Search Results (49)

To enhance the high-temperature resistance of silicone rubber and meet the application requirements of flexible conductive silicone rubber under elevated temperature conditions, this study adopts a chemical modification strategy by introducing phenyl groups into the molecular chains of silicone rubber to improve its thermal resistance. High-phenyl-content hydroxyl-terminated silicone oil (MPPS) was used as the polymer backbone, and vinylmethyldimethoxysilane (VDMS) served as the chain extender. Through a silanol condensation reaction, vinylmethylphenyl polysiloxane (VMPPS) with a crosslinkable structure was synthesized, providing reactive sites for subsequent vulcanization and molding. Subsequently, needle-like silver-coated glass fiber (AGF) conductive fillers were prepared via a green and environmentally friendly electroless silver plating method. These fillers were incorporated into the phenyl polysiloxane matrix to impart electrical conductivity to the phenyl silicone rubber while synergistically enhancing its thermal resistance. Finally, thermally resistant conductive silicone rubber was fabricated through high-temperature vulcanization, and the key properties of the material were systematically characterized. The synthesized phenyl polysiloxane exhibited a number-averaged molecular weight of up to 181,136, with a PDI of 2.43. When the loading of AGF reached 25 phr, the phenyl silicone rubber composite achieved the electrical percolation threshold, exhibiting a conductivity of 7.12 S/cm. With a further increase in AGF content to 35 phr, the composite demonstrated excellent thermal stability, with a 5% weight loss temperature of 478 °C and a residual mass of 37.36% at 800 °C. Moreover, after thermal aging at 100 °C for 72 h, the conductivity degradation of the phenyl silicone rubber was significantly lower than that of commercial silicone rubber, indicating outstanding electrical stability. This study provides an effective approach for the application of flexible electronic materials under extreme thermal environments. Full article

A series of Si-H- or Si-Vi-terminated, branched and linear oligomers containing Me₂SiO segments were prepared by equilibrium polymerization or non-equilibrium polymerization initiated by living anions, respectively. These oligomers were used to improve the defects of concentrated crosslinking points and the high hardness of crosslinked products when using phenyltris(dimethylsiloxy)silane or 1,1,5,5-tetramethyl-3,3-diphenyl trisiloxane as crosslinking agents in the preparation of silicone gel. NMR, FT-IR, and GPC characterized the structure and molecular weight information of the prepared oligomers. The effects of equilibrium polymerization and the anionic non-equilibrium ring-opening polymerization methods on the structure of oligomers were investigated in detail, together with the structure, the molar ratio of SiH to SiVi, and the phenyl content on the thermal properties and the transmittance retention yield of the silicone gel. The introduction of phenyl groups increases the glass transition temperature of silicone gel from −121.29 °C to −117.71 °C when the phenyl content increased from 0.88 wt% to 3.17 wt%. Meanwhile, the thermal decomposition temperature of silicone gel at 10% weight loss in the N₂ atmosphere increased from 440.5 °C to 480.0 °C. When the SiH/SiVi molar ratio is close to 1.0, the transmittance retention yield of the prepared silicone gel using Si-Vi-terminated phenyl T-shaped polysiloxane as the matrix and α, ω-dimethylsiloxyl-terminated PDMS as the crosslinking agent could reach 88.9% after 25 min of UV irradiation. Full article

Hydrogels, known for their outstanding water absorption, flexibility, and biocompatibility, have been widely utilized in various fields. Nevertheless, their application is still limited by their relatively low mechanical performance. This study has successfully developed a dual-network hydrogel with exceptional mechanical properties by embedding amino-functionalized polysiloxane (APSi) networks into a polyvinyl alcohol (PVA) matrix. This hydrogel effectively dissipates energy through dense sacrificial bonds between the networks, allowing for precise control over its tensile strength (ranging from 0.07 to 1.46 MPa) and toughness (from 0.06 to 2.17 MJ/m³) by adjusting the degree of crosslinking in the polysiloxane network. Additionally, the hydrogel exhibits excellent conductivity (10.97 S/cm) and strain sensitivity (GF = 1.43), indicating its potential for use in wearable strain sensors. Moreover, at the end of its life (EOL), the sensor waste can be repurposed as an adsorbent material for metal ions in water treatment, achieving the recycling of hydrogel materials and maximizing resource utilization. Full article

