Vinyl-functionalized polyborosiloxane for improving mechanical and flame-retardancy performances of silicone rubber foam composites

In this work, we first synthesized vinyl-terminated polyborosiloxane (pBS) filler, and then incorporated it into silicone rubber foam (SRF) matrix to prepare composite materials through a simple chemical dehydrogenative foaming method under ambient conditions. The pBS filler with reactive groups could form physical and chemical crosslinking networks in SRF, leading to an excellent dispersion level of pBS in the SRF matrix. Moreover, the inserted pBS could remarkably improve the mechanical and flame-retardancy properties of SRF-pBS composites. Intriguingly, the SRF-pBS6 foam containing 6 wt% of pBS possessed a uniform porous structure and balanced mechanical properties (σ_b = 65.4 kPa, ε_b = 56.7%, compression stress 97.1 kPa), thermal conductivity (0.102 W (m K)^?1), limiting oxygen index (29.8%) and UL-94 rating (V-0) among the prepared foams. In addition, the incorporated pBS (6 wt%) could synergistically catalyze the formation of a silicon–boron strengthened ceramic-like protective layer under fire and was capable of suppressing heat and smoke production in the SRF-pBS6 foam. The present work provides a promising way for developing high mechanical and flame-retardant polymeric foam materials with good thermal insulation. © 2021 Society of Industrial Chemistry.     

Synergistic effects of zinc oxide in intumescent flame retardant silicone rubber composites

Abstract

The synergistic effects of zinc oxide (ZnO) with intumescent flame retardant (IFR; based on phosphorus acid, melamine and pentaerythritol) in silicone rubber (SR) composites have been studied using limiting oxygen index, UL-94, cone calorimeter test and digital photographs. The results showed that 2·0 wt-% loading ZnO in the flame retardant SR composites could greatly reduce the peak values of heat release rate and smoke production rate, and form a compact char layer on the surface of the sample. Thus, a suitable amount of ZnO plays a synergistic effect with IFR in flame retardant SR composites system.     

Thermal stability and ablation properties of silicone rubber composites

Effects of incorporation of clay and carbon fiber (CF) into a high temperature vulcanized (HTV) silicone rubber, i.e., poly(dimethylsiloxane) (PDMS) containing vinyl groups, on its thermal stability and ablation properties were explored through thermogravimetric analyses (TGA) and oxy‐acetylene torch tests. Natural clay, sodium montmorillonite (MMT), was modified with a silane compound bearing tetra sulfide (TS) groups to prepare MMTS₄: the TS groups may react with the vinyl groups of HTV and enhance the interfacial interaction between the clay and HTV. MMTS₄ layers were better dispersed than MMT layers in the respective composites with exfoliated/intercalated coexisting morphology. According to TGA results and to the insulation index, the HTV/MMTS₄ composite was more thermally stable than HTV/MMT. However, addition of CF to the composites lowered their thermal stability, because of the high thermal conductivity of CF. The time elapsed for the composite specimen, loaded with a constant weight, to break off after the oxy‐acetylene flame bursts onto the surface of the specimen was employed as an index for an integrated assessment of the ablation properties, simultaneously taking into consideration the mechanical strength of the char and the rate of decomposition. The elapsed time increased in the order of: HTV < HTV/CF ≈ HTV/MMTS₄ < HTV/CF/MMTS₄ ≈ HTV/MMT < HTV/CF/MMT. This order was different from the increasing order of the thermal stability determined by TGA results and the insulation index. The decreased degree of crosslinking of the composites with MMTS₄ compared with that of the composite with MMT may be unfavorable for the formation of a mechanically strong char and could lead to early rupture of the HTV/MMTS₄ specimen. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Processibility and mechanical properties of micronized polytetrafluoroethylene reinforced silicone rubber composites

