Fundamentals aspects of crosslinking control of PDMS rubber at high temperatures using TEMPO nitroxide
type: Dataset
description: The control of macromolecular structure has recently become an important topic of polymer science from both an academic and an industrial point of view. Indeed, free-radical crosslinking of Polydimethyl-vinylmethyl-siloxane (vinyl-PDMS) rubber by organic peroxide suffers from premature crosslinking at high temperatures, which is called scorching. Consequently, the basic aim of the investigations described in this thesis is to widen and explore the network topology–crosslinking kinetics relationships and find a novel way to control free-radical crosslinking chemistry and topological parameters of final PDMS networks. The work is primarily focused on the extensive study of the crosslinking control of PDMS rubber at high temperatures. A novel composition using 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) and dicumyl peroxide (DCP) for scorch delay and control of the final network topology of the PDMS has been proposed. The work specified in this thesis is therefore directed to find a proper [TEMPO]/[DCP] ratio provided the development of a new biphasic material such as PA12/PDMS blend type TPV (Thermoplastic Vulcanizated). For this purpose a new method based on the relationship between the kinetics of the macro-radicals coupling [Rcc(t)] was derived from a fundamental kinetic model and the viscoelastic changes of the complex shear modulus (G’(t) and G”(t)). As a main result, the rheological modelling shows that this new method accurately predicts the time variation of complex shear modulus at any temperature and [TEMPO]/[DCP] ratio. Interestingly, addition of TEMPO to the TPV novel composition provided the PA12/PDMS blend compatibilization in the dynamic process and gives a new material having a controlled structure and morphology. A better insight in understanding the blend composition and the morphology development relationships is aimed at.
identifier: NNT: 2011LYO10002
issued: 2026-05-10T12:55:19.190227
language: en
modified: 2026-05-10T12:55:19.190232
contact point: Organization
  fn: CCSD
keyword: chimothechemical-sciencesother
keyword: compatibilisation
keyword: compatibilization
keyword: crosslinking
keyword: free-radical
keyword: infoeu-reposemanticsdoctoralthesis
keyword: modelisation
keyword: modelling
keyword: radicaux-libres
keyword: reticulation
keyword: tempo-nitroxide
keyword: tempo-nitroxyde
keyword: thermoplastic-vulcanizated
keyword: thermoplastique-vulcanise
keyword: theses
landing page: https://theses.hal.science/tel-00839605

Fundamentals aspects of crosslinking control of PDMS rubber at high temperatures using TEMPO nitroxide
type: Distribution
format: HTML
issued: 2026-05-10T12:55:19.196123
modified: 2026-05-10T12:55:19.175576
access URL: https://theses.hal.science/tel-00839605

test_moissonnage_selune
type: Agent