Polysiloxanes with silver nanoparticles (Ag NPs) have garnered attention for their distinctive physicochemical properties, which make them promising candidates for advanced material applications. This study presents a systematic investigation into the thermal properties and degradation mechanisms of polysiloxane/Ag nanocomposites, emphasising the innovative incorporation of Ag NPs directly into polysiloxane networks via in situ reduction of Ag⁺ ions by Si-H groups. Six polysiloxane matrices were synthesised by hydrosilylation of poly(methylhydrosiloxane) (PMHS) or poly(vinylsiloxane) (polymer V₃) with three cross-linking agents of varying molecular structures and functionality. Thermogravimetric analysis combined with mass spectrometry revealed that the introduction of Ag NPs alters the thermal properties of polysiloxane networks, primarily affecting the redistribution of Si bonds that occurs during the pyrolysis of these systems. Monitoring the pyrolysis process using FTIR spectroscopy allowed us to investigate the effect of the presence of Ag NPs on the degradation mechanism of the studied nanocomposites. The presence of the free-carbon phase and metallic silver phase in the Ag-containing silicon oxycarbide materials obtained was confirmed by Raman spectroscopy and XRD analyses, respectively. These findings demonstrate the possibility of fabricating Ag/SiOC materials with ceramic residues in the range of 43 to 84%. This work provides new insights into the thermal behaviour of polysiloxane/Ag nanocomposites and underscores their potential for high-performance applications in thermally demanding environments. Full article

Three-dimensional printing is ideally suited to produce unique and complex shapes. In this study, the material properties of polysiloxanes, commonly named silicones, produced additively by two different methods, namely, multi-jet fusion (MJF) and material extrusion (ME) with liquid printing heads, are investigated. The chemical composition was compared via Fourier-transform infrared spectroscopy, evolved gas analysis mass spectrometry, pyrolysis gas chromatography coupled to mass spectrometry, and thermogravimetry (TGA). Density and low-temperature flexibility, mechanical properties and crosslink distance via freezing point depression were measured before and after post-treatment at elevated temperatures. The results show significant differences in the chemical composition, material properties, as well as surface quality of the tested products produced by the two manufacturing routes. Chemical analysis indicates that the investigated MJF materials contain acrylate moieties, possibly isobornyl acrylate linking branches. The hardness of the MJF samples is associated with crosslinking density. In the ashes after TGA, traces of phosphorus were found, which could originate from initiators or catalysts of the curing process. The ME materials contain fillers, most probably silica, that differ in their amount. It is possible that silica also plays a role in the processing to stabilize the extrusion strand. For the harder material, a higher crosslink density was found, which was supported also by the other tested properties. The MJF samples have smooth surfaces, while the ME samples show grooved surface structures typical for the material extrusion process. Post-treatment did not improve the material properties. In the MJF samples, significant color changes were observed. Full article

Hydrogen is a dangerous gas as it reacts very easily with oxygen and may explode; therefore, the accumulation of hydrogen in confined spaces is a safety hazard. Composites consisting of unsaturated polymers and catalysts are a common getter, where the commonly used polymer is 1,4- diphenylethynyl benzene (DEB). Silicone rubber (SR) is a good carrier for hydrogen-absorbing materials due to its excellent chemical stability and gas permeability. In this work, polysiloxane, water, and a emulsifier are ultrasonically injected into a uniform emulsion, and the hydrogen getter DEB-Pd/C (Palladium on carbon) is then added. Under the catalysis of platinum (Pt), the cross-linking agent undergoes a hydrosilylation reaction to cross-link polysiloxane in emulsion to form silicone rubber. Then, the water was removed by freeze-drying, and the loss of water constructed a porous frame structure for silicone rubber, thus obtaining porous silicone rubber. The difference in hydrogen absorption performance between porous silicone rubber and ordinary silicone rubber was compared. It was found that, with the increase in water in the emulsion, the porous frame of silicone rubber was gradually improved, and the hydrogen absorption performance was improved by 243.4% at the highest, almost reaching the theoretical saturated hydrogen absorption capacity. Porous silicone rubber was prepared by emulsion mixing, which provided a new idea for further improving the hydrogen absorption performance of silicone rubber. Full article

Organosilicon polymers (silicones) are of enduring interest both as an established branch of polymer chemistry and as a segment of commercial products. Their unique properties were exploited in a wide range of everyday applications. However, current silicone trends in chemistry and materials engineering are focused on new smart applications, including stretchable electronics, wearable stress sensors, protective coatings, and soft robotics. Such applications require a fresh approach to methods for increasing the durability and mechanical strength of polysiloxanes, including crosslinked systems. The introduction of self-healing options to silicones has been recognized as a promising alternative in this field, but only carefully designed multifunctional systems operating with several different self-healing mechanisms can truly address the demands placed on such valuable materials. In this review, we summarized the progress of research efforts dedicated to the synthesis and applications of self-healing hybrid materials through multi-component systems that enable the design of functional silicon-based polymers for smart applications. Full article

