Hybrid nanocomposites based on novolac resin and octa(phenethyl) polyhedral oligomeric silsesquioxanes (POSS): miscibility, specific interactions and thermomechanical properties

Hybrid nanocomposites were prepared via solution blending of octaphenethyl POSS into novolac resin. The resulted hybrid blends were investigated by Fourier-transformed infrared spectra (FTIR), polarized optical microscopy (POM), wide X-ray diffraction and differential scanning calorimetry (DSC). FTIR results showed that there existed intermolecular hydrogen bond between the hydroxyl groups of the phenolic resin and POSS siloxane groups, which could promote POSS to disperse well in the polymer matrix up to 20 wt% POSS loading. At higher POSS loading, POSS would aggregate and lead to macrophase separation, which was demonstrated by POM, DSC and WXRD. Finally, hexamethylene tetramine was used to cure the novolac blends to form hybrid network phenolic nanocomposites. Dynamic mechanical analysis results showed that the storage modulus of the hybrid networks was improved up to 20 wt% POSS loading; the T _g was increased with increasing POSS content and higher than that of the control phenolic resin except that 5 wt% POSS loading. Thermo gravimetric analysis showed that the thermal stability of hybrid networks was also enhanced with the incorporation of POSS.     

Isothermal crystallization behavior of isotactic polypropylene blended with small loading of polyhedral oligomeric silsesquioxane

The isothermal crystallization kinetics and morphology development of isotactic polypropylene (iPP) blended with small loading of nanostructure of polyhedral oligomeric silsesquioxane (POSS) were studied with differential scanning calorimetry (DSC), polarized optical microscopy (POM), and wide-angle X-ray diffraction (WAXD). The crystallization behaviors of iPP/POSS composites presented an unusual crystallization behavior during isothermal and nonisothermal crystallization conditions. The exothermic morphologies of isothermal and nonisothermal crystallization of iPP/POSS composites changed remarkably with increasing POSS. Moreover, the developments of spherulitic morphology for iPP/POSS composites showed that the major dispersed POSS molecules became nanocrystals first and then aggregated together forming thread- or network-like morphologies, respectively, depending on POSS content, which was observed. It implies that these major POSS nanocrystals' morphologies appeared as an effective nucleating agent and promoted the nucleation rate of iPP, whereas the minor dispersed POSS molecules that had slight miscibility between iPP retarded the nucleation and growth rates of iPP in the remaining bulk region. Therefore, the isothermal crystallization showed a single exothermic peak at pure iPP and POSS-1.0, whereas at POSS-2.0 and POSS-3.0, displayed the multi-exothermic peaks during isothermal crystallization. These faces indicated that POSS molecules were both influence on the transport of iPP chain in the melted state and on the free-energy of formation the critical nuclei of iPP assisted by the POSS structures were observed. Therefore, we postulated that the crystallization mechanisms of multi-exothermic peaks in isothermal crystallization may proceed to combine the “nucleating agent inducing nucleation of iPP event assisted by the POSS domains” that the nucleation of iPP does occur preferentially on the surfaces of the POSS “threads” or “networks” structures, and “nucleation and growth of iPP in the remaining bulk melted iPP region retarded by dispersed POSS molecules”. Therefore, effects of POSS content on the isothermal and nonisothermal crystallization behaviors of iPP/POSS composites due to the POSS molecules partially miscible with iPP, at very small loading of POSS molecules, promoted or retarded the rates of nucleation and growth of iPP depending on the POSS content and crystallization temperature were discussed.     

Synthesis, morphology and photophysics of novel hybrid organic-inorganic polyhedral oligomeric silsesquioxane-tethered poly(fluorenyleneethynylene)s

