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Articles 1 - 11 of 11
Full-Text Articles in Engineering
Symmetry Breaking Of In-Plane Order In Confined Copolymer Mesophases, G. E. Stein, Eric W. Cochran, K. Katsov, G. H. Fredrickson, E. J. Kramer, X. Li, J. Wang
Symmetry Breaking Of In-Plane Order In Confined Copolymer Mesophases, G. E. Stein, Eric W. Cochran, K. Katsov, G. H. Fredrickson, E. J. Kramer, X. Li, J. Wang
Eric W. Cochran
Packing of spherical-domain block copolymer mesophases confined to a thin film is investigated as a function of the number of layers n. We find an abrupt transition from hexagonal to orthorhombic in-plane ordering of domains when n is increased from 4 to 5. As n increases further (up to 23 in this study), the symmetry of the orthorhombic phase asymptotically approaches that of the body-centered cubic (110) plane. These results are interpreted in terms of the energetics of competing packings in the bulk and at the film interfaces. Detailed structural and thermodynamic properties are obtained with self-consistent field theory.
Effect Of Chain Architecture And Surface Energies On The Ordering Behavior Of Lamellar And Cylinder Forming Block Copolymers, V. Khanna, Eric W. Cochran, A. Hexemer, G. E. Stein, G. H. Fredrickson, E. J. Kramer, X. Li, J. Wang, S. F. Hahn
Effect Of Chain Architecture And Surface Energies On The Ordering Behavior Of Lamellar And Cylinder Forming Block Copolymers, V. Khanna, Eric W. Cochran, A. Hexemer, G. E. Stein, G. H. Fredrickson, E. J. Kramer, X. Li, J. Wang, S. F. Hahn
Eric W. Cochran
We investigate the effect of surface energy and chain architecture on the orientation of microdomains in relatively thick films (600-800 nm) of lamellar and cylindrical block copolymers of poly(cyclohexylethylene) (C) and poly(ethylene) (E). The E block has 26 ethyl branches per 1000 backbone carbon atoms. Melt surface energies of the C and E blocks are 22.3 and 20.9 mJ/m 2, respectively. Grazing-incidence small-angle X-ray scattering (GISAXS), scanning force microscopy (SFM), and cross-sectional transmission electron microscopy (TEM) show that cylindrical and lamellar CEC triblock copolymers orient their microdomains normal to the surface throughout the film thickness. However, a lamellar CE diblock …
Semicrystalline Thermoplastic Elastomeric Polyolefins: Advances Through Catalyst Development And Macromolecular Design, Atsushi Hotta, Eric W. Cochran, Janne Ruokolainen, Vikram Khann, Glenn H. Fredrickson, Edward J. Kramer, Yong-Woo Shin, Fumihiko Shimizu, Anna E. Cherian, Phillip D. Hustad, Jeffrey M. Rose, Geoffrey W. Coates
Semicrystalline Thermoplastic Elastomeric Polyolefins: Advances Through Catalyst Development And Macromolecular Design, Atsushi Hotta, Eric W. Cochran, Janne Ruokolainen, Vikram Khann, Glenn H. Fredrickson, Edward J. Kramer, Yong-Woo Shin, Fumihiko Shimizu, Anna E. Cherian, Phillip D. Hustad, Jeffrey M. Rose, Geoffrey W. Coates
Eric W. Cochran
We report the design, synthesis, morphology, phase behavior, and mechanical properties of semicrystalline, polyolefin-based block copolymers. By using living, stereoselective insertion polymerization catalysts, syndiotactic polypropylene-block-poly(ethylene-co-propylene)-block-syndiotactic polypropylene and isotactic poly propylene-block-regioirregular poly propylene-block- isotactic polypropylene triblock copolymers were synthesized. The volume fraction and composition of the blocks, as well as the overall size of the macromolecules, were controlled by sequential synthesis of each block of the polymers. These triblock copolymers, with semicrystalline end-blocks and mid-segments with low glass-transition temperatures, show significant potential as thermoplastic elastomers. They have low Young's moduli, large strains at break, and better than 90% elastic recovery at …
Stability Of The Gyroid Phase In Diblock Copolymers At Strong Segregation, Eric W. Cochran, Carlos J. Garcia-Cervera, Glenn H. Fredrickson
Stability Of The Gyroid Phase In Diblock Copolymers At Strong Segregation, Eric W. Cochran, Carlos J. Garcia-Cervera, Glenn H. Fredrickson
Eric W. Cochran
The gyroid phase in diblock copolymers at strong segregation was stabilized. The intriguing topology of the network structure has inspired a diverse array of potential applications ranging from high-performance separation membranes to photonic crystals. The pressure field enforces incompressibility, while the exchange field is conjugate to the composition pattern in the melt. The Laplacian operator is treated implicitly with a fourth-order backward differentiation formula (BDF4), whereas the source term is discretized explicitly using fourth-order accurate Adams-Bashford.
