journal article·2026-03Open access

From filler–polymer interfacial rearrangements to silica enrichment: Microstructural origins of mechanical degradation in hydrothermally aged HTV silicone rubber

Manar Ramram, Lénaïk Belec, Jean-François Chailan, François Perseil Rouillard, François-Xavier Perrin

Abstract

This study presents the evolution of standard mechanical properties of a silica-filled silicone rubber subjected to cyclic ageing conditions, including vacuum phases at 80 °C and high-pressure steam phases at 134 °C. The observed changes in mechanical properties are associated with molecular and macromolecular-scale transformations reported in a previous study. Over the course of ageing, Shore A hardness increased in correlation with rising silica content. The observed loss of elastic recovery, indicated by the compression set, was linked to alterations in network topology, particularly due to complex rearrangements at the polymer–filler interfaces. Monotonic tensile tests at both low and high strain levels revealed the respective impacts of increasing silica content and polymer network hydrolysis. Additionally, the changes in the Mullins effect was associated with microstructural changes. The tensile behavior was modeled using a hyperelastic approach incorporating a hydrodynamic amplification factor, which supported a phenomenological understanding of the ageing effects on both monotonic tensile responses and the Mullins effect.
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Research context

OpenAlex topics: Polymer Nanocomposites and Properties · Elasticity and Material Modeling · Polymer crystallization and properties

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References (49)

Show source-provided references
1. Andriot · 2009
2. Silicone sealants and structural adhesives10.1016/S0143-7496(01)00018-5 ↗
3. Dvornic · 2000 · 185
4. A review on silicone rubber10.1007/s40009-013-0150-2 ↗
5. Influence of the microstructure of gums on the mechanical properties of silicone high consistency rubbers10.1002/pi.5131 ↗
6. The effect of bound rubber on vulcanization kinetics in silica filled silicone rubber10.1039/C6RA20063J ↗
7. Reinforcement of silicone rubber by particulate silica10.5254/1.3539660 ↗
8. Semiempirical relationships between properties and loading in filled elastomers10.5254/1.3536275 ↗
9. The influence of fumed silica properties on the processing, curing, and reinforcement properties of silicone rubber10.5254/1.3538299 ↗
10. Hydrolytic and thermal degradation study of some model and polymeric siloxane compounds
11. Brahami · 2022
12. Accelerated hydrothermal weathering of silicone rubber, EPDM, and their blends10.1002/app.1994.070540915 ↗
13. Chemical stress-relaxation of polydimethylsiloxane Elastomers110.1021/ja01647a052 ↗
14. Degradation of silicone rubbers with different hardness in various aqueous solutions10.1016/j.polymdegradstab.2014.07.011 ↗
15. Chemical aging of the silicone rubber in a simulated and three accelerated proton exchange membrane fuel cell environments10.1016/j.jpowsour.2012.05.105 ↗
16. Effect of water on life prediction of liquid silicone rubber seals in polymer electrolyte membrane fuel cell10.1016/j.jpowsour.2011.07.066 ↗
17. Patel · 2001 · 97
18. Acidic-thermal ageing effect on compression stress relaxation of silicone rubber10.1007/s11223-019-00113-5 ↗
19. Temperature and humidity effect on aging of silicone rubbers as sealing materials for proton exchange membrane fuel cell applications10.1016/j.applthermaleng.2016.05.095 ↗
20. Interpreting surface degradation of HTV silicone rubber filled with Micro/nano-silica under AC and DC voltages10.1007/s11664-020-08265-w ↗
21. Durability of crosslinked polydimethylsyloxanes: the case of composite insulators10.1088/1468-6996-8949/9/2/024406 ↗
22. Degradation and service-life prediction of silicone rubber in a highly alkaline environment simulating concrete10.1016/j.engfailanal.2022.106305 ↗
23. Hydrolytic crack in a rubbery network10.1016/j.eml.2019.100531 ↗
24. Mössbauer, NMR and ATR-FTIR spectroscopic investigation of degradation in RTV siloxane foams10.1016/j.polymdegradstab.2006.11.017 ↗
25. Aging mechanisms in RTV polysiloxane foams10.1016/j.polymdegradstab.2015.08.013 ↗
26. Pressure steam ageing of silica filled silicone rubber : degradation mechanisms10.1016/j.polymdegradstab.2025.111332 ↗
27. 1989 · 34
28. Effect of fumed silica surface area on silicone rubber reinforcement
29. Reinforcement studies—effect of silica structure on properties and crosslink density10.5254/1.3539687 ↗
30. Investigation of the hydrothermal stability of cross-linked liquid silicone rubber (LSR)10.1016/j.polymdegradstab.2005.04.016 ↗
31. Control of mullins stress softening in silicone elastomer composites by rational design of fumed silica fillers10.1016/j.compscitech.2021.108955 ↗
32. A theoretical basis for viscoelastic relaxation of elastomers in the long-time limit10.1021/ma00238a014 ↗
33. The theory of permanent set at elevated temperatures in natural and synthetic rubber vulcanizates10.1063/1.1707724 ↗
34. Elasticity recovery of crosslinked EPDM: influence of the chemistry and nanofillers10.1007/s00397-020-01246-0 ↗
35. Current perspectives on silicone rubber technology10.5254/1.3535846 ↗
36. A generalized tube model of rubber elasticity and stress softening of filler reinforced elastomer systems10.1002/1521-3919(20001201)9:9<742::AID-MATS742>3.0.CO;2-4 ↗
37. Tensile properties of fumed silica filled polydimethylsiloxane networks10.1016/j.compositesa.2013.06.016 ↗
38. Molecular theory of rubber elasticity10.1295/polymj.17.1 ↗
39. The tube model theory of rubber elasticity10.1088/0034-4885/51/2/003 ↗
40. Universal properties of filled rubbers: mechanisms for reinforcement on different length scales
41. Universal properties in filler-loaded rubbers10.5254/1.3538664 ↗
42. Correlation between the hierarchical structure evolution and mullins effect of filled rubber under variable amplitude loading10.1016/j.polymer.2023.125988 ↗
43. A review on the mullins effect10.1016/j.eurpolymj.2008.11.017 ↗
44. Breakage of carbon-rubber networks by applied stress10.1021/ie50508a034 ↗
45. Stress softening in carbon black-reinforced vulcanizates. Strain rate and temperature effects10.1002/app.1966.070100205 ↗
46. Slipping of molecules during the deformation of reinforced rubber10.5254/1.3542602 ↗
47. Stress softening experiments in silica-filled polydimethylsiloxane provide insight into a mechanism for the mullins effect10.1016/j.polymer.2005.09.039 ↗
48. New progress in the theory and model of carbon Black reinforcement of elastomers10.1002/app.20802 ↗
49. Correlation between mechanical properties and microscopic structures of an optimized silica fraction in silicone rubber10.1016/j.compscitech.2018.07.024 ↗