Self-Healing Elastomers: A sustainable solution for automotive applications

Utrera‐Barrios, Saul; Verdejo, Raquel; López–Manchado, Miguel A.; Santana, Marianella Hernández

doi:10.1016/j.eurpolymj.2023.112023

Cited by 28 publications

(12 citation statements)

References 139 publications

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“…Therefore, a more application-oriented approach is needed to realize the minimum modification of the existing processing technology. 16 It is well-known that sulfur vulcanization is the most important and still the most widely used process in the tire industry. In fact, controlling the cross-linking density is crucial for achieving the optimal balance between mechanical properties and the self-healing performance of sulfur-curved rubber.…”

Section: ■ Introductionmentioning

confidence: 99%

Self-Healing and Recyclable Vulcanized Polyisoprene Based on a Sulfur-Rich Copolymer Cross-Linking Agent Derived from Inverse Vulcanization

Huang,

Liu,

et al. 2024

ACS Sustainable Chem. Eng.

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The sulfur vulcanization process has been widely used in the rubber industry, but it is difficult to obtain self-healing and recyclable vulcanized rubber. The latter can be obtained by introducing a dynamic bond network, but it is difficult to achieve good self-healing and mechanical strength simultaneously. In this contribution, based on an inverse vulcanization reaction, a new type of sulfur-rich copolymer was synthesized by bulk copolymerization of thioctic acid and sulfur at elevated temperatures. During the vulcanization process, the carboxyl groups in the copolymer react with zinc oxide to form zinc carboxylate, which interacts with N-methylimidazole to vulcanize the polyisoprene rubber. The resulting vulcanized rubber exhibits exceptional mechanical strength and elastic properties, comparable to those of commercial polyisoprene, with a tensile strength of up to 24.2 MPa and an elastic recovery rate of 96.1%. Small molecule model reactions demonstrate that N-methylimidazole accelerates the disproportionation reaction of disulfide bonds and polysulfide bonds in the system, leading to the self-healing and recyclable properties of the novel vulcanized rubber. In the presence of nucleophilic catalysts, excellent self-healing and recycling performances of the obtained vulcanized polyisoprene can be realized. After the selfhealing process, the tensile strength and fracture strain of vulcanized polyisoprene recovered by 95.0 and 83.3%, respectively. After thermal compression repair at 120 °C for 6 h, the sample's tensile strength and elongation at break reached 95.0 and 83.3%, respectively, of the original sample. After the first recycling, the sample's tensile strength and elongation at break were restored to 69.8 and 84.8%, respectively, of the original sample. In the polyisoprene/carbon black composite, the sulfur-rich copolymer serves not only as a cross-linking agent but also generates sulfur radicals during vulcanization, which are captured by carbon black, thereby grafting onto the surface of carbon black. This greatly improves the dispersion of carbon black in the rubber matrix and enhances the interfacial adhesion of the composite. Thanks to the strong radical capture ability of carbon black, the amounts of N-methylimidazole and zinc oxide can be reduced (to 0.5 parts and 2 parts, respectively), avoiding stress concentration in the rubber network caused by excessive cross-linking and thus affecting the mechanical properties. In addition, the N-methylimidazole-catalyzed S−S bond disproportionation reaction also endows the polyisoprene/carbon black composite with dynamic properties.

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Section: ■ Introductionmentioning

confidence: 99%

Self-Healing and Recyclable Vulcanized Polyisoprene Based on a Sulfur-Rich Copolymer Cross-Linking Agent Derived from Inverse Vulcanization

Huang,

Liu,

et al. 2024

ACS Sustainable Chem. Eng.

