On the Use of Surfactant‐Complexed Chitosan for Toughening 3D Printed Polymethacrylate Composites

Abstract

This work reports a simple approach to prepare toughened 3D‐printed polymethacrylate (PMA) composites using surfactant‐modified chitosan (SMCS) particles at loadings between 2–10 wt%. Chitosan (CS) is modified with anionic surfactant, sodium dodecyl sulfate, via ionic complexation to facilitate compatibility and dispersion of CS to PMA matrix by non‐covalent interactions between the components. The study successfully demonstrates high‐accuracy 3D printing of composites with significant improvements in the overall mechanical properties. The composite with the best loading of 8 wt% SMCS shows a tensile modulus of 1.23 ± 0.05 GPa, a tensile strength at 49.8 ± 0.96 MPa, a yield stress at 33.3 ± 1.48 MPa, and a strain‐at‐failure 10.3 ± 0.61%, which are 45%, 40%, 32%, and 68% higher than neat PMA, respectively. This provides a significant improvement in toughness at 4.92 ± 0.55 MJ m−3 for the composite, 184% higher than that of neat PMA. The marked increase in toughness is due to enhanced filler‐matrix interactions which improve the ability of the 3D printed composite to absorb energy under tensile load. The results from this work provide new understandings into the strategies for design and preparation of stereolithography 3D printed materials reinforced with toughening fillers from renewable resources.

Mechanically and Thermally Enhanced 3D-Printed Photocurable Polymer Nanocomposites Containing Functionalized Chitin Nanowhiskers by Stereolithography

“…44,46,63 Tan δ values obtained from DMA experiments generally depict the structural transformation of the materials and are used to evaluate the glass transitions of polymer nanocomposites and highly crosslinked ones. 13,18,38 As shown in Figure 7C, samples containing the pCNW showed higher T g values than that of the neat MA, the result of which can be evidenced by the tan δ peak shift to higher temperatures. This T g increase with the filler concentration is generally attributed to the constrained segmental motions of MA chains as a result of enhanced filler− matrix interactions.…”

“…Higher nanofiller loadings promote excessive inter-filler interactions and formation of aggregates, which not only hinder an effective filler−matrix interaction but also act as stress concentrators that downgrade the abovementioned mechanical properties. 13,36,38 The tensile modulus is an important property that characterizes the rigidity of a given material. this work (i.e., 0.5 wt % pCNW) with previous literature results on SLA-printed MA composites with different fillers and wt% loading: 0.5 wt % GO, 11 1.0 wt % methacrylic acid-modified cellulose nanocrystal (MCNC), 21 1.5 wt % as-prepared CNW, 23 8.0 wt % surfactant-modified chitosan (SMCS), 38 5.1 wt % copper nanofiller (CuNF), 65 2.0 wt % wood flour (WF), 66 and 0.4 wt % lignin (L).…”

“…13,36,38 The tensile modulus is an important property that characterizes the rigidity of a given material. this work (i.e., 0.5 wt % pCNW) with previous literature results on SLA-printed MA composites with different fillers and wt% loading: 0.5 wt % GO, 11 1.0 wt % methacrylic acid-modified cellulose nanocrystal (MCNC), 21 1.5 wt % as-prepared CNW, 23 8.0 wt % surfactant-modified chitosan (SMCS), 38 5.1 wt % copper nanofiller (CuNF), 65 2.0 wt % wood flour (WF), 66 and 0.4 wt % lignin (L). shows that the addition of 0.5 wt % pCNW increases the tensile modulus of the neat MA from 0.85 ± 0.13 to 1.45 ± 0.13 GPa.…”

“…Standard resin from Formlabs was used and modified by adding pCNW fillers. The SLA printing via radical photopolymerization was set to an open-mode 38 operation at room temperature using a 50 μm printing resolution. The resulting 3Dprinted specimens were carefully removed from the built platform and washed with isopropanol to remove any uncured resin.…”

Additively manufactured high-performance polymeric materials and their potential use in the oil and gas industry

“…Typical photocurable resins used are thermosets such as epoxy and acrylate-based formulations usually composed of monomers/oligomers, crosslinkers, and initiators. [ 6 , 17 , 33 – 35 ]…”