Various micronized polytetrafluoroethylene (PTFE) powders were compounded with silicone rubber (MQ) and mechanical properties of the MQ/PTFE composites were evaluated. The fracture surface morphologies of prepared composites were also investigated using scanning electron microscopy (SEM). At a level of only 5 wt %, the fractured surface of MQ/PTFE composites show layered structure morphology. This structure effectively improves the tear strength of MQ but it also led to lower the tensile properties of the composites. The addition of fluorosilicone rubber (FMQ) as compatibilizer, tensile and tear strength of the composites improved considerably. However, tensile properties of the MQ/solution of sodium in liquid ammonia treated PTFE composite decreased compared with those of the untreated one. To investigate the production potential of extrusion process, an electric wire was extruded with MQ/PTFE/FMQ composites. During the curing process, volatile molecules lead to bubble and void formation of extruded layer depending on the filler shapes. The spherical PTFE powder was suitable for extrusion process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Ablation properties of zinc borate and aluminum hypophosphite filled silicone rubber composites

The ablative properties of epoxy modified silicone rubber composites filled with zinc borate (ZB) and aluminum hypophosphite (AHP) were studied. The decomposition of the added fillers and covering connection of residual on the substrate contribute to the improvement of heat insulation. The ablation test shows that the formation of a dense char layer with certain strength is key to improving the ablative properties. The optimal ablative performance is achieved when the concentration of ZB and AHP is 10 and 5 phr, respectively. Under such circumstances, the linear ablation rate is as low as 0.032 mm/s, which is about 61% lower than the pure silicone rubber. Furthermore, the structure and composition of the formed char layer were analyzed using X-ray diffraction analysis, scanning electron microscopy, and Fourier transform infrared spectroscopy.     

Improved dielectric and mechanical properties of Ti3C2Tx MXene/silicone rubber composites achieved by adding a few boron nitride nanoplates

MXenes have attracted great attentions in the fabrication of dielectric polymer composites because of their excellent electrical conductivity. However, the high dielectric loss tangent would suppress the application of such polymer-based composites. Incorporating insulating fillers might be a solution. Herein, Ti₃C₂T_x MXene/silicone rubber (SR) composites incorporated with boron nitride (BN) nanoplates were prepared. The homogeneous distribution of fillers was obtained in the composites, which was also thermally stable up to 400 °C. Dielectric constant of 7.06 (2.54 times of pure SR) and dielectric loss tangent of 0.00131 were achieved when the filling contents of MXene and BN in SR composite were 1.2 wt% and 5 wt%, respectively. The improved dielectric constant can be ascribed to the enhanced interfacial polarization and the formation of conductive network, while the low dielectric loss tangent can be due to the insulating interlayers of BN which could inhibit the transfer of free electrons from conductive fillers to the insulating polymer matrices. BN/MXene/SR composites displayed improved mechanical properties (tensile stress of 671 kPa and elongation at break of 353%) and good flexibility (elastic modulus of 540 kPa) due to the low filling content of fillers. This work is promising for preparing dielectric polymer composites in applications of electronic devices.     

Synergistic effects between red phosphorus and alumina trihydrate in flame retardant silicone rubber composites

Abstract

The synergistic flame retardant effects between red phosphorus (RP) and alumina trihydrate (ATH) in silicone rubber (SR) composites were evaluated using limiting oxygen index, UL 94 rating, cone calorimeter, thermogravimetric analysis and digital photographs. It has been found that the SR composite containing only ATH does not show good flame retardancy at 39·0 wt-% loading. The cone calorimeter results showed that the heat release rate, mass loss rate, mass and total heat release of SR/ATH/RP composites decrease greatly in comparison with the SR/ATH composites. The digital photographs demonstrated that 1·0 wt-%RP could promote the formation of the homogenous and compact char layer. Thus, a suitable amount of RP has a synergistic effect with ATH in the flame retardant SR composite system.     

