Addition Of Polyhedral Oligomeric Silsesquioxane Research Articles

Effect of POSS on morphology and properties of poly(2,6-dimethyl-1,4-phenylene oxide)/polyamide 6 blends

Poly(2,6-dimethyl-1,4-phenylene oxide)/polyamide 6 (PPO/PA6) (50/50 w) blends filled with epoxycyclohexyl polyhedral oligomeric silsesquioxane (POSS) were prepared via melt-mixing. The reactions between POSS and PPO/PA6 blends were studied by Fourier transform infrared spectroscopy, end group and gel content tests. The morphology of PPO/PA6/POSS composites was observed by field emission scanning electron microscope and transmission electron microscope. As a chain extender and a crosslinking agent for PA6, POSS largely affected the morphology of the composites, which was mainly dependent on the melt-viscosity ratio and interfacial tension between the components. With increasing POSS content from 2 to 4 phr, the morphology of the composites transformed from droplet/matrix to co-continuous morphology. The PPO/PA6/POSS composites with co-continuous morphology had the better mechanical properties than those with droplet/matrix morphology. Dynamic mechanical thermal analysis showed that the addition of POSS increased the T g of PA6.

Organic−Inorganic Hybrid Compounds Containing Polyhedral Oligomeric Silsesquioxane for Conservation of Stone Heritage

Alkoxysilane solutions based on tetraethoxysilane (TEOS) have been widely used for the consolidation of decaying heritage stone surfaces. TEOS-based products polymerize within the porous structure of the decaying stone, significantly increasing the cohesion of the grains of stone components. However, they suffer from practical drawbacks, such as crack formation of the gel during the drying phase due to the developing capillary force and dense gel fractures left inside of the stone. In this study, a TEOS-based stone consolidant containing functional (3-glycidoxypropyl)trimethoxysilane (GPTMS) and polyhedral oligomeric silsesquioxane (POSS) has been prepared in order to reduce gel crack formation during the drying phase. The addition of nanometer-sized POSS and/or GPTMS having a flexible segment reduces the capillary force developed during solvent evaporation. The properties of the TEOS/GPTMS/POSS composite solutions were compared with those of commercial products (Wacker OH and Unil sandsteinfestiger OH 1:1). The gelation time was similar to that of commercial consolidants, and the TEOS/GPTMS/POSS solution was stable over a period of up to 6 months. The addition of POSS and GPTMS provided a crack-free gel, while the gel from the commercial consolidants exhibited cracks after drying. The surface hydrophobicity of the treated decayed granite increased with the addition of POSS and GPTMS, and it was higher than that of the commercial product, implying the possibility of POSS and GPTMS as barriers to the penetration of water. This result implies that the TEOS/GPTMS/POSS solution showed a high suitability for the consolidation of granite heritage.

Polyhedral oligomeric silsesquioxane-reinforced polyurethane acrylate

Hybride nanocomposite films of polyhedral oligomeric silsesquioxane (POSS) and polyurethane acrylate (PUA) were prepared by introducing POSS into PUA by free-radical photopolymerization, to enhance thermo-mechanical properties of PUA. The addition of POSS to PUA resulted in increases in the following properties: elasticity, glass transition temperature, thermal stability and dimensional stability. With increasing POSS content, the elastic modulus and thermal stability of PUA films increased due to an increased crosslinking density and the reinforcing effect of POSS particles on the PUA, whereas the surface free energies of these films decreased. The water contact angle against water increased due to the enhancement of the hydrophobicity of the polymer surface, caused by the low surface energy of POSS molecular. However, at high POSS content the mechanical properties of the films were decreased, as a result of aggregation of the POSS particles.

Ethylene–Propylene–Silsesquioxane Thermoplastic Elastomers

AbstractPreparative methods for the incorporation of polyhedral oligomeric silsesquioxane (POSS) macromonomers into ethylene–propylene (EP) polymers have been developed that utilize metallocene polymerization. Analysis of these novel ethylene–propylene–POSS polymers using wide‐angle X‐ray diffraction reveals that pendant POSS groups off the polymer backbones aggregate with a phenyl periphery, and the polymers crystallize as anisotropically shaped nanocrystals. POSS particle aggregation is strongly dependent on the nature of the POSS peripheral group. X‐Ray studies suggest that aggregation of POSS in the EP elastomers did not occur with isobutyl and ethyl peripheries, as they disperse within the polymer matrix. The formation of POSS nanocrystals increases the mechanical properties of these thermoplastic elastomers. The tensile storage modulus increases significantly with the addition of POSS, as does the length of the rubbery plateau region. Tensile studies reveal an elongation at break of 720% for one EP‐phenyl POSS polymer sample, with the others between 400 and 500%.magnified image

Addition of POSS−T8to the Si(100) Surface

The interaction of the polyhedral oligomeric silsesquioxane (POSS) T8, (HSiO3/2)8 with the Si(100) surface has been studied using a cluster model, represented by the single dimer Si9H12 to represent the surface. Hartree−Fock (HF), density functional theory (DFT), and multi-configuration self-consistent field (MCSCF) wavefunctions have been used to optimize the geometries of stationary points on the potential energy surface. The HF and MCSCF wavefunctions are augmented by second-order perturbation theory for improved relative energies. The POSS reacts with the Si(100) surface saturating dangling bonds on the surface, yielding two possible addition products. One of these forms a Si−Si bond between the POSS and the dimer at the same time that a hydrogen atom is transferred from the POSS to the adjacent silicon atom of the same dimer, with no structural modification of the cage. The other product involves the opening of the POSS cage with the corresponding formation of a pair of Si−Si and Si−O bonds with the ...

