Comprehension and improvements of LSR type silicone elastomers

L'objectif de ces travaux de thèse était d'améliorer les performances d'étanchéité de connecteurs automobiles fabriqués en silicone. La première approche visait à comprendre les relations entre les structures chimiques présentes dans les formulations LSR et les propriétés mécaniques afin de proposer des additifs favorisant la résistance à la déchirure. Lors d'une étude préalable, nous avons étudié l'effet synergétique du platine et de la silice sur la dégradation thermique de formulations silicone. Ce travail a permis de décrire le mécanisme et de proposer de nouvelles formulations plus performantes en terme de taux de résidu après pyrolyse. Cette première étude alliée à d'autres techniques a permis d'analyser les structures chimiques présentes dans huit formulations commerciales. Nous avons également caractérisé la réactivité ainsi que la structure du réseau polymère obtenu après réticulation. Les relations liant les structures chimiques à la structure des réseaux ont été établies. Enfin, les propriétés mécaniques telles que la déformation rémanente à la compression, les propriétés ultimes (force et élongation à la rupture) et la résistance à la déchirure des matériaux ont été corrélées avec les différentes structures des réseaux.La seconde partie était dédiée à la synthèse d'un additif fonctionnel thermiquement activable permettant de réparer a posteriori une déchirure. Afin de sélectionner le meilleur système correspondant au cahier des charges, une revue complète de la bibliographie a été réalisée sur la réversibilité des fonctions urées et uréthanes, en portant une attention particulière sur la chimie des isocyanate bloqués. Deux molécules bloquantes ont été sélectionnées après étude de la réactivation thermique de la fonction isocyanate. Un monomère portant cette fonction isocyanate bloqué a été engagé dans une réaction de copolymérisation afin d'obtenir plusieurs générations d'additifs testés selon les normes appliquées aux connecteurs.This PhD work aimed at improving the water and air-proofing properties of automotive connectors made of silicones. The first approach consisted of understanding the relationships between the chemical structures added in the LSR formulations and their ultimate mechanical performances so as to propose additives which would improve tear resistance of the materials. In a preliminary study, we investigated the synergistic role of platinum catalyst and silica on the thermal degradation of silicone formulations. These investigations allowed us to describe the degradation mechanism and to suggest new formulations in order to improve the residue content at high temperature. This first study, combined with other techniques, allowed us to analyze the chemical structures present in eight commercial formulations. We also characterized the reactivities as well as the network topologies obtained after curing the formulations. Correlations between the chemical structures and the network topology were then established. Finally, some mechanical properties, i.e. the compression set, the ultimate properties (tensile strength and elongation at break) and the tear resistance of final materials were matched with network topologies. The second part was dedicated to the synthesis of a functional additive which could be thermally reactivated to heal a tear. In order to select the best system according to the strict specifications of this work, a complete literature review on the reversibility of urea and urethane bonds was done, with special emphasis on blocked isocyanate chemistry. After a study on the isocyanate group thermal reactivation, two blocking molecules were chosen. A monomer bearing this blocked isocyanate function was then copolymerized to obtain different generations of additives which were finally tested according to standard norms applied to connectors

Chemical Structure - Mechanical Properties of Commercial Liquid Silicone Rubbers

International audienc

Compréhension et améliorations d'élastomères silicone de type Liquid Silicone Rubber