胶料预处理对补强硅橡胶性能的影响

本文研究了胶料预处理的不同方式对硅橡胶补强的影响。结果表明：无论含羟基硅油与否,170℃预处理硅橡胶的拉伸强度最高,放置处理试样的拉伸强度介于未处理和170℃预处理之间;胶料预处理与否对不含羟基硅油的硅橡胶硬度没有影响。含羟基硅油的硅橡胶中,170℃预处理的试样硬度最低,未处理的试样硬度最高。含羟基硅油的硅橡胶断裂伸长率变化不大。不含羟基硅油的硅橡胶断裂伸长率为170℃预处理的试样最低。     

Thermal and mechanical properties of liquid silicone rubber composites filled with functionalized graphene oxide

To improve the thermal and mechanical properties of liquid silicone rubber (LSR) for application, the graphene oxide (GO) was proposed to reinforce the LSR. The GO was functionalized with triethoxyvinylsilane (TEVS) by dehydration reaction to improve the dispersion and compatibility in the matrix. The structure of the functionalized graphene oxide (TEVS‐GO) was evaluated by Thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectra, X‐ray diffraction (XRD), and energy dispersive X‐ray spectroscopy (EDX). It was found that the TEVS was successfully grafted on the surface of GO. The TEVS‐GO/LSR composites were prepared via in situ polymerization. The structure of the composites was verified by FTIR, XRD, and scanning electron microscopy (SEM). The thermal properties of the composites were characterized by TGA and thermal conductivity. The results showed that the 10% weight loss temperature (T₁₀) increased 16.0°C with only 0.3 wt % addition of TEVS‐GO and the thermal conductivity possessed a two‐fold increase, compared to the pure LSR. Furthermore, the mechanical properties were studied and results revealed that the TEVS‐GO/LSR composites with 0.3 wt % TEVS‐GO displayed a 2.3‐fold increase in tensile strength, a 2.79‐fold enhancement in tear strength, and a 1.97‐fold reinforcement in shear strength compared with the neat LSR. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42582.     

Modification of rubber powder with peroxide and properties of polypropylene/rubber composites

Waste tire powder was functionalized in the presence of various concentrations of allylamine and benzoyl peroxide. Fourier transform infrared spectroscopy studies confirmed the presence of allylamine on the surface of the rubber powder. The surface energy of the functionalized rubber powder revealed that the introduction of allylamine onto the rubber powder surface increased the surface activity. Improvements in the tensile strength, elongation at break, and storage modulus were observed for polypropylene/modified rubber powder/maleic anhydride grafted polypropylene, and this was attributed to an improvement in the compatibility due to the chemical interaction between the rubber powder and compatibilizer. Evidence for the reaction between the rubber surface and compatibilizer was observed in Fourier transform infrared studies. This peroxide‐initiated monomer‐grafting technique is feasible for large‐scale processes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2237–2243, 2007     

Magnetically aligning multilayer graphene to enhance thermal conductivity of silicone rubber composites

The increasing demand for packaging materials calls for new technologies to achieve excellent thermal conductivity of polymer composites with low content of thermal conductive filler. This article prepared a kind of magnetically functionalized multilayer graphene (Fe₃O₄@MG) via electrostatic interactions, which efficiently enhanced the thermal conductivity of silicone rubber (SR) composites by the alignment of Fe₃O₄@MG in an external magnetic field. The morphology and structure of the Fe₃O₄@MG together with the thermal conductivity of corresponding Fe₃O₄@MG/SR composites were systematically investigated by SEM, TEM, XRD, elemental mapping, and thermal conductivity tester. The obtained results showed that Fe₃O₄@MG was induced to form chain-like bundles in silicone rubber matrix under the applied magnetic field, which enhanced the MG–MG interaction, and formed effective thermal pathways in the alignment direction. Furthermore, as coating mass ratio of Fe₃O₄@MG increased, the thermal conductivity of randomly oriented Fe₃O₄@MG/silicone rubber composites (R-Fe₃O₄@MG/SR) decreased gradually, whereas the through-plane thermal conductivity of vertically aligned Fe₃O₄@MG/silicone rubber composites (V-Fe₃O₄@MG/SR) increased even filled with same contents of thermal conductive filler. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47951.     

