A developed SBS vitrimer for asphalt modification: Synergistic self-healing and aging resistance via dynamic covalent crosslinking

Guowei Hu; Ruiqi Chen; Zhifei Tan; Xueliang Jiang; Zhen Leng

doi:10.1016/j.cscm.2025.e05679

A developed SBS vitrimer for asphalt modification: Synergistic self-healing and aging resistance via dynamic covalent crosslinking

Guowei Hu
, Ruiqi Chen
, Zhifei Tan
, Xueliang Jiang
, Zhen Leng

Research output: Journal article publication › Journal article › Academic research › peer-review

1 Citation (Scopus)

Abstract

This study develops a styrene-butadiene-styrene (SBS) vitrimer via disulfide bond-mediated dynamic covalent crosslinking to address the inherent aging susceptibility and non-healing properties of conventional SBS in asphalt modification. Epoxidized SBS (eSBS) was synthesized and crosslinked with 4,4′-dithiodibutyric acid (DTBA) to construct covalent adaptable networks. Fourier-transform infrared spectroscopy (FTIR) confirmed successful vitrimer formation through ester bond formation (1734 cm−1 peak). Optical microscopy revealed rapid self-healing behavior in the optimized SBS vitrimer (SV3, 0.3 ‰ DTBA of the butadiene structural units in SBS), with surface notches fully closing within 50 min at 90 °C, whereas unmodified SBS exhibited no healing under identical conditions. Thermogravimetric analysis demonstrated comparable thermal stability between SV3 and pristine SBS, with maximum degradation temperatures (T_max) near 463 °C. Mechanically, SV3 achieved a 25 % increase in tensile strength while retaining 63 % elongation relative to SBS, along with 100 % creep recovery at 80–100 °C, contrasting with irreversible deformation in unmodified SBS. Aging resistance was evaluated via Rolling Thin Film Oven (RTFO) and Pressure Aging Vessel (PAV) tests. The SV3-modified binder (SV3mB) outperformed conventional SBS-modified binder (SBSmB), showing 54–58 % higher elastic recovery (R-value) and 19–20 % lower non-recoverable creep compliance (J_nr) post-RTFO aging. After PAV aging, SV3mB exhibited 46–105 % higher R-values and 62–70 % lower J_nr values. A healing index (H), derived from viscoelastic continuum damage (VECD) theory, quantified self-healing efficiency, revealing SV3mB’s superior damage mitigation under high strain (25 %–30 %) and extended fatigue life (N_f) due to dynamic bond exchange. These results demonstrate that SBS vitrimers enhance asphalt binder durability, aging resistance, and autonomous repair capabilities, offering transformative potential for pavement materials in extreme environmental conditions.

Original language	English
Article number	e05679
Journal	Case Studies in Construction Materials
Volume	24
DOIs	https://doi.org/10.1016/j.cscm.2025.e05679
Publication status	Published - Jul 2026

Keywords

Aging resistance
Reversible covalent bonds
SBS modified asphalt
Self-healing
Vitrimer

ASJC Scopus subject areas

Materials Science (miscellaneous)

More information

10.1016/j.cscm.2025.e05679

Cite this

@article{8e589ceae904444bb1563b946cb2d303,

title = "A developed SBS vitrimer for asphalt modification: Synergistic self-healing and aging resistance via dynamic covalent crosslinking",

abstract = "This study develops a styrene-butadiene-styrene (SBS) vitrimer via disulfide bond-mediated dynamic covalent crosslinking to address the inherent aging susceptibility and non-healing properties of conventional SBS in asphalt modification. Epoxidized SBS (eSBS) was synthesized and crosslinked with 4,4′-dithiodibutyric acid (DTBA) to construct covalent adaptable networks. Fourier-transform infrared spectroscopy (FTIR) confirmed successful vitrimer formation through ester bond formation (1734 cm−1 peak). Optical microscopy revealed rapid self-healing behavior in the optimized SBS vitrimer (SV3, 0.3 ‰ DTBA of the butadiene structural units in SBS), with surface notches fully closing within 50 min at 90 °C, whereas unmodified SBS exhibited no healing under identical conditions. Thermogravimetric analysis demonstrated comparable thermal stability between SV3 and pristine SBS, with maximum degradation temperatures (Tmax) near 463 °C. Mechanically, SV3 achieved a 25 \% increase in tensile strength while retaining 63 \% elongation relative to SBS, along with 100 \% creep recovery at 80–100 °C, contrasting with irreversible deformation in unmodified SBS. Aging resistance was evaluated via Rolling Thin Film Oven (RTFO) and Pressure Aging Vessel (PAV) tests. The SV3-modified binder (SV3mB) outperformed conventional SBS-modified binder (SBSmB), showing 54–58 \% higher elastic recovery (R-value) and 19–20 \% lower non-recoverable creep compliance (Jnr) post-RTFO aging. After PAV aging, SV3mB exhibited 46–105 \% higher R-values and 62–70 \% lower Jnr values. A healing index (H), derived from viscoelastic continuum damage (VECD) theory, quantified self-healing efficiency, revealing SV3mB{\textquoteright}s superior damage mitigation under high strain (25 \%–30 \%) and extended fatigue life (Nf) due to dynamic bond exchange. These results demonstrate that SBS vitrimers enhance asphalt binder durability, aging resistance, and autonomous repair capabilities, offering transformative potential for pavement materials in extreme environmental conditions.",

keywords = "Aging resistance, Reversible covalent bonds, SBS modified asphalt, Self-healing, Vitrimer",

author = "Guowei Hu and Ruiqi Chen and Zhifei Tan and Xueliang Jiang and Zhen Leng",

note = "Publisher Copyright: {\textcopyright} 2025 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license. http://creativecommons.org/licenses/by/4.0/",

year = "2026",

month = jul,

doi = "10.1016/j.cscm.2025.e05679",

language = "English",

volume = "24",

journal = "Case Studies in Construction Materials",

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TY - JOUR

T1 - A developed SBS vitrimer for asphalt modification

T2 - Synergistic self-healing and aging resistance via dynamic covalent crosslinking