A series of novel hybrid organic-inorganic light-emitting materials, polyhedral oligomeric silsesquioxane-tethered poly(fluorenyleneethynylene)s, were successfully synthesized via Sonagashira coupling reaction. The chemical structures of these copolymers were determined by ¹H NMR and FT-IR spectra. The morphologies of these copolymers were studied in details using TEM and WAXD. The WAXD data showed that POSS formed aggregation instead of crystallization in the polymer matrix, indicating the significant effect of the backbone constraint on POSS crystallization. Furthermore, it also revealed that the interchain interaction weakened and the interchain distance increased after introducing POSS groups. The TEM data indicated that POSS aggregates were well dispersed in polymer matrix. In accordance with the morphological investigation, the results of UV-vis absorption and photoluminescence emission spectra of these copolymers showed that the tendency toward planar conformation of conjugated backbones reduced to a certain extent due to weakened interchain interaction. Accordingly, these copolymers exhibited the enhanced quantum yields in the solid state. In addition, owing to the thermal and oxygen stability of hybrid POSS, the thermal spectral stability of these polymers was also improved greatly.     

Phenolic Resin/Octa(aminophenyl)-T<Subscript>8</Subscript>-Polyhedral Oligomeric Silsesquioxane (POSS) Hybrid Nanocomposites: Synthesis,Morphology, Thermal and Mechanical Properties

Octa(aminophenyl)-T₈-polyhedral silsesquioxane, 1, can serve as a cross-linking agent for organic polymeric resins. Amino functional groups of 1 can form chemical bonds or hydrogen-bonds to appropriate matrix polymers or resins. Various resole phenolic resin/1 nanocomposites (0, 1, 3, 6, and 12 wt% 1) were prepared. Hydrogen bonding between phenolic hydroxyls and the amino groups of 1 in these nanocomposites were investigated by FT-IR. The aggregation morphologies of 1 within these samples were examined using SEM, TEM, and Wide Angle X-ray Diffraction (WAXD) studies. Small quasispherical nanometer-sized POSS particles which were further aggregated into clusters, like individual grapes in a bunch, formed into phase-separated domains as large as 400 nm in diameter as the loading of 1 increased. These particles exhibited a broad 2θ = 5.8° WAXD peak indicating the presence of some crystalline order within the nanoparticles of 1 making up the aggregates. This corresponds to an average crystalline plane lattice distance of 17.5 Å. However, extraction of the finely powdered nanocomposites by refluxing THF failed to remove 1 indicating the vast majority of 1 must be chemically bound. Thus, the aggregates must have resin within their structure. The storage modulus (E') in both the glassy and rubbery regions, thermal stability, and glass transition temperature of the composites were improved by 1 wt% 1. However, at high loadings of 1, these properties gradually decreased. Surface extractions by THF removed only a portion of the 1 in the surface regions based on X-EDS analyses for Si, suggesting that a portion of 1 might chemically bond into the phenolic resin matrix during the cure. As the loading of 1 increased, the content of 1 at specific surface locations gradually tends to increase and confirmed excellent dispersion of 1 in the micron size-scale at all locations.     

Dispersion of a novel phenolic rigid organic filler in isotactic polypropylene matrix by solution-mixing and melt-mixing

A novel phenolic rigid organic filler (named KD) with a high melting point was dispersed in an isotactic polypropylene (iPP) matrix by solution-mixing and/or melt-mixing. A series of KD/iPP blends was prepared with or without addition of maleic anhydride-grafted polypropylene (MAPP) as a compatibilizer. Influences of MAPP and mixing methods on the filler dispersion were studied using polaried optical microscope (POM), scanning electron microscope (SEM) and tensile test. The filler particles are always inclined to form large irregular aggregates in the iPP matrix due to their significant differences in polarity and solubility in solvent. However, an iPP/MAPP/KD (PMK) blend containing filler particles with a quasi-spherical shape (~97.8 nm in diameter) and narrow particle size distribution (polydispersity index= 1.076) was successfully prepared by incorporating MAPP to reduce the interfacial tension and surface free energy between the dispersion phase and the continuous phase, and adopting a spray-drying method after solution-mixing to suppress the increase of the size of the dispersed phase during the removal of solvent.     