L'objectif de ces travaux de thèse était d'améliorer les performances d'étanchéité de connecteurs automobiles fabriqués en silicone. La première approche visait à comprendre les relations entre les structures chimiques présentes dans les formulations LSR et les propriétés mécaniques afin de proposer des additifs favorisant la résistance à la déchirure. Lors d'une étude préalable, nous avons étudié l'effet synergétique du platine et de la silice sur la dégradation thermique de formulations silicone. Ce travail a permis de décrire le mécanisme et de proposer de nouvelles formulations plus performantes en terme de taux de résidu après pyrolyse. Cette première étude alliée à d'autres techniques a permis d'analyser les structures chimiques présentes dans huit formulations commerciales. Nous avons également caractérisé la réactivité ainsi que la structure du réseau polymère obtenu après réticulation. Les relations liant les structures chimiques à la structure des réseaux ont été établies. Enfin, les propriétés mécaniques telles que la déformation rémanente à la compression, les propriétés ultimes (force et élongation à la rupture) et la résistance à la déchirure des matériaux ont été corrélées avec les différentes structures des réseaux.La seconde partie était dédiée à la synthèse d'un additif fonctionnel thermiquement activable permettant de réparer a posteriori une déchirure. Afin de sélectionner le meilleur système correspondant au cahier des charges, une revue complète de la bibliographie a été réalisée sur la réversibilité des fonctions urées et uréthanes, en portant une attention particulière sur la chimie des isocyanate bloqués. Deux molécules bloquantes ont été sélectionnées après étude de la réactivation thermique de la fonction isocyanate. Un monomère portant cette fonction isocyanate bloqué a été engagé dans une réaction de copolymérisation afin d'obtenir plusieurs générations d'additifs testés selon les normes appliquées aux connecteurs.This PhD work aimed at improving the water and air-proofing properties of automotive connectors made of silicones. The first approach consisted of understanding the relationships between the chemical structures added in the LSR formulations and their ultimate mechanical performances so as to propose additives which would improve tear resistance of the materials. In a preliminary study, we investigated the synergistic role of platinum catalyst and silica on the thermal degradation of silicone formulations. These investigations allowed us to describe the degradation mechanism and to suggest new formulations in order to improve the residue content at high temperature. This first study, combined with other techniques, allowed us to analyze the chemical structures present in eight commercial formulations. We also characterized the reactivities as well as the network topologies obtained after curing the formulations. Correlations between the chemical structures and the network topology were then established. Finally, some mechanical properties, i.e. the compression set, the ultimate properties (tensile strength and elongation at break) and the tear resistance of final materials were matched with network topologies. The second part was dedicated to the synthesis of a functional additive which could be thermally reactivated to heal a tear. In order to select the best system according to the strict specifications of this work, a complete literature review on the reversibility of urea and urethane bonds was done, with special emphasis on blocked isocyanate chemistry. After a study on the isocyanate group thermal reactivation, two blocking molecules were chosen. A monomer bearing this blocked isocyanate function was then copolymerized to obtain different generations of additives which were finally tested according to standard norms applied to connectors.MONTPELLIER-Ecole Nat.Chimie (341722204) / SudocSudocFranceF

Looking Over Liquid Silicone Rubber: 1. Network topology versus Chemical formulations

International audienceThis study proposes a comprehensive study on liquid silicone rubber (LSR) formulations to unravel which components (among functional polydimethylsiloxane polymers and modified silica fillers) improve the mechanical properties of the final materials. In this first part, various industrial products have been deformulated using conventional chemical analyses. The silica content and their surface chemistry were assessed by TGA. Architecture and molar mass of polymers were deduced from (29)Si NMR and SEC in toluene, respectively. Relative concentrations of hydride and vinyl reactive groups and stoichiometric imbalance (r = n(SiH)/n(SiVi)) were quantified by proton NMR. Stoichiometric imbalance is slightly higher than 1.5 for cross-linker with hydride functions well redistributed along the chain, whereas for some formulations, r's as high as 3.7 were implemented. These variations has strong implications on the cross-linking density of the final material, since the remaining hydride groups react together and decrease the molar mass between cross-links. From the comparison between formulations, it was shown that hardness adjustment is mainly performed by playing on two parameters: filler content and molar mass between cross-linking points for hardness ranging from 20 to 30 Shore A. Above this limit, it is necessary to modify the silica surface with reactive groups, such as vinyl functions. Surprisingly, two formulations were shown to use a dual cross-linking catalysis systems, peroxide and platinum, leading to efficient and full cure even at lower temperature (typically 140 °C). Network topologies were estimated from the predicted chemistry of the materials in a final discussion part

Chemical Structure - Mechanical Properties of Commercial Liquid Silicone Rubbers

International audienc

Task-Specific Ionic Liquids with Lactate Anion Applied to Improve ZnO Dispersibility in the Ethylene-Propylene-Diene Elastomer

Task-specific ionic liquids (TSILs) are ionic liquids with structures and, consequently, properties and behaviors designed for particular applications. In this work, task-specific ILs with alkylammonium or benzalkonium cations and carboxyl groups in the form of lactate anions were used to promote the homogeneous dispersion of the curatives in the elastomer matrix. The reaction of carboxyl groups of TSILs with zinc oxide, which acts as a vulcanization activator, was confirmed. This interaction improved the solubility and dispersibility of zinc oxide particles in the ethylene-propylene-diene (EPDM) monomer matrix, which consequently affected the curing characteristics of rubber compounds. Most importantly, TSILs increased the efficiency of vulcanization by shortening the time, lowering the temperature and increasing the enthalpy of this process, while maintaining safe processing of elastomer composites. EPDM vulcanizates containing TSILs with lactate anion were characterized by satisfactory functional properties

Looking over Liquid Silicone Rubbers: (1) Network Topology vs Chemical Formulations

