Background <p>The relationship between molecular-scale chain scission and bulk viscoelasticity in soft polymer networks remains incompletely understood, particularly in multiple network elastomers, where energy dissipation arises from the interaction between irreversible chain-scission damage and reversible time-dependent mechanics.</p> Objective <p>This study aims to elucidate how cumulative, progressive chain-scission damage influences bulk viscoelasticity in double network elastomers through both experiments and constitutive modeling.</p> Methods <p>A non-swelling, platinum-cured silicone double network elastomer was synthesized and served as a model system to investigate damage-induced effects on viscoelasticity. Cyclic tensile loading was applied to introduce systematically controlled chain-scission damage. The changes in viscoelastic properties were characterized via stress relaxation tests and dynamic mechanical analysis. A constitutive model coupling hyperelasticity with damage-induced viscosity through stretch-mediated chain-scission kinetics and chain-length-dependent disentanglement kinetics was established to describe the observed damage-viscosity coupling.</p> Results <p>Experiments revealed that cumulative bond breaking in the double network elastomer contributes not only to Mullins-type softening but also to measurable increases in apparent relaxation time and viscoelastic dissipation rate. The proposed model successfully reproduced damage-related effects, including both irreversible primary hysteresis caused by network damage and narrower, persistent secondary hysteresis due to damage-induced viscoelastic dissipation.</p> Conclusion <p>Although the damage-induced viscoelastic dissipation was small compared to the energy directly dissipated by bond breaking, our results provide direct experimental evidence and quantification that internal molecular damage can modulate bulk time-dependent constitutive behavior. These findings lay the foundation for predictive modeling of dissipative mechanics mediated by damage–viscoelasticity coupling in complex multiple network elastomers.</p>

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Effect of Controlled Chain-Scission Damage on Viscoelasticity in Double Network Elastomers

  • B. Zhang,
  • B. Zhu,
  • C.-Y. Hui,
  • A. T. Zehnder

摘要

Background

The relationship between molecular-scale chain scission and bulk viscoelasticity in soft polymer networks remains incompletely understood, particularly in multiple network elastomers, where energy dissipation arises from the interaction between irreversible chain-scission damage and reversible time-dependent mechanics.

Objective

This study aims to elucidate how cumulative, progressive chain-scission damage influences bulk viscoelasticity in double network elastomers through both experiments and constitutive modeling.

Methods

A non-swelling, platinum-cured silicone double network elastomer was synthesized and served as a model system to investigate damage-induced effects on viscoelasticity. Cyclic tensile loading was applied to introduce systematically controlled chain-scission damage. The changes in viscoelastic properties were characterized via stress relaxation tests and dynamic mechanical analysis. A constitutive model coupling hyperelasticity with damage-induced viscosity through stretch-mediated chain-scission kinetics and chain-length-dependent disentanglement kinetics was established to describe the observed damage-viscosity coupling.

Results

Experiments revealed that cumulative bond breaking in the double network elastomer contributes not only to Mullins-type softening but also to measurable increases in apparent relaxation time and viscoelastic dissipation rate. The proposed model successfully reproduced damage-related effects, including both irreversible primary hysteresis caused by network damage and narrower, persistent secondary hysteresis due to damage-induced viscoelastic dissipation.

Conclusion

Although the damage-induced viscoelastic dissipation was small compared to the energy directly dissipated by bond breaking, our results provide direct experimental evidence and quantification that internal molecular damage can modulate bulk time-dependent constitutive behavior. These findings lay the foundation for predictive modeling of dissipative mechanics mediated by damage–viscoelasticity coupling in complex multiple network elastomers.