Synthesis and characterization of UV-cured epoxy acrylate/POSS nanocomposites

In this study, epoxy acrylate (EA)/vinyl-polyhedral oligomeric silsesquioxane (POSS) nanocomposites were prepared through in situ polymerization and by UV-curing technique. The vinyl-POSS monomers were added to EA matrix by physically blending at loadings between 0 wt.% and 15 wt.%. The microstructure of the EA/vinyl-POSS composites was studied by X-ray diffraction (XRD) measurements, and the result indicated that the separate POSS domains were present in EA/POSS composites. Aggregates were observed in the nanocomposites by SEM and the EDS results indicated that there were vinyl-POSS molecules existing in the EA matrix. TEM images further proved there were both POSS aggregates and monomers dispersed in the EA matrix. The kinetics of the photopolymerization was investigated by real time FTIR spectroscopy. The DSC analysis showed that the increasing POSS content caused a decrease on the composite's glass transition temperature. TGA measures confirmed that the degradation mechanism of EA was not affected by POSS and the nanocomposites thermal stability was slightly improved with the increasing of POSS loadings. It can be seen that the degradation rate slowed down with the increasing of POSS content and the 50% mass loss temperature of EA/POSS hybrids all increased conspicuously relative to plain EA.     

Hemi-telechelic and telechelic organic/inorganic poly(ethylene oxide) hybrids based on polyhedral oligmeric silsesquioxanes (POSSs): Synthesis,morphology and self-assembly

Amphiphilic hemi-telechelic and telechelic poly(ethylene oxide) (PEO) hybrids based on polyhedral oligmeric silsesquioxane (POSS) were prepared via the copper-catalyzed azide–alkyne “click” reaction. Thermal properties of POSS–PEO were characterized using differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The result shows that the thermal properties of telechelic POSS–PEO are effectively enhanced by POSS. The morphology of the POSS-containing PEO hybrid crystals was investigated using polarized optical microscopy (POM), and the results indicate that it is much easier for the POSS in the telechelic POSS–PEO hybrids (T-POSS–PEO) to form quite large aggregates, which act as nucleating agents during the crystallization of the PEO chains. The self-assembly behavior of POSS–PEO in water was also studied using transmission electron microscopy (TEM). The results reveal that hemi-telechelic POSS–PEO hybrids (HT-POSS–PEO) can self-assemble into spherical aggregates, whereas the T-POSS–PEO hybrids self-assemble into ellipsoidal aggregates.     

Crystallization and morphology study of polyhedral oligomeric silsesquioxane (POSS)/polysiloxane elastomer composites prepared by melt blending

Composites of poly(methylvinylsiloxane) (“silicone”) elastomers with polyhedral oligomeric silsesquioxane (POSS) were prepared by melt blending. One goal was to establish conditions that would lead to morphologies different from that of a simple filler dispersed in a polymer matrix for the purposes of reinforcement. To this end, the study focused on the dispersion and state of POSS in silicone rubber blends as determined by X-ray diffraction (XRD), polarizing optical microscopy (POM), scanning electron microscopy (SEM), and analysis using a rubber processing analyzer (RPA). Of particular interest were the thermal stability of POSS macromers, and the effects of mixing temperature and subsequent vulcanization of the polysiloxane. The results showed that highly crystalline POSS macromers could undergo condensation reactions at 230 °C in air, leading to partially amorphous structures. Also, POSS crystals apparently dissolved in the polysiloxane at high temperatures and POSS crystals with hexahedral or flake-like structures recrystallized out upon cooling. Both crystallites and POSS molecules co-existed in these blends, with the amount of dispersed molecular POSS being increased at higher temperatures. The POSS molecules exhibited some physical interactions with the polysiloxane uncross-linked chains, but phase separation was induced by the process of cross-linking. In this curing process, POSS molecules could react with the polysiloxane, resulting in decreases in cross-link density. The original POSS crystals could also be dissolved in the polysiloxane during the initial curing stages, but recrystallization upon cooling gave regenerated crystals that were roughly spherical.     