This study proposes a comprehensive study on liquid silicone rubber (LSR) formulations to unravel which components (among functional polydimethylsiloxane polymers and modified silica fillers) improve the mechanical properties of the final materials. In this first part, various industrial products have been deformulated using conventional chemical analyses. The silica content and their surface chemistry were assessed by TGA. Architecture and molar mass of polymers were deduced from ²⁹Si NMR and SEC in toluene, respectively. Relative concentrations of hydride and vinyl reactive groups and stoichiometric imbalance (<i>r</i> = <i>n</i>_SiH/<i>n</i>_SiVi) were quantified by proton NMR. Stoichiometric imbalance is slightly higher than 1.5 for cross-linker with hydride functions well redistributed along the chain, whereas for some formulations, <i>r</i>’s as high as 3.7 were implemented. These variations has strong implications on the cross-linking density of the final material, since the remaining hydride groups react together and decrease the molar mass between cross-links. From the comparison between formulations, it was shown that hardness adjustment is mainly performed by playing on two parameters: filler content and molar mass between cross-linking points for hardness ranging from 20 to 30 Shore A. Above this limit, it is necessary to modify the silica surface with reactive groups, such as vinyl functions. Surprisingly, two formulations were shown to use a dual cross-linking catalysis systems, peroxide and platinum, leading to efficient and full cure even at lower temperature (typically 140 °C). Network topologies were estimated from the predicted chemistry of the materials in a final discussion part

Looking over Liquid Silicone Rubbers: 2. Mechanical properties vs. network topology

International audienceIn the previous paper of this series, eight formulations were analyzed under their un-cross-linked forms to relate Liquid Silicone Rubber (LSR) chemical compositions to material network topologies. Such topologies were confirmed by swelling measurements and hardness evaluation on vulcanized samples. In this article, characterizations of cross-linked materials is further done using different mechanical measurements on final materials, including dynamic mechanical analysis, compression set, stress-strain behavior and tear resistance. It was shown that the compression set value is mainly related to the chains motion: increasing the filler-polymer interactions and/or decreasing the dangling/untethered chains content positively impact the compression resistance. Elongation at break depends on the molar mass between cross-linking points, showing an optimum value set at around 20,000 g.mol-1 i.e. the critical mass between entanglements. The distribution of elastic strands into the network has strong implications on the stress-strain curves profiles. By generating bimodal networks, the ultimate properties are enhanced. The materials cured by hydride addition on vinyl groups catalyzed by peroxide exhibit poorer compression set and tensile strength values, respectively due to post-cross-linking reaction and broad polydispersity index of elastic network chains. A final discussion relates these final mechanical properties to network topologies

Thermal Analysis and SEM Microscopy Applied to Studying the Efficiency of Ionic Liquid Immobilization on Solid Supports

Ionic liquids (ILs) are widely used in elastomer composites, primarily as vulcanization activators or accelerators, crosslinkers, conductive additives, or dispersing agents of fillers. The aim of this work was to study the efficiency of ionic liquid immobilization on filler surfaces using different techniques of thermal analysis and scanning electron microscopy (SEM). Ionic liquid, such as 1-decyl 3-methylimidazolium bromide (DmiBr) was grafted on the surface of silica, calcium oxide, and carbon black to improve the dispersion degree of their particles in the elastomeric matrix. Thermal analysis and SEM microscopy revealed a key role in determining the efficiency of the filler modification with ILs dissolved in acetone. Identifying the weight loss associated with thermal decomposition of DmiBr in modified fillers, allowed the calculation of the efficiency of their modification and compare the surface reactivity of studied fillers with DmiBr. Silica and carbon black exhibited high and comparable ability for interaction with ionic liquid. SEM images showed that particles of DmiBr-modified fillers were quite homogeneously dispersed in the elastomer matrix and exhibited good adhesion to the elastomer

Task-Specific Ionic Liquids with Lactate Anion Applied to Improve ZnO Dispersibility in the Ethylene-Propylene-Diene Elastomer

Task-specific ionic liquids (TSILs) are ionic liquids with structures and, consequently, properties and behaviors designed for particular applications. In this work, task-specific ILs with alkylammonium or benzalkonium cations and carboxyl groups in the form of lactate anions were used to promote the homogeneous dispersion of the curatives in the elastomer matrix. The reaction of carboxyl groups of TSILs with zinc oxide, which acts as a vulcanization activator, was confirmed. This interaction improved the solubility and dispersibility of zinc oxide particles in the ethylene-propylene-diene (EPDM) monomer matrix, which consequently affected the curing characteristics of rubber compounds. Most importantly, TSILs increased the efficiency of vulcanization by shortening the time, lowering the temperature and increasing the enthalpy of this process, while maintaining safe processing of elastomer composites. EPDM vulcanizates containing TSILs with lactate anion were characterized by satisfactory functional properties