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Bates, Frank S

Publications and source records attributed to Bates, Frank S.

8 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Layered zeolite materials and methods related thereto

A novel oxide material (MIN-I) comprising YO.sub.2; and X.sub.2O.sub.3, wherein Y is a tetravalent element and X is a trivalent element, wherein X/Y=O or Y/X=30 to 100 is provided. Surprisingly, MIN-I can be reversibly deswollen. MIN-I can further be combined with a polymer to produce a nanocomposite, depolymerized to produce predominantly fully exfoliated layers (MIN-2), and pillared to produce a pillared oxide material (MIN-3), analogous to MCM-36. The materials are useful in a wide range of applications, such as catalysts, thin films, membranes, and coatings.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Nanoscale Mixing of Soft Solids

Assessing the state of mixing on the molecular scale in soft solids is challenging. Concentrated solutions of micelles formed by self-assembly of polystyrene-block-poly(ethylene-alt-propylene) (PS-PEP) diblock copolymers in squalane (C{sub 30}H{sub 62}) adopt a body-centered cubic (bcc) lattice, with glassy PS cores. Utilizing small-angle neutron scattering (SANS) and isotopic labeling ({sup 1}H and {sup 2}H (D) polystyrene blocks) in a contrast-matching solvent (a mixture of squalane and perdeuterated squalane), we demonstrate quantitatively the remarkable fact that a commercial mixer can create completely random mixtures of micelles with either normal, PS(H), or deuterium-labeled, PS(D), cores on a well-defined bcc lattice. The resulting SANS intensity is quantitatively modeled by the form factor of a single spherical core. These results demonstrate both the possibility of achieving complete nanoscale mixing in a soft solid and the use of SANS to quantify the randomness.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2013

Large Amplitude Oscillatory Shear of Block Copolymer Spheres on a Body-Centered Cubic Lattice: Are Micelles Like Metals?

Small-angle X-ray diffraction experiments have uncovered a remarkable mechanism of grain alignment during plastic deformation of ordered sphere-forming diblock copolymer micelles when subjected to large amplitude dynamic shearing. A nearly monodisperse poly(styrene-b-ethylene-alt-propylene) (SEP) diblock copolymer with block molecular weights of 42,000 and 60,000 was mixed with squalane (C{sub 30}H{sub 62}), an EP selective solvent, at a concentration of 10 wt %. After high temperature annealing, the sample formed an ordered polydomain morphology containing glassy S cores at room temperature. SAXS powder patterns confirm body-centered cubic (BCC) symmetry and reveal the development of a complex array of two-dimensionally resolved Bragg reflections following the application, and cessation, of oscillatory shearing. These diffraction results are interpreted on the basis of the classic mechanism of crystalline slip, which accounts for plastic deformation of ductile materials such as metals. Four distinct slip systems are shown to be active in this work, suggesting a robust basis for deforming and mixing of soft ordered solids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Radical-cured block copolymer-modified thermosets

Poly(ethylene-alt-propylene)-b-poly(ethylene oxide) (PEP-PEO) diblock copolymers were synthesized and added at 4 wt % to 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane (BisGMA), a monomer that cures using free radical chemistry. In separate experiments, poly(ethylene glycol) dimethacrylate (PEGDMA) was combined as a secondary monomer with BisGMA and the monomers were loaded with 4 wt % PEP-PEO. The diblock copolymers self-assembled into well-dispersed spherical micelles with PEP cores and PEO coronas. No appreciable change in the final extent of cure of the thermosets was caused by the addition of diblock copolymer, except in the case of BisGMA, where the addition of the block copolymer increased extent of cure by 12%. Furthermore, the extent of cure was increased by 29% and 37% with the addition of 25 and 50 wt % PEGDMA, respectively. Elastic modulus and fracture resistance were also determined, and the values indicate that the addition of block copolymers does not significantly toughen the thermoset materials. This finding is surprising when compared with the large increase in fracture resistance seen in block copolymer-modified epoxies, and an explanation is proposed.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Structure and Mechanical Behavior of Elastomeric Multiblock Terpolymers Containing Glassy, Rubbery, and Semicrystalline Blocks