Polysiloxane with multiple acryloxyl groups at the terminal site of the polymer chain was synthesized by the condensation reaction between hydroxyl-terminated polysiloxane and acryloyl chloride and used to improve the cross-linking density of UV-curable silicone materials initiated from dual acryloxy-terminated symmetric polysiloxane or single acryloxy-terminated asymmetric polysiloxane with the mixture of Irgacure 1173 and Irgacure 184 at a mass ratio of 1:1 as the photoinitiator. The effects of factors such as initiator composition, UV irradiation time, structure, and molecular weight of linear dual acryloxy-terminated or single acryloxy-terminated asymmetric siloxane oligomers on the gelation yield, thermal properties, water absorption, and water contact angle of UV-cured film were investigated. The synthesized cross-linking density modifier can be copolymerized with acryloxy-functionalized linear polysiloxanes under the action of a photoinitiator to increase the cross-link density of UV-cured products effectively. Both linear dual acryloxy-terminated or single acryloxy-terminated asymmetric siloxane oligomers can be copolymerized with cross-link density modifiers within 20 s of UV irradiation. The gelation yields of the UV-cured products obtained from the dual acryloxy-terminated siloxane oligomers were greater than 85%, and their surface water contact angles increased from 72.8° to 95.9° as the molecular weight of the oligomers increased. The gelation yields of UV-cured products obtained from single acryloxy-terminated asymmetric siloxane oligomers were less than 80%, and their thermal stabilities were inferior to those obtained from the dual acryloxy-terminated siloxane oligomers. However, the water contact angles of UV-cured products obtained from these single acryloxy-terminated asymmetric siloxane oligomers were all greater than 90°. Full article

The development of membrane materials with high transport and separation properties for the removal of higher hydrocarbons from gas mixtures is an important and complex task. This work examines the effect of a cross-linking agent on the structure and transport properties of polydecylmethylsiloxane (C10), a material characterized by high selectivity towards C₃₊ hydrocarbons. C10 was cross-linked with various diene hydrocarbons, such as 1,7-octadiene (C10-OD), 1,9-decadiene (C10-DD), 1,11-dodecadiene (C10-DdD), and vinyl-terminated polysiloxanes, of different molecular weights: 500 g/mol (C10-Sil500) and 25,000 g/mol (C10-Sil25-OD). Using a number of characterization methods (IR-spectroscopy, WAXS, DSC, toluene sorption, and gas permeability), it was revealed that a change in the type and length of the cross-linking agent (at the same mole concentration of cross-linking agent) led to a significant change in the structure of the polymer material. The nature of cross-linking agent affected the arrangement of the decyl side-groups of the polymer, resulting in noticeable differences in the solubility, diffusivity, permeability, and selectivity of tested gases (N₂, CH₄, C₂H₆, and C₄H₁₀). For instance, an increase in the length of the hydrocarbon cross-linker was associated with a drop of n-butane permeability from 5510 (C10-OD) to 3000 Barrer (C10-DdD); however, the transition to a polysiloxane cross-linker led to an increase in corresponded permeability up to 8200 Barrer (C10-Sil25-OD). The n-butane/nitrogen selectivity was significantly higher for diene-type cross-linkers, and the maximum value was achieved for 1,7-octadiene (α(C₄H₁₀/N₂) = 104). Full article

Organosilicon polymers (silicones) are an important part of material chemistry and a well-established commercial product segment with a wide range of applications. Silicones are of enduring interest due to their unique properties and utility. Recently, new application areas for silicone-based materials have emerged, such as stretchable electronics, wearable stress sensors, smart coatings, and soft robotics. For this reason, research interest over the past decade has been directed towards new methods of crosslinking and increasing the mechanical strength of polyorganosiloxanes. The introduction of self-healing mechanisms may be a promising alternative for such high-value materials. This approach has gained both growing research interest and a rapidly expanding range of applications. Inherent extrinsic and intrinsic self-healing methods have been used in the self-healing of silicones and have resulted in significant advances in polymer composites and coatings, including multicomponent systems. In this review, we present a summary of research work dedicated to the synthesis and applications of self-healing hybrid materials containing polysiloxane segments, with a focus on antimicrobial and antifouling coatings. Full article