Physical gelation in ethylene-propylene copolymer melts induced by polyhedral oligomeric silsesquioxane (POSS) molecules

The rheological behavior of ethylene-propylene (EP) copolymers containing polyhedral oligomeric silsesquioxane (POSS) molecules was investigated by means of wide-angle X-ray diffraction (WAXD), oscillatory shear, stress and strain controlled rheology in the molten state and dynamic mechanical analysis (DMA) in the solid state. WAXD results showed that the majority of POSS molecules in the EP melt were present in the crystal form. Oscillatory shear results showed that the EP/POSS nanocomposites exhibited a solid-like rheological behavior compared with the liquid-like rheological behavior in the neat resin, i.e. POSS caused physical gelation in EP. While POSS exhibited only a minimum effect on the flow activation energy of EP, the high POSS concentration samples were found to induce higher yield stress than the neat resin. This behavior was similar to the Bingham rheology, indicative of a structured fluid. DMA results indicated that the presence of POSS increased the Young's modulus as well as the T_g of the EP copolymer. These results suggested that two types of interactions contributed to the physical gelation in EP/POSS melts were present: the strong particle-to-particle interactions between the POSS crystals and the weak particle-to-matrix interactions between the POSS crystals and the EP matrix.     

Multilayered confinement of iPP/TPOSS and nylon 6/APOSS blends

A series of isotactic polypropylene and nylon 6 blends with silsesquioxane (POSS) additives were produced, then layered to nanometer thicknesses to test the effects of confinement upon polymer property modification. POSS is shown to be a poor filler, lacking solubility and favorable interaction with the polymer matrices. It was initially hypothesized that under extreme confinement and orientation, such as in melt-spun fibers, or confined within 2D nanoscale layers, that POSS would undergo forced-assembly into elongated, rebar-like reinforcement structures, or even act as crosslinking molecules for the polymer chains. The current results, however, show POSS existing as large, phase separated aggregates, in order to minimize interactions with the polymer matrix; the aggregates behave as debonded hard particles upon tensile deformation. POSS has been previously shown to enhance the properties of polymer matrices in which the POSS molecules have been grafted to, or copolymerized within the chain, but this is not the case for these POSS blends. In comparison to results from the iPP/DBS/TPOSS system, in which POSS is unable to directly interact with the polymer matrix, and the nylon 6/APOSS system, in which POSS can potentially form hydrogen bonds with the polymer matrix, the results are similar and reveal that POSS blends are largely incompatible with the polymer matrix. Small improvements in blend properties can be made via functionalization of the POSS cage, in order to enhance interactions, but these improvements are quite limited.     

Mild processing and characterization of silica epoxy hybrid nanocomposite

Previous research has shown that the inclusion of the spherical silica (SiO₂) nanoparticles into epoxy resin can achieve simultaneous improvement of fracture toughness and modulus. However, the glass transition temperature of the nanocomposite was significantly decreased when loading the nanosilica was higher than 5 wt.%. This perhaps was caused by utilization of the ultrasonication probe in the processing of these materials. In this paper, milder processing procedures were applied to make spherical silica epoxy nanocomposites while investigating if the homogeneous dispersion and morphology of the individual silica nanoparticle dispersed in the epoxy matrix could still be achieved. The results show that even at high loading of the silica nanoparticle, such as 30 wt.% silica, the perfect morphology of the nanocomposite could still be achieved with these milder processing conditions which indicates that ultrasonication is not needed. With the use of milder processing conditions, the glass transition temperature of the nanocomposite of 5 wt.% silica loading did not change, and the drop in the T_g was minimal for silica loading up to 15%, but some effects of self-polymerization of the epoxy were noted on T_g up to 30 wt.% loading of silica. Thermal analysis and flammability testing of the resulting materials suggest that nanosilica has only an inert filler effect (dilution of fuel) on flammability reduction and char yield increase, not a synergistic decrease in heat release as is often observed for clays and carbon nanotubes/nanofibers. So the mild and easy processing procedure only achieved uniform nanoscale morphology with excellent dispersion in the final nanocomposite, but also the effect on the change in the T_g can be minimized as nanosilica loading was increased.     