Multiblock copolymers containing glassy poly(cyclohexylethylene) (C), rubbery poly(ethylene-alt-propylene) (P), and semicrystalline poly(ethylene) (E) were synthesized by sequential anionic polymerization of styrene, isoprene, and butadiene followed by catalytic hydrogenation. The resulting CECPCEC (denoted XPX) and CECP (XP) multiblock copolymers each contain 50 vol % of P and equal amounts of C and E. These materials have been studied by dynamic mechanical spectroscopy (DMS), transmission electron microscopy (TEM), small- and wide-angle X-ray scattering (SAXS and WAXS), differential scanning calorimetry (DSC), and tensile deformation to characterize the morphology, phase behavior, and mechanical properties. Microphase separation in these compounds is induced by crystallization of E and/or chemical incompatibility between the three blocks, leading to a new type of morphology which contains continuous region of P and continuous region of microphase-separated X, resulting in mechanically resilient materials. High molecular weight block copolymers microphase separate with two different length scales associated with segregation between C and E and X and P. These structural features produce a nonclassical scaling relationship for the C-E domain spacing, d {approx} N{sup 0.31}, where N is the degree of polymerization of CEC portion. The role of semicrystalline E domains during uniaxial deformation has been exposed with WAXS experiments, which support a two-step mechanism involving recoverable and nonrecoverable deformation to different extents. Strain hardening is observed in double-anchored XPX, but not in single-anchored XP, at large tensile strains.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Dodecagonal Quasicrystalline Morphology in a Poly(styrene-b-isoprene-b-styrene-b-ethylene oxide) Tetrablock Terpolymer

A dodecagonal quasicrystalline (QC) morphology is identified in a poly(styrene-b-isoprene-b-styrene-b-ethylene oxide) (SISO) tetrablock terpolymer based on evidence provided by transmission electron microscopy (TEM), small-angle X-ray scattering, and dynamic mechanical spectroscopy measurements. The QC state occurs at temperatures between those associated with simple hexagonal order (HEX) and the {sigma}-phase (P4{sub 2}/mnm), T{sub HEX} < T{sub QC} < T{sub {sigma}} < T{sub ODT}, where T{sub ODT} is the order-disorder transition temperature. All three morphologies are formed from spherical domains containing an O core surrounded by a shell of S that screens unfavorable segment-segment interactions with an I-rich matrix. TEM analysis reveals a QC morphology with 12-fold rotational symmetry but devoid of long-range translational order, along with locally coordinated structures consistent with dodecagonal quasicrystalline approximants. The SISO molecular architecture decouples control over the domain shape and interdomain interactions, leading to a multiplicity of packing symmetries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Hierarchically structured bicontinuous polymeric microemulsions

We recently described the synthesis and phase behavior of a new type of CECEC-P multiblock copolymer composed of glassy poly(cyclohexylethylene) (C), semicrystalline poly(ethylene) (E), and elastomeric poly(ethylene-alt-propylene) (P) with symmetric (equal volume) CECEC and P sequences (G. Fleury and F. S. Bates, Macromolecules, 2009, 42, 3598-3610). Here we report the formation and characterization of a multicontinuous structure based on the blending of CEC triblock copolymer and P homopolymer with such a hexablock copolymer along the 50:50 (CEC/P) isopleth. These materials produce a sequence of phases that are correlated with the volume fraction of CECEC-P as evidenced by SAXS and TEM measurements. A percolating bicontinuous mesostructure was identified at volume fractions of hexablock copolymer, f{sub CECEC-P} = 0.10 and 0.125, within the composition range known to result in a bicontinuous morphology in A-B/A/B systems. A solid product was formed by cooling the initially homogeneous ternary mixture from above the melting temperature of the E blocks to room temperature. Crystallization of E leads to microphase separation of C and E and simultaneous ejection of P from CEC (and CECEC) at a larger length scale. The mechanical properties of these materials are inferior to what is anticipated based on pure CEC triblock copolymer, attributable to the low molecular weight and irregular structure of the C/E region sequences. Nevertheless, this study establishes a procedure for producing bicontinuous yet structurally asymmetric materials based on the microemulsion process and extends the concept of a microemulsion to multiblock copolymers.

36 MATERIALS SCIENCE↗