AU - Hu, Guowei

AU - Chen, Ruiqi

AU - Tan, Zhifei

AU - Jiang, Xueliang

AU - Leng, Zhen

PY - 2026/7

Y1 - 2026/7

N2 - This study develops a styrene-butadiene-styrene (SBS) vitrimer via disulfide bond-mediated dynamic covalent crosslinking to address the inherent aging susceptibility and non-healing properties of conventional SBS in asphalt modification. Epoxidized SBS (eSBS) was synthesized and crosslinked with 4,4′-dithiodibutyric acid (DTBA) to construct covalent adaptable networks. Fourier-transform infrared spectroscopy (FTIR) confirmed successful vitrimer formation through ester bond formation (1734 cm−1 peak). Optical microscopy revealed rapid self-healing behavior in the optimized SBS vitrimer (SV3, 0.3 ‰ DTBA of the butadiene structural units in SBS), with surface notches fully closing within 50 min at 90 °C, whereas unmodified SBS exhibited no healing under identical conditions. Thermogravimetric analysis demonstrated comparable thermal stability between SV3 and pristine SBS, with maximum degradation temperatures (Tmax) near 463 °C. Mechanically, SV3 achieved a 25 % increase in tensile strength while retaining 63 % elongation relative to SBS, along with 100 % creep recovery at 80–100 °C, contrasting with irreversible deformation in unmodified SBS. Aging resistance was evaluated via Rolling Thin Film Oven (RTFO) and Pressure Aging Vessel (PAV) tests. The SV3-modified binder (SV3mB) outperformed conventional SBS-modified binder (SBSmB), showing 54–58 % higher elastic recovery (R-value) and 19–20 % lower non-recoverable creep compliance (Jnr) post-RTFO aging. After PAV aging, SV3mB exhibited 46–105 % higher R-values and 62–70 % lower Jnr values. A healing index (H), derived from viscoelastic continuum damage (VECD) theory, quantified self-healing efficiency, revealing SV3mB’s superior damage mitigation under high strain (25 %–30 %) and extended fatigue life (Nf) due to dynamic bond exchange. These results demonstrate that SBS vitrimers enhance asphalt binder durability, aging resistance, and autonomous repair capabilities, offering transformative potential for pavement materials in extreme environmental conditions.

AB - This study develops a styrene-butadiene-styrene (SBS) vitrimer via disulfide bond-mediated dynamic covalent crosslinking to address the inherent aging susceptibility and non-healing properties of conventional SBS in asphalt modification. Epoxidized SBS (eSBS) was synthesized and crosslinked with 4,4′-dithiodibutyric acid (DTBA) to construct covalent adaptable networks. Fourier-transform infrared spectroscopy (FTIR) confirmed successful vitrimer formation through ester bond formation (1734 cm−1 peak). Optical microscopy revealed rapid self-healing behavior in the optimized SBS vitrimer (SV3, 0.3 ‰ DTBA of the butadiene structural units in SBS), with surface notches fully closing within 50 min at 90 °C, whereas unmodified SBS exhibited no healing under identical conditions. Thermogravimetric analysis demonstrated comparable thermal stability between SV3 and pristine SBS, with maximum degradation temperatures (Tmax) near 463 °C. Mechanically, SV3 achieved a 25 % increase in tensile strength while retaining 63 % elongation relative to SBS, along with 100 % creep recovery at 80–100 °C, contrasting with irreversible deformation in unmodified SBS. Aging resistance was evaluated via Rolling Thin Film Oven (RTFO) and Pressure Aging Vessel (PAV) tests. The SV3-modified binder (SV3mB) outperformed conventional SBS-modified binder (SBSmB), showing 54–58 % higher elastic recovery (R-value) and 19–20 % lower non-recoverable creep compliance (Jnr) post-RTFO aging. After PAV aging, SV3mB exhibited 46–105 % higher R-values and 62–70 % lower Jnr values. A healing index (H), derived from viscoelastic continuum damage (VECD) theory, quantified self-healing efficiency, revealing SV3mB’s superior damage mitigation under high strain (25 %–30 %) and extended fatigue life (Nf) due to dynamic bond exchange. These results demonstrate that SBS vitrimers enhance asphalt binder durability, aging resistance, and autonomous repair capabilities, offering transformative potential for pavement materials in extreme environmental conditions.

KW - Aging resistance

KW - Reversible covalent bonds

KW - SBS modified asphalt

KW - Self-healing

KW - Vitrimer

UR - https://www.scopus.com/pages/publications/105029834371

U2 - 10.1016/j.cscm.2025.e05679

DO - 10.1016/j.cscm.2025.e05679

M3 - Journal article

AN - SCOPUS:105029834371

SN - 2214-5095

VL - 24

JO - Case Studies in Construction Materials

JF - Case Studies in Construction Materials

M1 - e05679

ER -

A developed SBS vitrimer for asphalt modification: Synergistic self-healing and aging resistance via dynamic covalent crosslinking

Abstract

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ASJC Scopus subject areas

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