Synergistic effect of three‐dimensional multi‐walled carbon nanotube–graphene nanofiller in enhancing the mechanical and thermal properties of high‐performance silicone rubber

The homogeneous dispersion of nanofillers and filler–matrix interfacial interactions are important factors in the development of high‐performance polymer materials for various applications. In the present work, a simple solution‐mixing method was used to prepare multi‐walled carbon nanotube (MWCNT)–graphene (G) (3:1, 1:1, 1:3) hybrids followed by their characterization through wide‐angle X‐ray diffraction, transmission electron microscopy and thermogravimetric analyses. Subsequently, MWCNT–G (1:1) hybrid was used as reinforcing filler in the formation of silicone rubber (VMQ) nanocomposites by solution intercalation, and their morphology and properties were investigated. Our findings showed that MWCNT–G (0.75 wt%)/VMQ composite exhibited significant improvements in tensile strength (110%) and Young's modulus (137%) compared to neat VMQ. The thermal stability of MWCNT–G (1 wt%)/VMQ was maximally improved by 154 °C compared to neat VMQ. Differential scanning calorimetry demonstrated the maximum improvement of glass transition temperature (4 °C), crystallization temperature (8 °C) and melting temperature (5 °C) for MWCNT–G (1 wt%)/VMQ nanocomposite with respect to neat VMQ. Swelling measurements confirmed that the crosslink density and solvent resistance were a maximum for hybrid nanocomposites. Such improvements in the properties of MWCNT–G/VMQ nanocomposites could be attributed to a synergistic effect of the hybrid filler. © 2013 Society of Chemical Industry     

Transport properties and mechanical behavior of poly(methyl‐phenylsiloxane) membranes as a function of methyl to phenyl groups ratio

Membranes based on dimethyl and methyl‐phenylsiloxane were synthesized and then fully characterized. Transport properties and mechanical behavior were determined as a function of different methyl/phenyl group ratios and the effects of these groups on results were established. Membrane transport properties were evaluated from n‐hexane absorption studies. Static tensile stress–strain deformation measurements, stress–hysteresis determination, and stress–relaxation studies were performed to assess the mechanical behavior of these membranes. The results indicate that both physical–mechanical and transport properties are strongly affected by the methyl group content. The increase of the phenyl groups in the polymer chain impairs mechanical properties as a result of which decrease in crosslinking degree and gas permeability due to the diminution in free volume and penetrant solubility. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1624–1633, 2002     

The network structure of silicone release coatings

Silicone release coatings are used by the pressure-sensitive adhesive industry for labeling applications. A background discussion of silicone release coatings is presented. Methodology for determining the network structure of photolytically cured systems prepared by the cationic ring opening polymerization of an epoxy silicone fluid is described. Under typical polymerization conditions, these networks contain no unreached epoxides and have very low degrees of polymerization (D _p), indicating that termination is competitive with propagation. A method has also been developed to determine the network structure of thermally cured systems prepared by the platinum-catalyzed hydrosilylation of silicone vinyl compounds with silicone hydrides. The nature of the cross-links and the types of residual functionality have been determined and the systems have been shown to undergo a postcure.This paper was presented at the Second International Topical Workshop, Advances in Silicon-Based Polymer Science.     

3D-Printed Silicone Substrates as Highly Deformable Electrodes for Stretchable Li-Ion Batteries

Stretchable energy storage devices receive a considerable attention at present due to their growing demand for powering wearable electronics. A vital component in stretchable energy storage devices is its electrode which should endure a large and repeated number of mechanical deformations during its prolonged use. It is crucial to develop a technology to fabricate highly deformable electrode in an easy and an economic manner. Here, the fabrication of stretchable electrode substrates using 3D-printing technology is reported. The ink for fabricating it contains a mixture of sacrificial sugar particles and polydimethylsiloxane resin which solidifies upon thermal curing. The printed stretchable substrate attains a porous structure after leaching the sugar particles in water. The resulting printed porous stretchable substrates are then utilized as electrodes for Li-ion batteries (LIBs) after loading them with electrode materials. The batteries with stretchable electrodes exhibit a decent electrochemical performance comparable to that of the conventional electrodes. The stretchable electrodes also exhibit a stable electrochemical performance under various mechanical deformations and even after several hundreds of stretch/release cycles. This work provides a feasible route for constructing LIBs with high stretchability and enhanced electrochemical performance thereby providing a platform for realizing stretchable batteries for next generation wearable electronics.     

Blends of high‐density polyethylene with solid silicone additive

Silicone masterbatch (SMB) is a pelletized formulation containing 50% of an ultrahigh molecular‐weight polydimethylsiloxane dispersed in polyethylene. This SMB is designed to be used as an additive in polyethylene‐compatible systems to impart benefits such as processing improvement and modification of surface characteristics. In this work, binary blends of high‐density polyethylene (HDPE) and SMB were prepared by melt‐mixing technique to study the influence of this masterbatch on the processing and mechanical properties of HDPE. Ternary blends were also prepared by the addition of silane‐grafted polyethylene (HDPE‐VTES) as compatibilizer. The blends were analyzed by melting flow rate (MFR), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and tensile tests. Data of final torque and MFR showed that SMB improved the processability of pure HDPE. DSC results showed differences in crystalline behavior between binary and ternary blends. In the former, the degree of crystallinity increased up to 10 wt % of SMB content; beyond this concentration, it decreased. In ternary blends, a reverse behavior was observed. The morphologic study showed silicone particles uniformly distributed in HDPE matrix. With high SMB concentration, the addition of HDPE‐VTES significantly reduced the size of silicone particles. In the range of SMB composition studied, the mechanical properties of blends lower slightly compared to pure HDPE. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2347–2354, 2002     