Morphology and rheological behaviors of poly(ethylene terephthalate) nanocomposites containing polyhedral oligomeric silsesquioxanes

AbstractPoly(ethylene terephthalate) (PET)/polyhedral oligomeric silsesquioxane (POSS) nanocomposites were prepared by in situ polymerization. Light scattering measurement suggested that there is significant change in molecular weight arising from gel formation by chemical crosslinking during polymerization. The thermal decomposition temperatures of the composites measured at 5 wt % weight loss were 5–10°C higher than that of PET. There is no significant change in other thermal properties. Scanning electron microscopy observations suggest that there is obvious phase separation in PET/POSS composites, composites containing 1 wt % of disilanolisobutyl and trisilanolisobytyl‐POSS show fine dispersions of POSS (30–40 nm in diameter), which arise from strong interfacial interactions between POSS and PET during polymerization. The viscosity of the composites increased with the addition of POSS. The observation of a plateau region of composites containing 1 wt % of POSS in the plot of log G′ vs. log G″ indicates strong interfacial interactions between POSS and PET. Sixty‐three percent and 41% increase in tensile strength and 300 and 380% increase in modulus were achieved in the composites containing 1 wt % of disilanol‐ and trisilanol‐POSS, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Properties of epoxy networks derived from the reaction of diglycidyl ether of bisphenol A with polyhedral oligomeric silsesquioxanes bearing OH‐functionalized organic substituents

AbstractA polyhedral oligomeric silsesquioxane (POSS), consisting mainly of a mixture of octahedra, nonahedra, and decahedra with bulky and flexible organic substituents, with three secondary hydroxyls per organic group, was used to modify epoxy networks produced by the homopolymerization of diglycidyl ether of bisphenol A in the presence of benzyldimethylamine. Several physical, thermal, and mechanical properties of the cured materials containing 0, 10, 30, and 50 wt % POSS were determined. The addition of POSS increased the elastic modulus and the yield stress measured in uniaxial compression tests, mainly because of the increase in the cohesive energy density produced by hydrogen bonding through the hydroxyl groups. A constant yield stress/elastic modulus ratio equal to 0.03 was observed for different POSS concentrations and test temperatures. The glass‐transition temperature decreased with POSS addition because of the flexibility of organic branches present in the POSS structure and the decrease in the crosslink density (determined from the rubbery modulus). Although a combination of a reduction in the glass‐transition temperature (plasticization) with an increase in the glassy modulus (antiplasticization) is a well‐known phenomenon, what is original is that in this case it was not the result of the suppression (or reduction in intensity) of subglass relaxations but was produced by an increase in the cohesive energy density. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1451–1461, 2003

Crystallization studies of isotactic polypropylene containing nanostructured polyhedral oligomeric silsesquioxane molecules under quiescent and shear conditions

AbstractCrystallization studies at quiescent and shear states in isotactic polypropylene (iPP) containing nanostructured polyhedral oligomeric silsesquioxane (POSS) molecules were performed with in situ small‐angle X‐ray scattering (SAXS) and differential scanning calorimetry (DSC). DSC was used to characterize the quiescent crystallization behavior. It was observed that the addition of POSS molecules increased the crystallization rate of iPP under both isothermal and nonisothermal conditions, which suggests that POSS crystals act as nucleating agents. Furthermore, the crystallization rate was significantly reduced at a POSS concentration of 30 wt %, which suggests a retarded growth mechanism due to the molecular dispersion of POSS in the matrix. In situ SAXS was used to study the behavior of shear‐induced crystallization at temperatures of 140, 145, and 150 °C in samples with POSS concentrations of 10, 20, and 30 wt %. The SAXS patterns showed scattering maxima along the shear direction, which corresponded to a lamellar structure developed perpendicularly to the flow direction. The crystallization half‐time was calculated from the total scattered intensity of the SAXS image. The oriented fraction, defined as the fraction of scattered intensity from the oriented component to the total scattered intensity, was also calculated. The addition of POSS significantly increased the crystallization rate during shear compared with the rate for the neat polymer without POSS. We postulate that although POSS crystals have a limited role in shear‐induced crystallization, molecularly dispersed POSS molecules behave as weak crosslinkers in polymer melts and increase the relaxation time of iPP chains after shear. Therefore, the overall orientation of the polymer chains is improved and a faster crystallization rate is obtained with the addition of POSS. Moreover, higher POSS concentrations resulted in faster crystallization rates during shear. The addition of POSS decreased the average long‐period value of crystallized iPP after shear, which indicates that iPP nuclei are probably initiated in large numbers near molecularly dispersed POSS molecules. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2727–2739, 2001