-life and as manufacturing defects. We have recently introduced a method to use oxygen itself along with an appropriate catalyst selectively to disassemble such fully-cured composite wastes to recover both ordered carbon fiber sheets and organic materials suitable for re-manufacturing of second-life resin systems.
more »
« less
- NSF-PAR ID:
- 10434771
- Date Published:
- Journal Name:
- SAMPE 2023
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Carbon fiber reinforced polymer (CFRP) composites have been increasingly used in many vehicles such as airplanes, automobiles, and ships due to the advantages of high-strength, high-modulus, lightweight, and corrosion resistance. CFRP structures enhance the vehicle's performance, energy-efficiency, comfort, and safety. However, a common safety concern is how the CFRP materials perform when the vehicle is in fire and if there are enough time to safely evacuate the passengers. The elevated temperature can soften and decompose the polymer matrix, delaminate the CFRP laminate, and burn the CFRP through the contact with oxygen. As a result, the thermal and flammability response of CFRP is important for considering CFRP for vehicle applications; and some specialty high-temperature or flame/smoke/toxicity-proven resins have been investigated for CFRP parts manufacturing due to the needs. In this paper, a novel flame resistant hypothesis of utilizing the unique nano/micro- interlocked fiber reinforcing structure of the long-range carbon nanofiber z-threaded CFRP (ZT-CFRP) composite laminates for improving the flammability performance will be investigated. The carbon nanofibers (CNT) and carbon nanotubes (CNT), which have excellent thermal and mechanical properties, will be dispersed in an epoxy resin and will zig-zag thread through a carbon fiber fabric using an electrical/flow assisted impregnation process to create the unidirectional ZT-CFRP prepregs, respectively, which will be further processed into ZT-CFRP composite laminates. The UL-94 flammability test will be employed to characterize the ZT-CFRP laminates' flammability performance against the control baseline data of the regular CFRP, all without using any flame retardant chemicals. An impressive self-extinguishing flammability characteristic of the CNF based ZT-CFRP samples has been distinctly identified from all the samples. The UL-94 testing results and the effectiveness of using the long-range nanofiber z-threading strategy for enabling the novel nano/microstructure-induced flame resistant and self-extinguishing characteristics will be discussed.more » « less
-
Carbon fiber reinforced polymer (CFRP) composites have been increasingly used to replace metal parts in many industries such as aerospace, marine, automotive, and sporting goods. The CFRP parts compared with their metallic counter parts have the advantages of lightweight, significantly higher tensile strength, stiffer, and corrosion resistant. On the other hand, compared with many metal parts, the CFRP parts have many well-known disadvantages including the lower toughness, lower through-thickness tensile and shear strengths, lower thermal conductivity, lower electrical conductivity, and lower operating temperature. These disadvantages have made the conversion from metal parts into CFRP parts challenging and costly to design, manufacture, and maintain. The use of nanoparticles in polymer has been studied in the recent two decades. Carbon nanotubes (CNTs) and carbon nanofibers (CNFs) have been dispersed in various thermoset and thermoplastic polymers and improved the mechanical, electrical, and thermal properties; however, the properties were not comparable to CFRP. Later, researchers tried to infuse CNTs or CNFs into either carbon fiber preforms [1] or glass fiber preforms [2] for improving the mechanical properties. But the results were marginal and with great uncertainty due to the challenges of nanoparticle dispersion, filtering, and alignment while being infused through the fiber preform. The glass fiber preform experiments ended with relatively more consistent improvement than the carbon fiber preform experiments since that the glass fiber preform has significantly larger pores than the carbon fiber preform' s. The small pore size presented a great challenge for infusing millions of unaligned long CNTs or CNFs through the carbon fiber preform without being filtered. To infuse long CNFs or CNTs through the carbon fiber preform and achieve reliable improvements, especially for 55% or higher carbon fiber volume fraction with increasingly tighter pores, an innovative plan for the processing and nano-reinforcing strategy is necessary. The z-threading