Preparation and surface properties of silicone-modified polyester-based polyurethane coats

A series of novel silicone-modified polyesters (SPE) were prepared by substituting part of diol with low molecular weight hydroxyl-terminated poly(dimenthylsiloxane) (PDMS). Then, isophorone diisoclanate (IPDI) as hard segments and 1,4-butanediol as chain extender were added to SPE to prepare a silicone-modified polyurethane (SPU). The effects of the type of diol, diacid, and hydroxyl-terminated PDMS, and the amount of hydroxyl-terminated PDMS on the preparation and surface properties of SPU were investigated. It was found that the amount of PDMS incorporated into a polyester chain was relatively higher when 1,6-hexanediol (HDO) and 1,10-decandiol (DDO) were used as diol and the PDMS with lower molecular weight was used as organosilicone compound. Consequently, the SPU coats with HDO as diol, adipic acid (AA) as diacid, and short chain PDMS as silicone segment had the lowest surface-free energy since it had the highest and most homogeneous distribution of silicone segments at its top layer surfaces.     

Transient effects in dynamic modulus measurement of silicone rubber,part 2: Effect of mean strains and strain history

The strain‐dependent dynamic storage modulus of a poly(dimethyl‐siloxane‐co‐methylvinyl‐siloxane‐co‐methylphenyl‐siloxane)‐based silicone elastomer (PVMQ), which is reinforced with fumed silica and crosslinked with peroxide, is investigated. The time dependence of the dynamic storage modulus on the magnitude of the mean strain at a particular test condition is investigated. The dynamic modulus results are shown to depend on the time of cycling as well as the relative magnitudes of the dynamic and mean strains. The relaxation of the force required to maintain the mean strain is observed to depend on the magnitude of the dynamic strains and the data are shown to be consistent with static stress relaxation experiments in the limit of zero dynamic strain. Recovery of the dynamic modulus from the exposure to higher strain cycling is seen to be facilitated by dynamic cycling with higher cycling strains yielding faster recovery rates. The observed phenomena are interpreted in terms of the role of entanglements in the polymer phase on the dynamic behavior of the elastomer material. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2197–2204, 2007     

3D‐Printed Silicone Materials with Hydrogen Getter Capability

Organic getters are used to reduce the amount of reactive hydrogen in applications such as nuclear plants and transuranic waste. The present study examines the performance of getter loaded silicone elastomers in reducing reactive hydrogen gas from the gas phase and their capability of being 3D printed using direct ink writing techniques. The samples are placed in closed vessels and exposed to hydrogen atmosphere at pressures of 580 torr and 750 mtorr and at a temperature of 25 °C. The hydrogen consumption is measured as a function of time and normalized to getter concentration in the polymer. The performance of the getter‐loaded silicone elastomer containing 1,4‐bis[phenylethynyl]benzene (DEB) as the organic getter and Pd/C catalyst (ratio of 3:1 DEB to catalyst) decreases with increasing the resin's curing temperature. Chemical analysis suggests that DEB reacts with the silicone resin at high temperatures. In addition, it is demonstrated that the increased surface area of 3D printed composites results in improved getter performance.     

Investigating the surface properties of polyurethane based anti‐graffiti coatings against UV exposure

A permanent anti‐graffiti coating based on a polyurethane resin was prepared by incorporating different levels of an OH‐functional silicone modified polyacrylate additive. Static contact angle measurements and dynamic mechanical thermal analysis (DMTA) were employed to evaluate surface free energy and mechanical properties of the coating specimens, respectively. Effect of ageing condition on the graffiti properties of the coating samples was evaluated utilizing an accelerated weathering test. Color changes, surface morphology, and variations in the mechanical properties were also examined prior to and after being exposed to UV irradiation for 864 h in a QUV chamber. Results showed that surface free energy of the samples decreased with replacement of polyol with additive up to 5 mol %. A Scanning electron microscope equipped with energy dispersive X‐ray detector revealed that for the samples containing more than 5 mol % additive, there was an enrichment of silicone at the interface of films and air. At long exposure times and higher concentrations of additive, depreciation of graffiti properties was seen. DMTA and attenuated total reflectance‐fourier transform infra‐red studies before and after ageing showed that the silicone additive tended to degrade while it could cause an increase in crosslinking density. Water contact angles and atomic force microscopy images after ageing revealed that the cause of the depletion in anti‐graffiti properties was attributed to the deterioration of the silicone additive. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

An investigation of scratch testing of silicone elastomer coatings with a thickness gradient

Silicone elastomer coatings are currently being investigated as foul release coatings on ships hulls. Previous tests on silicone duplex elastomer coatings used a progressive load scratch test. It has been shown that the durability of uniform silicone duplex elastomer coatings is a function of thickness, indentation modulus, and stylus and that the failure mechanism depended on coating thickness and stylus. When applying silicone coatings to a ship's hull, there are regions on the ship where the coating is not uniform. This article investigates the effect of a thickness gradient on the durability of a single layer silicone elastomer coating. In these tests, a constant normal load was used as the stylus moved transversely to the surface. It was found that when the scratch test started in the silicone coating and proceeded in the direction of decreasing coating thickness (“Elastomer to Metal”), there was first a scratch tract followed by the initiation of detachment of the coating, then by gross detachment of the coating. When the scratch started on the exposed aluminum surface and proceeded into the silicone in the direction of increasing coating thickness (“Metal to Elastomer”), there was first gross detachment of the coating, followed by recovery (i.e., silicone coating is intact) and a scratch tract into the silicone. It was also found that the coefficient of friction was much higher in the silicone when the scratch test was going in the direction of decreasing coating thickness as opposed to the scratch test going in the opposite direction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012