Percolation phenomena in polymers containing dispersed iron

Metal‐polymer composites based on polyethylene (PE), polyoxymethylene (POM), polyamide (PA) and a PE/POM blend as matrix and dispersed iron (Fe) as filler have been prepared by extrusion of the appropriate mechanical mixtures, and their electrical conductivity, dielectric properties and thermal conductivity have been investigated. The filler spatial distribution is random in the PE‐Fe, POM‐Fe and PA‐Fe composites. In the PE/POM‐Fe composite the polymer matrix is two‐phase and the filler is contained only in the POM phase, resulting in an ordered distribution of dispersed Fe in the volume of polymer blend. The transition through the percolation threshold ?_c is accompanied by a sharp increase of the values of conductivity σ, dielectric constant ε′ and dielectric loss tangent tan δ. The critical indexes of the equations of the percolation theory are close to the theoretical ones in the PE‐Fe and POM‐Fe composites, whereas they take unusually high values in the PE/POMFe composite. Thus, t in the equation σ ～ (φ – φ_c)^t is 2.9–3.0 in the systems characterized by random distribution of dispersed filler and 8.0 in the PE/POM‐Fe system. The percolation threshold φ_c depends on the kind of polymer matrix, becoming 0.21, 0.24, 0.29 and 0.09 for the composites based on PE, POM, PA and PE/POM, respectively. Also the thermal parameters of the PE/POM‐Fe composite are different from those of all other composites. A model explaining the unusual electrical characteristics of the composite based on the polymer blend (PE/POM‐Fe) is proposed, in agreement with the results of optical microscopy.     

Epoxy nanocomposites with octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane

The POSS-containing nanocomposites of epoxy resin were prepared via the co-curing reaction between octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane (OpePOSS) and the precursors of epoxy resin. The curing reactions were started from the initially homogeneous ternary solution of diglycidyl ether of bisphenol A (DGEBA), 4,4′-Diaminodiphenylmethane (DDM) and OpePOSS. The nanocomposites containing up to 40 wt% of POSS were obtained. The homogeneous dispersion of POSS cages in the epoxy matrices was evidenced by scanning electronic microscopy (SEM), transmission electronic microscopy (TEM) and atomic force microscopy (AFM). Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) showed that at the lower POSS concentrations (<30 wt%) the glass transition temperatures (T_gs) of the nanocomposites almost remained invariant whereas the nanocomposites containing POSS more than 40 wt% displayed the lower T_gs than the control epoxy. The DMA results show that the moduli of the nanocomposites in glass and rubbery states are significantly higher than those of the control epoxy, indicating the nanoreinforcement effect of POSS cages. Thermogravimetric analysis (TGA) indicates that the thermal stability of the polymer matrix was not sacrificed by introducing a small amount of POSS, whereas the properties of oxidation resistance of the materials were significantly enhanced. The improved thermal stability could be ascribed to the nanoscaled dispersion of POSS cages and the formation of tether structure of POSS cages with epoxy matrix.     

Preparation and characterization of polystyrene‐based magnetic nanocomposites. Thermal,mechanical and magnetic properties

In this paper we report results on both material preparation and characterization of a polystyrene‐based magnetic nanocomposite material. CoFe₂0₄ mineralized sulfonated polystyrene was prepared by in‐situ precipitation and oxidation of Co⁺² and Fe⁺² within a sulfonated polystyrene resin. The magnetic oxide particles of nanometer size were characterized by wide angle X‐ray diffraction (WAXD). Polystyrene‐based composite films were obtained by dispersion of the finely milled mineralized resin in a polystyrene matrix from the melt state (compositions ranging from 0 to 50 wt% of mineralized resin). The thermal and mechanical properties of the nanocomposite films were determined by TGA, DSC, and stress‐strain testing. The magnetic characterization of the samples was also performed. No significant changes in thermal stability, glass transition temperature or mechanical properties of the polystyrene matrix occur as a consequence of the content in mineralized resin. These results show that the filler acts as aninert diluent for the polymer matrix. On the other hand, the magnetic characterization of the samples reveals the presence of nanoparticles with diameters ranging from 3 to 8 nm, showing, at room temperature, coercive field values of around 800 Oe and saturation magnetization between 120 and 420 emu/g. The combination of these properties suggests the use of these systems in the preparation of magnetic recording materials with high recording density.     

