Thermolatent Heterogeneous Epoxy–Acid Formulation for the Manufacture of Preimpregnated Sheets and Composites with Vitrimer Properties
Quentin-Arthur Poutrel,
Ianis Retailleau,
Ugo Lafont
et al.
Abstract:The goal of this work is to develop carbon fiber-reinforced
polymer
(CFRP) composites showing vitrimer properties and manufacturable by
the prepreg technique. Since their invention in 2011, epoxy vitrimer
matrices have shown an appealing potential to produce CFRPs with healing,
adhesion, and recycling abilities. While techniques such as resin
infusion or resin transfer molding have been successfully applied,
production of composites by handling of preimpregnated sheets requires
a specific set of properties whi… Show more
“…In both Leibler et al. and following studies with the epoxy-acid vitrimer systems, ,,− as discussed in the previous paragraph, FTIR is generally used to track the formation of ester groups, but due to the limited resolution, only a broad and single peak from 1675 to 1775 cm –1 , centered at 1732 cm –1 , was observed and assigned to the absorption of ester groups from esterification reactions (Figure S1c). In fact, this peak is the result of an overlap between the absorption of the carbonyl group in acids and formed ester groups.…”
We used atomic force microscopy-based infrared spectroscopy (AFM-IR) and nanomechanical mapping (AFM-NM) to image the surface of a vitrimer, specifically dicarboxylic acid-cured diglycidyl ether of bisphenol A (DGEBA), to assess the curing process of a surface layer and compared this to the process in the bulk. We identified the β-hydroxy esters with various functionalities that are the key to form the cross-links for a system, including difunctional DGEBA and carboxylic acids. The IR peaks of the carbonyl group in generated ester groups are distinguished clearly from those in acids, allowing us to quantitatively assess the curing process at the surface and in the bulk. The initial curing at the surface exhibits a gradual cross-linking and is found to be lower than a rapid cross-linking in the bulk due to a relatively lower concentration of the β-hydroxy esters with high functionalities. This curing process leads to a smaller chemically and mechanically heterogeneous nanostructure at the surface relative to the bulk. After multiple reprocessings, a substantial number of esters lacking dynamic exchange capability form in the bulk, which decrease the flowability and reprocessability of the vitrimers and therefore the mechanical properties.
“…In both Leibler et al. and following studies with the epoxy-acid vitrimer systems, ,,− as discussed in the previous paragraph, FTIR is generally used to track the formation of ester groups, but due to the limited resolution, only a broad and single peak from 1675 to 1775 cm –1 , centered at 1732 cm –1 , was observed and assigned to the absorption of ester groups from esterification reactions (Figure S1c). In fact, this peak is the result of an overlap between the absorption of the carbonyl group in acids and formed ester groups.…”
We used atomic force microscopy-based infrared spectroscopy (AFM-IR) and nanomechanical mapping (AFM-NM) to image the surface of a vitrimer, specifically dicarboxylic acid-cured diglycidyl ether of bisphenol A (DGEBA), to assess the curing process of a surface layer and compared this to the process in the bulk. We identified the β-hydroxy esters with various functionalities that are the key to form the cross-links for a system, including difunctional DGEBA and carboxylic acids. The IR peaks of the carbonyl group in generated ester groups are distinguished clearly from those in acids, allowing us to quantitatively assess the curing process at the surface and in the bulk. The initial curing at the surface exhibits a gradual cross-linking and is found to be lower than a rapid cross-linking in the bulk due to a relatively lower concentration of the β-hydroxy esters with high functionalities. This curing process leads to a smaller chemically and mechanically heterogeneous nanostructure at the surface relative to the bulk. After multiple reprocessings, a substantial number of esters lacking dynamic exchange capability form in the bulk, which decrease the flowability and reprocessability of the vitrimers and therefore the mechanical properties.
“…Among the array of chemistries available, two of them gather considerable attention for composite applications: − transesterification and disulfide exchanges. These chemistries have been particularly studied , with some composite processes already tested such as pultrusion, impregnation, − and resin transfer molding (RTM), − to name a few. For instance, Chabert et al prepared vitrimer-based glass-fiber composite plates via resin transfer molding .…”
Initially
bound for landfill or incineration due to strong limitations
in their repair or recycling, thermoset composite materials have recently
received considerable attention in order to improve their end-of-life.
In this respect, vitrimers appear to be a solution of choice, as they
possess the capability for topological reconfiguration through an
associative exchange mechanism, imparting them glass-like properties
at high temperatures. However, despite these advances, studies with
particular focus on the process such as pultrusion, impregnation,
and resin transfer molding (RTM) remain scarce. In this work, a detailed
reactivity study was conducted on a vitrimer formulation based on
disulfide exchange chemistry toward the RTM process, which includes
the development of a time–temperature–transformation
(TTT) diagram. On this basis, vitrimer plates were successfully prepared
by RTM, yielding thermal and mechanical properties similar to the
reference epoxy resin. Additionally, while exhibiting very competitive
properties, the resulting vitrimer materials demonstrated the ability
to be reshaped and reprocessed. This work covers resin formulation,
reactivity, implementation into the RTM process and, ultimately, material
and mechanical characterization.
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