Ablation properties of aluminum silicate ceramic fibers and calcium carbonate filled silicone rubber composites

The ablative performance of aluminum silicate ceramic fiber (ASF) and calcium carbonate (CaCO₃) filled silicone rubber composites prepared through a two‐roll mill was examined. The properties of the composites were investigated by thermogravimetry, thermal conductivity measurements, and oxyacetylene torch testing. After the material was burnt, the structure and composition of the char were analyzed by Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy (SEM). The results of the ablation test showed that the ablation resistance improved greatly in an appropriate filler scope. Combined with SEM, it was proven that a firm, dense, and thermal insulation layer, which formed on the composites surface during the oxyacetylene torch test, was a critical factor in determining the ablation properties. Thermogravimetric analysis revealed that the thermal stability of the composites was enhanced by the incorporation of ASF and CaCO₃. The thermal conductivity measurements showed that the silicone rubber composites had a very low thermal conductivity ranging from 0.206 to 0.442 W m^?1 K^?1; this significantly prevented heat from transferring into the inner matrix at the beginning of the burning process. The proportion of 20/40 phr (ASF/CaCO₃) was optimum for improving the ablation resistance of the silicone rubber composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41619.     

Facile preparation and flame retardancy mechanism of cyclophosphazene derivatives for highly flame-retardant silicone rubber composites

A novel and efficient flame retardant cyclophosphazene derivative Hexa (p-acetamidophenoxy) cyclotriphosphazene (HACP) was successfully prepared via a facile one-step reaction. The chemical structure of HACP was characterized and confirmed by FT-IR, ¹H and ¹³C NMR. Then the as-prepared HACP was incorporated into addition-cure liquid silicone rubber (ALSR) matrix to prepare highly flame-retardant rubber composites. It was found that the incorporation of HACP can significantly enhance the flame resistance of ALSR. Typically, the ALSR composites filled with 30 phr HACP achieved UL-94 V-0 rating and meanwhile the total heat release and total smoke release were decreased by 26.9% and 41.5%, respectively. Moreover, the flame-retardant mechanism of ALSR/HACP composites was investigated by TGA, Py-GCMS, FT-IR, SEM and EDX, confirming that HACP plays a significant role in capturing free-radicals and forming protective layers. This work designed a novel cyclophosphazene-based flame retardant to significantly enhance the flame retardancy of ALSR, which may offer some valuable inspiration for the fabrication of highly flame-retardant polymer composites.     

Electrical and thermal properties of silicone rubber composites filled with Cu-coated carbon fibres and functional carbon nanotubes

ABSTRACT

The thermal and electrical conductivities of SR composites containing Cu-CFs and f-MWNTs were studied. The Cu-CFs and f-MWNTs were prepared by chemical deposition and the coupling method, respectively. Both the fillers were characterised by FT-IR, XRD and SEM and the results showed that the Cu layers were deposited on the surface of the CFs and the MWNTs were successfully modified. In addition, the results of thermal and electrical conductivities for SR composites showed that the hybrid fillers system exhibited a better enhancement on thermal and electrical conductivities for SR composites than the single filler system. The maximum thermal conductivity and the least volume resistivity of SR/Cu-CFs/f-MWNTs composites could reach 3.86?W (m?K)^?1 and 3.5?×?10³?Ω?cm, respectively. Based on the experimental results, we recognised the improvement of intrinsical thermal and electrical conductivities of CFs and the good dispersion of MWNTs contributed to the formation of densified 3D conducting networks. Thus, the hybrid fillers system could synergistically enhance the thermal and electrical conductivities of SR composites. We believe, this study could provide an effective way for the design of high conductive polymer composites.     