Morphology and thermal properties of inorganic-organic hybrids involving epoxy resin and polyhedral oligomeric silsesquioxanes

The organic-inorganic hybrids involving epoxy resin and polyhedral oligomeric silsesquioxanes (POSS) were prepared via in situ polymerization of diglycidyl ether of bisphenol A (DGEBA) and 4,4′-diaminodiphenylmethane (DDM) in the presence of the two structurally similar POSS monomers. The organic groups on silsesquioxane cage are aminophenyl and nitrophenyl groups, respectively. The curing reactions were started from the initially homogeneous mixture of DGEBA, DDM and the POSS cages. The inorganic-organic hybrids containing up to 20 wt% of POSS were obtained. The morphologies of the resulting hybrids were quite dependent on the types of R groups in the POSS monomers. The phase separation induced by polymerization occurred in the hybrids containing octanitrophenyl POSS (OnpPOSS) and the spherical particles of POSS-rich phase (<0.5 μm in diameter) were uniformly dispersed the continuous epoxy matrix as shown by scanning electronic microscopy. In marked contrast to the OnpPOSS-containing hybrids, the octaaminophenyl POSS (OapPOSS)-containing nanocomposites exhibited a homogeneous morphology. Differential scanning calorimetry and dynamic mechanical analysis showed that the glass transition temperatures (T_g) of the POSS-containing hybrids were lower than that of the control epoxy. The moduli of glass states for the hybrids are significantly higher than that of the control epoxy. For the OapPOSS epoxy nanocomposites the storage moduli of the rubbery plateau were higher than that of the control epoxy when the contents of POSS are less than 20 wt%, indicating the nanoreinforcement effect of POSS cages. Thermogravimetric analysis indicates that the thermal stability of the polymer matrix was not much sacrificed by introducing a small amount of POSS, whereas the properties of oxidation resistance of the materials were significantly enhanced. The OapPOSS epoxy nanocomposites displayed more pronounced improvement than the OnpPOSS hybrids, which could be ascribed to the nanoscaled dispersion of POSS cages and the formation of tether structure of POSS cages with epoxy matrix.     

Synthesis,Morphology and Viscoelastic Properties of Epoxy/Polyhedral Oligomeric Silsesquioxane (POSS) and Epoxy/Cyanate Ester/POSS Nanocomposites

TriSilanolPhenyl-polyhedral oligomeric silsesquioxane (POSS-1) (C₄₂H₃₈O₁₂Si₇), 1–15 wt%, was incorporated into aliphatic epoxy resin (Clearstrem Products, Inc.) with aliphatic diamine curing agents and cured. This epoxy resin was also blended with an equal weight (50/50 w/w) of aromatic cyanate ester resin, Lonza’s PT-15, and 1–15 wt% of POSS-1 and cured. These composites were characterized by FT-IR, X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (X-EDS), dynamic mechanical thermal analysis (DMTA) and three-point bending flexural tests. XRD and X-EDS measurements were consistant with partial molecular dispersion of the POSS units in the continuous matrix phase, together with POSS aggregates. TEM and SEM show that POSS-1-enriched nanoparticles are present in the matrix resins of both the epoxy/POSS and epoxy/cyanate ester/POSS-1 composites. The storage bending moduli, E′, in the rubbery region and the glass transition temperatures, T_g, of epoxy and epoxy/cyanate ester 1-5% POSS-1 composites are higher than those of the reference resins. Small amounts (≤5 wt%) of POSS-1 improved E′ and T_g of both systems and raised flexural strengths and moduli.     

Dielectric properties and morphology of polymer composites filled with dispersed iron

The dielectric properties and the structure of various metal–polymer composites, based on a polymer matrix of polyamide (PA), polyethylene (PE), polyoxymethylene (POM), or blend PE/POM filled with dispersed iron (Fe) particles, have been investigated in this work. In PE–Fe, PA–Fe, and POM–Fe composites the filler spatial distribution is random. In the PE/POM–Fe composites, the polymer matrix is two‐phase and the filler particles are localized only in the POM phase, resulting in an ordered distribution of the dispersed filler particles within the blend. The concentration and frequency dependence of the dielectric permittivity, ε′, and the dielectric loss tangent, tanδ, are described in terms of the percolation theory. The experimental values of the critical exponents (namely, s, r, and y) are in good agreement with those predicted by the theory for the composites with random filler distribution. The PE/POM–Fe composites demonstrate low value of the percolation threshold, P_C, and high values of the critical exponents r and y. This is attributed to the specific structure of these composites. A schematic model for the morphology of the composites studied has been proposed. This model explains the peculiar behavior of the PE/POM–Fe composites by assuming ordered distribution of the filler particles in a binary polymer matrix. The proposed model is in good agreement with the results of optical microscopy. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3013–3020, 2003     

