Shawn H. Phillips

Structural development during deformation of polyurethane containing polyhedral oligomeric silsesquioxanes (POSS) molecules

A unique polyurethane (PU) elastomer containing inorganic polyhedral oligomeric silsesquioxane (POSS) molecules as molecular reinforcements in the hard segment was investigated by means of wide-angle X-ray diffraction (WAXD), small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) techniques. The mechanical properties of POSS modified polyurethane (POSS-PU) were also compared to those of polyurethane without POSS. The crystal structures of two different POSS molecules were first determined by X-ray powder diffraction analysis, yielding a rhombohedral cell with aa 11.57 A ˚, aa 95.58 for octacyclohexyl-POSS (1,3,5,7,9,11,13,15octacyclohexylpentacyclo[9.5.1.13,9.15,15.17,13] octasiloxane) and aa 11.53 A ˚, aa 95.38 for hydrido-POSS (1-[hydridodimethylsiloxy]3,5,7,9,11,13,15-heptacyclohexylpentacyclo [9.5.1.13,9.15,15.17,13] octasiloxane). WAXD results showed that reflection peaks distinct to POSS crystal diffraction were seen in POSS-modified polyurethane, which suggests that POSS molecules formed nanoscale crystals in the hard domain. During deformation, the average size of POSS crystals in POSS-PU was found to decrease while elongation-induced crystallization of the soft segments was observed at strains greater than 100%. The SAXS results showed microphase structure typical of segmented

Nanoscale reinforcement of polyhedral oligomeric silsesquioxane (POSS) in polyurethane elastomer

A unique class of polyurethane (PU) elastomer containing inorganic molecules (polyhedral oligomeric silsesquioxane, POSS) as molecular reinforcement in the hard segment was investigated by means of wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) techniques. WAXD results indicate that POSS molecules form nanoscale crystals showing distinct reflection peaks. The formation of POSS crystals is probably prompted by the microphase separation between solid-like hard segments and rubbery soft segments in PU. The microphase separation of hard and soft segments was observed by SAXS, which shows a long period of 111 A for 34 wt% POSS-PU and 162 A for 21 wt% POSS-PU, and hard segment domains with sizes of about 34 A for both of them. WAXD results from a series of POSS compounds with a corner substituted by a functional group of varying length were compared with POSS-PU, which also confirms the presence of nanoscale POSS crystals in the polymer matrix. © 2000 Society of Chemical Industry

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 Youngs modulus as well as the Tg 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.

Time-resolved shear behavior of end-tethered Nylon 6–clay nanocomposites followed by non-isothermal crystallization

Abstract Simple shear of end-tethered Nylon 6–clay nanocomposites and the preservation of these effects into the crystalline state is reported. Typical conditions leading to mesoscopic (clays) and molecular (polymer chains) orientation of these systems at relatively low shear rates and at temperatures immediately above the nominal melting point showed a morphological change proportional to the shear time in the molten state. Gradual alignment of the through-view SAXS patterns indicated the rotation of the end-tethered clay along the shear direction. High temperature relaxation of clay after shear was substantially longer than the polymer. Thus, non-isothermal crystallization into the crystalline state could be used to preserve the orientation of the clay induced by shear. It was found that most of the clay planar alignment in Nylon 6–clay nanocomposites rendered the γ crystal habit, which is typically associated with the extended chain crystallization. Nylon 6, on the other hand, crystallized into the α habit commonly associated with quiescent crystals involving folded chains. The shear results were compared with quiescent crystallization, where the Nylon 6 nanocomposites exhibited the preferential γ habit and the Nylon 6 homopolymer exhibited mixed α/γ habits.

Synthesis and Characterization of Segmented Polyurethanes Containing Polyhedral Oligomeric Silsesquioxanes Nanostructured Molecules

Segmented polyurethanes based on diphenylmethane-4,4′-diisocyanate and polytetra-methylene glycol were synthesized using a mixture of polyhedral oligomeric silsesquioxane (POSS)-diol and 1,4-butanediol as chain extenders. The polymers were characterized by differential scanning calorimetry, wide-angle x-ray diffraction (WAXD), small-angle x-ray scattering (SAXS) and tensile property tests. Microphase separation between the hard and soft segment domains was observed in all the samples by SAXS. The increase of the POSS concentration was found to weaken the microphase separation between the domains and increase the T g of the soft segments. The WAXD results showed that when the POSS concentration was greater than 10 wt%, the 101 diffraction peak from the POSS crystals could be observed, which suggested the formation of POSS nanocrystals in the hard domain. The tensile property tests showed that polyurethanes containing the nanostructured POSS molecules had higher moduli, but lower maximum elongation ratios.

In situ oxygen atom erosion study of a polyhedral oligomeric silsesquioxane-polyurethane copolymer

The surface of a polyhedral oligomeric silsesquioxane-polyurethane copolymer has been characterized in situ using X-ray photoelectron spectroscopy before and after exposure to incremental fluences of oxygen atoms produced by a hyperthermal oxygen atom source. The data indicate that the atomic oxygen initially attacks the cyclopentyl groups that surround the polyhedral oligomeric silsesquioxane cage most likely resulting in the formation and desorption of CO and/or CO2 and H2O from the surface. The carbon concentration in the near-surface region is reduced from 72.5 at.% for the as-entered surface to 37.8 at.% following 63 h of O-atom exposure at a flux of 2.0 × 1013 O atom/cm2-s. The oxygen and silicon concentrations are increased with incremental exposures to the O-atom flux. The oxygen concentration increases from 18.5 at.% for the as-entered sample to 32.6 at.% following the 63-h exposure, and the silicon concentration increases from 8.1 to 11.1 at.% after 63 h. The data reveal the formation of a silica layer on the surface, which serves as a protective barrier preventing further degradation of the polymer underneath with increased exposure to the O-atom flux.

