Synergistic effect of chemically modified CNC nanofiller concentration on the mechanical and thermal properties of additively manufactured PLA-TPU-CNC composites

Paul Eric C. Maglalang; Blessie A. Basilia; Paul Eric C. Maglalang; Blessie A. Basilia

doi:10.3934/matersci.2025024

AIMS Materials Science

2025, Volume 12, Issue 3: 514-561. doi: 10.3934/matersci.2025024

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Research article

Synergistic effect of chemically modified CNC nanofiller concentration on the mechanical and thermal properties of additively manufactured PLA-TPU-CNC composites

Paul Eric C. Maglalang ^1,2,
Blessie A. Basilia ^{1
,
,}

1.
School of Chemical, Biological, and Materials Engineering and Sciences, Mapúa University, 658 Muralla St., Intramuros Manila, 1002 Philippines
2.
Industrial Technology Development Institute—Department of Science and Technology (DOST), Compound General Santos Avenue, Bicutan, Taguig City, 1631 Philippines

Received: 13 April 2025 Revised: 21 May 2025 Accepted: 04 June 2025 Published: 27 June 2025

The continual application of renewable cellulose nanoparticles has led to several advancements in their performance as a reinforcing component for the fabrication of high-performance additively manufactured nanocomposite products. Nonetheless, incorporating hydrophilic cellulose nanocrystals into hydrophobic thermoplastics, such as polylactic acid and thermoplastic urethane, remains a substantial challenge for achieving successful and smooth compatibility as an additional component in 3D-printed composites. This study has successfully investigated the effects of chemically modified cellulose nanocrystals at concentrations of 0.05%, 1%, and 3% when blended with hexadecyltrimethylammonium bromide and polylactic acid-thermoplastic urethane (PLA-TPU) at an 80:20 ratio. This study demonstrates the use of a fused deposition modeling (FDM) printer to manufacture 3D-printed PLA-TPU-CNC (cellulose nanocrystal) composites through additive manufacturing. The composite with 0.05% modified CNC exhibits 19.12 MPa higher tensile strength and 58.3% higher flexural strength than the unmodified one. Furthermore, the PLA-TPU blend with 1% modified CNC obtained the highest Izod impact strength, 63.43 MPa. The 3D-printed composite with 1% modified CNC displayed significantly better compressive strength than other modified variations and concentrations in the unmodified group. Composites with 1% unmodified CNC exhibited 2.33% higher heat deflection than blended PLA-TPU. The composites with 0.05% modified CNC showed an increase of 1.12% compared to the PLA-TPU blend and a modest increase of up to 2.71% compared to the other modified CNC concentrations. The composite with 1% modified CNC was superior to all the variations in terms of hardness, with a 29.6% increase above the 1% unmodified composite. The utilization of cationic surfactants, such as hexadecyltrimethylammonium bromide (HDTMA-Br), enhances CNC infiltration, interfacial adhesion, and hydrophobicity control, thereby improving the mechanical performance of the composites and making them suitable for specific medical and engineering material designs and applications. The F-statistics for all concentration levels yielded a ratio substantially greater than the F-critical value, and the p-value was considerably less than 0.05, indicating a significant and favorable design criterion.
Citation: Paul Eric C. Maglalang, Blessie A. Basilia. Synergistic effect of chemically modified CNC nanofiller concentration on the mechanical and thermal properties of additively manufactured PLA-TPU-CNC composites[J]. AIMS Materials Science, 2025, 12(3): 514-561. doi: 10.3934/matersci.2025024

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Abstract

The continual application of renewable cellulose nanoparticles has led to several advancements in their performance as a reinforcing component for the fabrication of high-performance additively manufactured nanocomposite products. Nonetheless, incorporating hydrophilic cellulose nanocrystals into hydrophobic thermoplastics, such as polylactic acid and thermoplastic urethane, remains a substantial challenge for achieving successful and smooth compatibility as an additional component in 3D-printed composites. This study has successfully investigated the effects of chemically modified cellulose nanocrystals at concentrations of 0.05%, 1%, and 3% when blended with hexadecyltrimethylammonium bromide and polylactic acid-thermoplastic urethane (PLA-TPU) at an 80:20 ratio. This study demonstrates the use of a fused deposition modeling (FDM) printer to manufacture 3D-printed PLA-TPU-CNC (cellulose nanocrystal) composites through additive manufacturing. The composite with 0.05% modified CNC exhibits 19.12 MPa higher tensile strength and 58.3% higher flexural strength than the unmodified one. Furthermore, the PLA-TPU blend with 1% modified CNC obtained the highest Izod impact strength, 63.43 MPa. The 3D-printed composite with 1% modified CNC displayed significantly better compressive strength than other modified variations and concentrations in the unmodified group. Composites with 1% unmodified CNC exhibited 2.33% higher heat deflection than blended PLA-TPU. The composites with 0.05% modified CNC showed an increase of 1.12% compared to the PLA-TPU blend and a modest increase of up to 2.71% compared to the other modified CNC concentrations. The composite with 1% modified CNC was superior to all the variations in terms of hardness, with a 29.6% increase above the 1% unmodified composite. The utilization of cationic surfactants, such as hexadecyltrimethylammonium bromide (HDTMA-Br), enhances CNC infiltration, interfacial adhesion, and hydrophobicity control, thereby improving the mechanical performance of the composites and making them suitable for specific medical and engineering material designs and applications. The F-statistics for all concentration levels yielded a ratio substantially greater than the F-critical value, and the p-value was considerably less than 0.05, indicating a significant and favorable design criterion.

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