Influence of Catalyst Content and Epoxy/Carboxylate Ratio on Isothermal Creep of Epoxy Vitrimers
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials and Epoxy Vitrimer Formulation
2.2. Experimental Characterization
3. Thermomechanical Characterization of Epoxy Vitrimers
3.1. Thermal Characterization
3.2. Static and Dynamic Mechanical Characterization
3.3. Isothermal Creep of Zn2+ Epoxy Vitrimers
4. Assessment of the Recyclability and Reshaping (3R Analysis)
4.1. Mechanical Recycling
4.2. Composites Thermoforming
5. Discussion
5.1. Effect of Catalyst Content
- (i)
- T < Tg
- both parameters decrease due to the greater energy absorbed by the active polymer chains, and the viscous slippage of the molecules becomes easier to achieve;
- (ii)
- Tg < T < Tv
- the E2 and η2 increase with the temperature due to the more significant orientation of polymer chains along the creep loading direction, which results in an orientational hardening; and
- (iii)
- T > Tv
- a further reduction of retardancy parameters is observed only in the case of vitrimeric systems (AV-5 and AV-10) due to the molecular flow induced by the transesterification reaction. This effect depends on the amount of zinc acetate content [51].
5.2. Effect of Stoichiometry
6. Conclusions
- The glass transition temperature of the vitrimeric system slightly reduces by 5% and 15% for polymers AV5 and AV10, respectively, compared to A, and increases by 4% and 13% for polymers BV5 and BV10, respectively, compared to B.
- The storage modulus and damping ratio trends with temperature of the vitrimeric systems indicate that at low temperatures, the polymer behaves like a thermoset, whereas at high temperatures, above Tg, the polymer flows resemble the behavior of a thermoplastic polymer.
- Evident creep of samples subjected to tensile load was found at different temperatures. The presence of metallic ions strongly catalyzes the ester-interchange reaction, particularly in the balanced systems (AV5 and AV10).
- The creep analysis according to Burger’s model showed that the elastic and viscous parameters are affected by the epoxy/acyl group and the catalyst content. The highest flow at a high temperature was obtained for the balanced stoichiometric ratio and 10% of zinc acetate due to the higher molecular mobility promoted by transesterification reactions.
- The induced flow at temperatures above Tv enables the recyclability of the polymer and its composites. By applying adequate temperature and pressure to the material, it can be reshaped and reformed, maintaining a similar performance to the pristine material.
Author Contributions
Funding
Institutional Review Board Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Sample Codex | LY 3508 [phr] | Aradur 917-1 [phr] | 960-1 acc. [phr] | Epoxy/Acyl Ratio, r [-] | ZnAc2 * [%] |
---|---|---|---|---|---|
A | 100 | 40 | 3 | 1.0 | 0 |
AV-5 | 100 | 40 | 3 | 1.0 | 5 |
AV-10 | 100 | 40 | 3 | 1.0 | 10 |
B | 100 | 70 | 3 | 0.6 | 0 |
BV-5 | 100 | 70 | 3 | 0.6 | 5 |
BV-10 | 100 | 70 | 3 | 0.6 | 10 |
Description | T @ 10% Decomposition [°C] | T @ Maximum Decomposition [°C] | Char Yield @800 °C [wt%] | Tg, DSC [°C] | Reaction Enthalpy [J/g] | Tpeak [°C] |
---|---|---|---|---|---|---|
A | 369 | 410 | 7.04 | 111.2 | 216.6 ± 1.2 | 130 ± 5 |
AV-5 | 333 | 405 | 13.13 | 105.1 | 242.5 ± 1.6 | 140 ± 1 |
AV-10 | 325 | 402 | 15.15 | 94.3 | 270.3 ± 2.0 | 139 ± 2 |
B | 371 | 416 | 5.44 | 111.5 | 282.7 ± 1.1 | 137 ± 4 |
BV-5 | 337 | 413 | 12.55 | 115.6 | 287.5 ± 1.9 | 150 ± 5 |
BV-10 | 341 | 414 | 13.98 | 126.3 | 280.2 ± 2.6 | 145 ± 3 |
Elastic Modulus [MPa] | Ultimate Strain [mm/mm] | Ultimate Stress [MPa] | |
---|---|---|---|
A | 2704 ± 5 | 0.028 ± 0.002 | 68.3 ± 0.7 |
AV-5 | 2596 ± 8 | 0.027 ± 0.003 | 61.5 ± 0.6 |
AV-10 | 2087 ± 7 | 0.024 ± 0.005 | 57.2 ± 0.5 |
B | 3059 ± 11 | 0.036 ± 0.004 | 83.2 ± 1.0 |
BV-5 | 2998 ± 6 | 0.027 ± 0.004 | 74.2 ± 0.7 |
BV-10 | 3018 ± 5 | 0.020 ± 0.003 | 58.5 ± 0.6 |
@35 °C | @170 °C | ||||||
---|---|---|---|---|---|---|---|
Tg, DMA [°C] | E″ [Mpa] | E″ [Mpa] | Tanδ [-] | E′ [Mpa] | E″ [Mpa] | Tanδ [-] | |
A | 105.6 ± 1.1 | 1899 ± 33 | 22.1 ± 0.3 | 0.0116 ± 0.0002 | 5.14 | 0.02 | 0.004 |
AV-5 | 108.8 ± 0.9 | 2221 ± 56 | 28.5 ± 0.5 | 0.0128 ± 0.0001 | 12.08 | 1.43 | 0.118 |
AV-10 | 101.0 ± 0.7 | 2484 ± 47 | 33.4 ± 0.3 | 0.0135 ± 0.0003 | 11.89 | 3.08 | 0.259 |
B | 117.3 ± 0.8 | 1867 ± 29 | 26.7 ± 0.2 | 0.0143 ± 0.0003 | 9.20 | 0.02 | 0.002 |
BV-5 | 119.1 ± 1.5 | 2369 ± 21 | 31.5 ± 0.4 | 0.0133 ± 0.0004 | 10.88 | 1.61 | 0.148 |
BV-10 | 113.6 ± 0.6 | 2698 ± 37 | 30.7 ± 0.1 | 0.0114 ± 0.0002 | 6.70 | 3.48 | 0.518 |
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Palmieri, B.; Cilento, F.; Amendola, E.; Valente, T.; Dello Iacono, S.; Giordano, M.; Martone, A. Influence of Catalyst Content and Epoxy/Carboxylate Ratio on Isothermal Creep of Epoxy Vitrimers. Polymers 2023, 15, 3845. https://doi.org/10.3390/polym15183845
Palmieri B, Cilento F, Amendola E, Valente T, Dello Iacono S, Giordano M, Martone A. Influence of Catalyst Content and Epoxy/Carboxylate Ratio on Isothermal Creep of Epoxy Vitrimers. Polymers. 2023; 15(18):3845. https://doi.org/10.3390/polym15183845
Chicago/Turabian StylePalmieri, Barbara, Fabrizia Cilento, Eugenio Amendola, Teodoro Valente, Stefania Dello Iacono, Michele Giordano, and Alfonso Martone. 2023. "Influence of Catalyst Content and Epoxy/Carboxylate Ratio on Isothermal Creep of Epoxy Vitrimers" Polymers 15, no. 18: 3845. https://doi.org/10.3390/polym15183845