Silicon elastomers with excellent self-healing and reprocessing abilities are highly desirable for the advancement of next-generation energy, electronic, and robotic applications. In this study, a dual cross-linked self-healing polysiloxane elastomer was facilely fabricated by introducing an exchangeable imine bond and boroxine into polydimethylsiloxane (PDMS) networks. The PDMS elastomers exhibited excellent self-healing properties due to the synergistic effect of dynamic reversible imine bonds and boroxine. After healing for 2 h, the mechanical strength of the damaged elastomers completely and rapidly recovered at room temperature. Furthermore, the prepared PDMS elastomers could be repeatedly reprocessed multiple times under milder conditions without significant degradation in mechanical performance. In addition, a stretchable and self-healable electrical sensor was developed by integrating carbon nanotubes (CNTs) with the PDMS elastomer, which can be employed to monitor multifarious human motions in real time. Therefore, this work provides a new inspiration for preparing self-healable and reprocessable silicone elastomers for future flexible electronics. Full article

The known ferrocenyl-containing silicone materials have redox activity and electrical conductivity at the level of antistatic materials, but they are incapable of self-healing due to their irreversible cross-linking, which significantly reduces their application area. The development of novel self-healing ferrocenyl-containing silicone rubbers (FSRs) is a promising area of research that extends the possibilities of their application as protective coatings. In this work, a new method was developed to synthesize FSRs with different ferrocenyl unit content (25 and 50 mol.%) by anionic copolymerization of cyclic octamethylcyclotetrasiloxane (D₄), cyclic tetraferrocenyl-substituted 1,3,5,7-tetramethyltetrasiloxane (Fc₄D₄), and bicyclic cross-linking agent (bis-D₄). The optimal concentrations of the cross-linking agent and ferrocenyl-substituted unit content for FSRs are 5 wt.% and 25 mol.%, respectively. The FSRs exhibit tensile strength and elongation at break up to 0.1 MPa and 215%. The FSRs possess both self-healing at room and/or elevated temperatures (100 °C) and redox activity (Fc/Fc⁺ transformations at E⁰ = 0.43 V) and conductivity at the antistatic level (ca. 10⁻¹⁰–10⁻¹¹ S·cm⁻¹). The thermal properties of the FSRs were studied. The proposed approach is relevant for the creation of new functional silicone materials as flexible, self-healing, and antistatic protective coatings. Full article

Liquid crystal elastomers (LCEs) are shape-morphing materials whose large and reversible shape transformations are caused by the coupling between the mobile anisotropic properties of liquid crystal (LC) units and the rubber elastic of polymer networks. Their shape-changing behaviors under certain stimuli are largely directed by the LC orientation; therefore, various strategies have been developed to spatially modulate the LC alignments. However, most of these methods are limited as they require complex fabrication technologies or have intrinsic limitations in applicability. To address this issue, programmable complex shape changes in some LCE types, such as polysiloxane side-chain LCEs, thiol-acrylate main-chain LCEs, etc., were achieved by using a mechanical alignment programming process coupled with two-step crosslinking. Here, we report a polysiloxane main-chain LCE with programmable 2- and 3D shape-changing abilities that were created by mechanically programming the polydomain LCE with two crosslinking steps. The resulting LCEs exhibited a reversible thermal-induced shape transformation between the initial and programmed shapes due to the two-way memory between the first and second network structures. Our findings expand on the applications of LCE materials in actuators, soft robotics, and smart structures where arbitrary and easily programmed shape morphing is needed. Full article

It is challenging to improve the water resistance, flame retardancy, mechanical performance, and balance of halogen-free flame-retardant polypropylene (PP) composites. For this purpose, a linear vinyl polysiloxane (PD) was synthesized and then self-crosslinked under benzoyl peroxide to prepare surface-coated ammonium polyphosphate (APP@PD). Apparently, this linear vinyl polysiloxane self-crosslinking coating strategy was completely different from the commonly used sol-gel-coated APP with silane monomers. After coating, the water contact angles (WCA) of APP and APP@PD were 26.8° and 111.7°, respectively, showing high hydrophobicity. More importantly, PP/APP@PD/dipentaerythritol (DPER) showed a higher limiting oxygen index (LOI) and better UL-94 V-0 rate in comparison with PP/APP/DPER composites. After water immersion at 70 °C for 168 h, only PP/APP@PD/DPER kept the UL-94 V-0 rate and lowered the deterioration of the LOI, reflecting the better water-resistance property of APP@PD. Consistently, the cone calorimeter test results displayed a 26.2% and 16.7% reduction in peak heat release rate (PHRR) and total smoke production (TSP), respectively. Meanwhile, the time to peak smoke production rate (T_PSPR) increased by 90.2%. The interfacial free energy (IFE) between APP@PD and PP was calculated to evaluate the interfacial interaction between PP and APP@PD. A reduction of 84.2% in the IFE between APP@PD and PP is responsible for the improvement in compatibility and the increase in flame retardancy, water resistance, and mechanical properties of the composites. Full article