strategy [3, 4, 5] has been reported to have consistent experimental successes in achieving the statistically meaningful improvement in multifunctional properties. The manufacturing steps of the CNF z-threaded CFRP (ZT-CFRP) are: (1) disperse the CNFs in a resin, (2) use a strong electrical field to align the CNFs in either the B-stage epoxy film or a CNF/resin impregnated sponge layer, whereas the CNFs are aligned in the through-thickness direction of the film or sponge layer. (3) place the resin film or sponge layer on a preheated dry carbon fiber fabric and press the resin film into the hot carbon fabric and allow the resin flow to carry the well-aligned CNFs to thread through the pores in the carbon fabric. (4) cool down the resin saturated and CNF z-threaded carbon fiber fabric to obtain the ZT-CFRP prepreg. (5) use the ZT-CFRP prepreg to make the ZT-CFRP laminate. Compared with the traditional CFRP, the ZT-CFRP laminates were reported of having improvement in the Mode-I delamination toughness, interlaminar shear strength, longitudinal compressive strength, through-thickness electrical conductivity, through-thickness thermal conductivity, and can reach the carbon fiber volume fraction of 55-80%. It is an effective approach to achieve a multifunctional CFRP for potentially expanding CFRP's applications.more » « less
-
null (Ed.)Abstract Pellet-based extrusion deposition of carbon fiber-reinforced composites at high material deposition rates has recently gained much attention due to its applications in large-scale additive manufacturing. The mechanical and physical properties of large-volume components largely depend on their reinforcing fiber length. However, very few studies have been done thus far to have a direct comparison of additively fabricated composites reinforced with different carbon fiber lengths. In this study, a new additive manufacturing (AM) approach to fabricate long fiber-reinforced polymer (LFRP) was first proposed. A pellet-based extrusion deposition method was implemented, which directly used thermoplastic pellets and continuous fiber tows as feedstock materials. Discontinuous long carbon fibers, with an average fiber length of 20.1 mm, were successfully incorporated into printed LFRP samples. The printed LFRP samples were compared with short fiber-reinforced polymer (SFRP) and continuous fiber-reinforced polymer (CFRP) counterparts through mechanical tests and microstructural analyses. The carbon fiber dispersion, distribution of carbon fiber length and orientation, and fiber wetting were studied. As expected, a steady increase in flexural strength was observed with increasing fiber length. The carbon fibers were highly oriented along the printing direction. A more uniformly distributed discontinuous fiber reinforcement was found within printed SFRP and LFRP samples. Due to decreased fiber impregnation time and lowered impregnation rate, the printed CFRP samples showed a lower degree of impregnation and worse fiber wetting conditions. The feasibility of the proposed AM methods was further demonstrated by fabricating large-volume components with complex geometries.more » « less
-
more » « less
Abstract Composites play progressively significant roles across a spectrum of applications involving high‐performance materials and products within industries such as aerospace, naval, automotive, construction, missiles, and defense technology. Notably, oriented fiber composites have garnered substantial attention due to their advantageous attributes like a high strength‐to‐weight ratio and controlled anisotropy. Nonetheless, challenges persist in uneven fiber alignment, fiber clustering within the matrix material, and constraints on fiber volume, impeding the mass production of oriented fiber‐reinforced composites. In this study, we present a novel approach to 3D printing of uniformly aligned short fiber reinforcement in a composite of heavily loaded carbon and nylon. Capitalizing on the additive manufacturing potential of rapidity and precision, the extrusion process induces carbon fiber (CF) alignments in filaments via shear forces. The 3D‐printed structures that were created displayed impressive potential for customization. They consistently demonstrated improved mechanical and thermal properties when compared to the original nylon structures. Our methodology for producing uniformly dispersed and aligned short fiber reinforcement in polymer composites promises to propel the advancement of design and manufacturing for high‐performance composite materials and components.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Conference Paper:
- https://doi.org/10.33599/nasampe/s.23.0206