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“…CANs exhibit similar performance to conventional thermosets under normal conditions but can undergo dynamic covalent bond exchange reactions in response to external stimuli like heat , and solvents, enabling stress relaxation and flow. In addition to recyclability, CANs can endow materials other properties such as self-healing, , shape memory, and self-welding . While CANs based on dynamic Diels–Alder chemistry were initially reported by Wudl and Chen, CANs have rapidly evolved through the utilization of various existing or specially designed DCBs, such as ester exchange, , boronic ester bonds, disulfide bonds, imine bonds, and acetal bonds.…”

Section: Introductionmentioning

confidence: 99%

Biobased Recyclable Rubbers With Shape Memory, Self-welding, and Damping Properties by Cross-Linking Epoxidized Natural Rubber with Succinic Anhydride

Zou,

Yao,

Zhang

et al. 2023

ACS Sustainable Chem. Eng.

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“…The polymers that have been studied for their self-healing properties are usually elastomers, such as polyurethanes, which have excellent self-healing properties. − The macroscopic scratch healing experiment is a conventional way to characterize self-healing properties, where the cut polymer recovers after a period of heating, − and the scratch healing experiment has been widely used to study vitrimers. ,,− However, some experiments do not achieve nearly perfect healing results as in the case of self-healing elastomers, and the vast majority of epoxy vitrimer still remains a thin seam after self-healing. ,− Therefore, the self-healing performance of the vitrimer needs to be studied more thoroughly.…”

Section: Introductionmentioning

confidence: 99%

“…The polymers that have been studied for their self-healing properties are usually elastomers, 28 such as polyurethanes, which have excellent self-healing properties. 29−32 The macroscopic scratch healing experiment is a conventional way to characterize self-healing properties, where the cut polymer recovers after a period of heating, 29−33 experiment has been widely used to study vitrimers.…”

Section: Introductionmentioning

confidence: 99%

Imine-Containing Epoxy Vitrimer Cured by Active Ester: Properties and Theoretical Analysis

Liu,

Cui

et al. 2023

ACS Appl. Polym. Mater.

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Vitrimers are polymers possessing a covalent adaptable network (CANs) that can undergo a topological structural transformation under specific conditions, enabling material reprocessing. In this study, an active ester hardener containing imine bonds (TAI) was synthesized, and subsequently, epoxy resin with CANs (epoxy vitrimer, DGEBA/TAI) was prepared, which exhibited excellent thermal stability (initial degradation temperature of 364 °C and char yield at 800 °C of 30%), low water absorption (0.25 wt %), and good dielectric properties (dielectric constant of 3.37 and dielectric loss of 0.013). A comparative scratch healing test between the epoxy vitrimer and conventional epoxy resin showed that the hard vitrimer could not demonstrate self-healing ability and that scratch healing was derived from deformation recovery. The performance of such hard vitrimers should focus on recycling and reprocessing rather than a self-healing capability. Thus, the resin could be effectively recycled and reused by a hot pressing or solvent method, resulting in recycled resins with good tensile strength (70 MPa for hot-press welding and 58 MPa for solvent recycling) compared to the originals (69 MPa). In addition, the vitrimer materials allow shape reconfiguration through a network structure transformation, and an alternative analytical method was proposed to obtain the relaxation time of the vitrimer by fitting the equation of the stress relaxation curve, which could mitigate some of the interferences and provide a method for data reliability verification of the viscoelastic properties of the vitrimer.

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Self-Healing Elastomers: A sustainable solution for automotive applications

Cited by 28 publications

References 139 publications

Self-Healing and Recyclable Vulcanized Polyisoprene Based on a Sulfur-Rich Copolymer Cross-Linking Agent Derived from Inverse Vulcanization

Self-Healing and Recyclable Vulcanized Polyisoprene Based on a Sulfur-Rich Copolymer Cross-Linking Agent Derived from Inverse Vulcanization

Biobased Recyclable Rubbers With Shape Memory, Self-welding, and Damping Properties by Cross-Linking Epoxidized Natural Rubber with Succinic Anhydride

Imine-Containing Epoxy Vitrimer Cured by Active Ester: Properties and Theoretical Analysis

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