RTV-133硅橡胶在电器生产中的应用

简单地介绍了缩合型双组分室温硫化硅橡胶的特性和硫化反应机理，并结合军用和民用电器产品的灌注应用情况，详细地叙述了其配制和灌注工艺。     

Improving properties of silicone rubber composites using macromolecular silane coupling agent (MMSCA)

Two types of vinyl silicone oil (VSO), allyl‐capped hyperbranched polycarbosilane (HBP), and triethoxysilane (TES) were employed to synthesize macromolecular silane coupling agent (MMSCA) by hydrosilylation. VSOs, HBP, and the hydrosilylated products were used as crosslinker, respectively, to improve weak mechanical properties of silicone rubber (SR). Structures of the crosslinkers were studied by gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), and nuclear magnetic resonance (NMR). Crosslinking density test and scanning electron microscope (SEM) observation showed an increased interaction between silicone rubber and fumed silica by the use of MMSCA. Mechanical properties of the resulted composites using MMSCAs were increased to varying degrees compared with those possessing crosslinkers without ethoxy group. MMSCAs were effective for further property enhancements of composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43415.     

Ablative properties and mechanisms of hot vulcanised silicone rubber (HVSR) composites containing different fillers

Hot vulcanised silicone rubber (HVSR) composites were prepared using silicon carbide (SiC), hafnium oxide (HfO₂), zirconium oxide (ZrO₂) and zirconium boride (ZrB₂) as fillers, respectively. The tensile properties and the ablative response of the composites were examined. Tensile tests indicated that the tensile strength of HVSR was increased by the incorporation of ZrB₂. The linear ablation rate of the composites increased in the order HVSR/ZrB₂?2?2?2 and HVSR/ZrO₂, respectively, compared to that of 333?K for the blank HVSR. Scanning electron microscopy and X-ray diffraction results showed that the dense and rigid ceramic layer was hard to peel off under the high pressure and shearing forces of ablative gases. The HVSR/ZrB₂ specimens exhibited the best ablation resistance among all the composites involved in this work.     

Peel strength improvement of silicone rubber film by plasma pretreatment followed by graft copolymerization

Here we discuss the improvement in the peel strength of silicone rubber film by O₂ plasma pretreatment followed by grafting with hydrophilic monomers: acrylamide (AAm) and acrylic acid (AA). The peroxides concentration after O₂ plasma treatment was determined by the 1,1-diphenyl-2-picrylhydrazyl (DPPH) method. ESCA analysis was carried out to confirm the existence of AAm. The peroxides concentration and hence the peel strength increased with increasing plasma treatment power and time, reached a maximum value, and then decreased with further increasing plasma treatment power and time. Peel strength of the silicone film with 3M-600 tape was observed to increase with grafting time; however, it was found to decrease with overgrafting. The maximum peel strength of 384.4 g/cm was found for the 20 W, 10 min plasma treated, AAm grafted film with maximum peroxides concentration of 4.86 x 10^-9 mol/cm² and also with maximum nitrogen-to-carbon ratio (N/C) of 0.247. Hydrolysis experiments show that -NH₂ provides higher contribution to adhesion than -COOH does and the grafting degree of AA is lower than that of AAm. The relationship between the degree of grafting and peel strength can be well explained by the mechanical interlocking theory of adhesion.     

Effect of hollow glass beads on density and mechanical properties of silicone rubber composites

In this work, low density hollow glass beads (HGB)/silicon rubber (SR) composites were prepared by solution method and flocculation process. The prepared samples were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, tensile test, and friction test. The results show that the densities of SR composites decrease from 1.140 to 0.792 g/cm³ with the addition of HGB. By comparing theoretical density with true density, it can be estimated that the ratio of shattered HGB increase from 8.79% to 24.76%. Especially, the mechanical properties of SR composites were improved by surface modification of HGB. By adding surface-modified HGB at 5 and 10 wt%, the tensile strengths of SR composites were enhanced by 17.8% and 28.2%, respectively. In addition, tear strength, shore A hardness, compression set, and friction property were significantly ameliorated. Furthermore, the mechanism of surface-modified HGB in mechanical properties was analyzed.