Novel elastomer‐dumbbell functionalized POSS composites: Thermomechanical and Morphological Properties

Nanocomposites consisting of poly(styrene‐b‐butadiene‐b‐styrene) (SBS) and polyhedral oligomeric silsesquioxanes (POSS) were prepared using a solvent dispersion method. Dumbbell‐shaped POSS fillers were prepared using diacyl chlorides to bridge the POSS molecules. Infrared spectroscopy confirmed functionalization. Scanning electron microscopy revealed an increase in filler aggregation with concentration, with preferential phase selectivity. Polydispersity increased with filler concentration while d spacing was influenced by phase selectivity and domain‐filler compatibility. Functionalized POSS improved thermal stability by imparting restrictions of SBS chain motions. Tensile stress–strain analysis revealed an increase in modulus, yield strength, and strain hardening with filler concentration, while creep deformation decreased and permanent strain increased with POSS content. Storage modulus, loss modulus, and glass transition temperature increased with filler content due to effective SBS–POSS interaction. Nanocomposite properties were influenced by filler concentration, the phase of the filler was dispersed throughout and the length of the alkyl “barbell” on the dumbbell‐shaped POSS. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Uniform dispersion of nano-Al2O3 particles in the 3D graphene network of ternary nanocomposites

The interconnected 3D graphene network framework wrapping homogeneous dispersion of nano-Al₂O₃ particles was successfully designed in the phenolic resin-based ternary nanocomposite. Firstly, the solvothermal method was used to prepare graphene hybrid with highly dispersive nano-Al₂O₃ particles in a mixed solvent of ethanol absolute and deionized water. Nano-Al₂O₃ particles were homogeneously dispersed in the 3D graphene network framework when the volume ratio of ethanol absolute and deionized water was 1:1. Then the phenolic resin monomer was impregnated into the graphene hybrid by the appropriate heating process. Finally, the nano-Al₂O₃ particles/3D graphene/phenolic resin ternary nanocomposite was fabricated by in-situ polymerization. The homogeneous dispersion of nano-Al₂O₃ particles was well maintained in the nanocomposite. The nanocomposite possesses high mechanical properties. The nanocomposite leads to 35.02% and 31.50% increases in hardness and compressive strength than that directly dispersed nano-Al₂O₃ particles in the phenolic resin, respectively.     

Engineering properties of Novolac resin‐PMMA{poly(methyl methacrylate)} IPN system

Full and semi interpenetrating polymer networks (IPNs) based on phenol‐formaldehyde resin (Novolac) and poly(methyl methacrylate) have been made by in situ sequential technique of IPN formation. These systems of different compositions were characterized with respect to their mechanical properties, such as, ultimate tensile strength (UTS), percentage elongation at break, modulus, and toughness. Thermal properties were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Extent of phase mixing of the two polymers was envisaged from the micrographs obtained by polarizing light microscopy (PLM). The effects of variation of the blend ratios on the above‐mentioned properties were examined. There was a decreasing trend of modulus and UTS with consequent increases in elongation at break and toughness for both types of IPNs with increase in proportions of PMMA. Lowering of glass transition temperatures (with respect to pure crosslinked Novolac resin) of the IPNs with increasing proportions of PMMA was observed, indicating a plasticizing influence of PMMA on the rigid and brittle matrix of phenolic resin. The TGA thermograms exhibit lowering in thermal stability of the IPNs with respect to pure phenolic resin in the regions of higher temperatures. With increase in proportion of PMMA the onset of degradation of the IPNs is shifted towards lower temperature zone. The surface morphology as revealed by PLM indicates distribution of discrete domains of PMMA in the phenolic resin matrix. The two phase interfaces are quite sharp at higher concentrations of PMMA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2764–2774, 2004