Polyhedral Oligomeric Silsesquioxane (POSS) Styrene Macromers

Four polyhedral oligomeric silsesquioxane (POSS) macromers, R7Si8O12styrene (R=isobutyl, cyclopentyl, cyclohexyl, or phenyl), containing a single polymerizable styrene unit were synthesized from the POSS-trisilanols R7Si7O9(OH)3 in a high yield and purity. The base-assisted reaction to produce these macromers appears to be general for POSS-trisilanols of this type. However, in some cases it may be necessary to control the rate at which the base is introduced during reaction to prevent unwanted side reactions that decompose the trisilanol. Cyclohexyl-, cyclopentyl-, and isobutyl-substituted POSS-stryenes (at 30 wt% or approximately 4 mol% loadings) undergo free radical bulk polymerizations with styrene to produce polymers that show variation in the modulus above the glass transition temperature. The phenylPOSS derivative is too insoluble in styrene to undergo this polymerization. The effect on the modulus is more pronounced for the copolymers containing 30 wt% cycloalkylPOSS than that seen with isobutylPOSS, which is similar to that for bulk polymerized polystyrene. The effect of the group at the POSS cage on bulk polymer properties has been noted before and is presumed to arise from differences in polymer microstructure.

SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF A REMARKABLY STABLE, ANIONIC,INCOMPLETELY CONDENSED SILSESQUIOXANE FRAMEWORK

The reaction of [(C 6 H 11 ) 7 Si 7 O 9 (OH) 3 ] 1 (2 equiv.) with [(C 6 H 11 ) 7 Si 7 O 9 (OTl ) 3 ] 3 affords a conproportionation product that reacts with [PPh 4 ]Cl, [PBu n 4 ]Cl and [NBu n 4 ]Br to produce the corresponding salts of [(C 6 H 11 ) 7 Si 7 O 10 (OH ) 2 ] - 5 (i.e. the monoanion derived from deprotonation of 1); a single-crystal X-ray diffraction study of the [(NBu n 4 ] + salt of 5 indicates that the molecules exist as isolated ion pairs with strong intramolecular hydrogen bonding; implications of this result for the chemistry of silica are discussed.

Hybrid Inorganic/Organic Diblock Copolymers. Nanostructure in Polyhedral Oligomeric Silsesquioxane Polynorbornenes.

Our main approach to the synthesis and study of hybrid organic/inorganic materials involves incorporating nano-size inorganic polyhedral oligomeric silsesquioxane (POSS) clusters into various polymeric resins. A typical POSS cluster is a discrete silicon and oxygen framework solubilized with organic groups and contains a single reactive site. This lone site of reactivity is used to covalently attach the inorganic macromers pendent to a polymer backbone without causing any crosslinking. This strategy permits the synthesis of melt processable, linear hybrid polymers containing pendent inorganic clusters, and allows us to study the effect these clusters have on chain motion, polymer properties and morphology. The synthesis of norbornenyl-based (POSS) macromers, their ring opening metathesis copolymerizations with varying amounts of norbornene, and analysis of the effect of the pendent POSS group is presented. Ring opening metathesis polymerization permits the easy synthesis of both random and diblock copolymers. Transmission electron microscopy (TEM) clearly images POSS-rich domains against the POSSfree regions. Major differences in polymer morphology are observed as the amount of inorganic POSS is varied, between random and diblock copolymers, as well as between polymers that differ only in the solubilizing cycloalkyl groups on the POSS cluster.

New Insightl into the Structure-Property Relationships of Hybrid (Inorganic/Organic) Poss™ Thermoplastics

Abstract : The demand for multi-purpose, high-performance polymer systems has resulted in a need for advancing polymer properties beyond what traditional systems can offer. Only through control/alteration at the molecular level can one maximize property enhancements to meet current military and commercial needs. Over the last seven years the Air Force Research Laboratory has developed and incorporated discrete Si-O frameworks (POSS = Polyhedral Oligomeric Silsesquioxanes) into traditional organic polymer systems. This research has resulted in new hybrid inorganic-organic polymer systems with remarkable enhancements in mechanical and physical properties including dramatic increases in both glass transition and decomposition temperatures, reduced flammability, increased moduli and oxidation resistance. We have shown that these enhancements result from the chemical composition (Si-O core) and size (^15 A in diameter) of the POSS frameworks, and can be copolymerized, grafted, or even blended using traditional processing methods. Recently, we have focused our efforts on understanding and controlling the molecular level interactions between POSS frameworks and the polymer matrix. The development of new POSS monomers has allowed us to study how functionality, size, and geometry enhances the bulk properties of these hybrid materials. For example, increasing the solubility of side groups on the POSS framework results in greater POSS-polymer matrix interactions and increased Tg and storage moduli. Recent studies with POSS blends have resulted in increases in hardness, and reductions in dielectric constants and coefficients of thermal expansion. New results in polymer synthesis, characterization, and applications will be discussed with a strong emphasis on the versatility of this new nanotechnology to many polymer systems.