Temperature Dependence Of Order, Disorder, And Defects In Laterally Confined Diblock Copolymer Cylinder Monolayers, Matthew R. Hammond, Eric W. Cochran, Glenn H. Fredrickson, Edward J. Kramer
Temperature Dependence Of Order, Disorder, And Defects In Laterally Confined Diblock Copolymer Cylinder Monolayers, Matthew R. Hammond, Eric W. Cochran, Glenn H. Fredrickson, Edward J. Kramer
Eric W. Cochran
Monolayer arrays of polystyrene-poly(2-vinylpyridine) diblock copolymer cylinders with excellent orientational order and a very low density of dislocations are prepared by cooling slowly from above the bulk order - disorder temperature (ODT) ∼212°C within silicon oxide channels one cylinder spacing a in depth and 2 μm in width. The translational order of this array, however, is short range with a correlation length of ∼12a. If such an array is heated to a temperature above the glass transition temperature of the block copolymer (100°C) but well below the ODT, a finite density of thermally generated dislocations is observed, which leads to …
Ordered Network Phases In Linear Poly(Isoprene-B-Styrene-B-Ethylene Oxide) Triblock Copolymers, Thomas H. Epps Iii, Eric W. Cochran, Travis S. Bailey, Ryan S. Waletzko, Cordell M. Hardy, Frank S. Bates
Ordered Network Phases In Linear Poly(Isoprene-B-Styrene-B-Ethylene Oxide) Triblock Copolymers, Thomas H. Epps Iii, Eric W. Cochran, Travis S. Bailey, Ryan S. Waletzko, Cordell M. Hardy, Frank S. Bates
Eric W. Cochran
The equilibrium phase behavior of 43 linear poly(isoprene-b-styrene-b- ethylene oxide) (ISO) triblock copolymer melts, with molecular weights that place these materials near the order-disorder transition, is reported. Ordered phase morphologies were characterized using small-angle X-ray scattering, transmission electron microscopy, dynamic mechanical spectroscopy, and static birefringence measurements. Interpretation of these results was aided by a modeling technique that facilitates resolution of reciprocal and real-space experimental data, leading to definitive three-dimensional morphological structures. Three distinct multiply continuous network morphologies are identified across a range of compositions between 0.1 ≤ f o ≤ 0.3, situated between two-domain and three-domain lamellae, where f o …
Network Phases In Abc Triblock Copolymers, Thomas H. Epps Iii, Eric W. Cochran, Cordell M. Hardy, Travis S. Bailey, Ryan S. Waletzko, Frank S. Bates
Network Phases In Abc Triblock Copolymers, Thomas H. Epps Iii, Eric W. Cochran, Cordell M. Hardy, Travis S. Bailey, Ryan S. Waletzko, Frank S. Bates
Eric W. Cochran
Many naturally occurring and engineered products are influenced by network structures. Collagen networks provide a scaffold for living tissue, while swollen arrays of physically cross-linked polypeptides constitute gelatin, the familiar dessert and electrophoresis medium. Although the associated mesh sizes differ by several orders of magnitude, these examples share a common feature: three-dimensional connectivity that imparts mechanical rigidity. Intercalating additional interconnected components can yield broader functions, e.g., ionic or electrical conductivity, optical band gaps, and tailored heat and mass transfer.
Shear-Induced Network-To-Network Transition In A Block Copolymer Melt, Eric W. Cochran, Frank S. Bates
Shear-Induced Network-To-Network Transition In A Block Copolymer Melt, Eric W. Cochran, Frank S. Bates
Eric W. Cochran
The tricontinuous (10, 3)c shear-induced network-to-network transition in a block copolymer melt was analyzed using small-angle x-ray scattering. Investigations show that field-induced network-to-network phase transition was unprecedented in soft condensed matter. It was found that shear transforms were used for self-assembling the soft material into a single crystal (10, 3)d network. The results show the delicate nature of block copolymers phase behavior, where candidate morphologies were spaced closely together on the free energy surface.
Consequences Of Block Number On The Order-Disorder Transition And Viscoelastic Properties Of Linear (Ab)N Multiblock Copolymers, Lifeng Wu, Eric W. Cochran, Timothy P. Lodge, Frank S. Bates
Consequences Of Block Number On The Order-Disorder Transition And Viscoelastic Properties Of Linear (Ab)N Multiblock Copolymers, Lifeng Wu, Eric W. Cochran, Timothy P. Lodge, Frank S. Bates
Eric W. Cochran
The effect of block number on the order-disorder transition (ODT) and viscoelastic properties were studied for linear (AB) n multiblock copolymers. A series of symmetric poly(styrene-b-isoprene) n multiblocks ((SI) n, n = 1-10) were synthesized by anionic polymerization, and their order-disorder transition temperatures (T ODT) were located using dynamic mechanical spectroscopy. As n increases, T ODT approaches an asymptotic value, consistent with random phase approximation calculations. A systematic difference between the experimental and theoretical results is attributable to the effects of fluctuations, independent of the number of blocks. Addition of up to 20 vol % of a nonselective solvent depresses …
Design Of Abc Triblock Copolymers Near The Odt With The Random Phase Approximation, Eric W. Cochran, David C. Morse, Frank S. Bates
Design Of Abc Triblock Copolymers Near The Odt With The Random Phase Approximation, Eric W. Cochran, David C. Morse, Frank S. Bates
Eric W. Cochran
Leibler’s random phase approximation for block copolymers, modified so as to be applicable to linear multiblock copolymers, has been quantitatively compared to data from three linear ABC/ACB triblock copolymer melts: poly(cyclohexylethylene-b-ethylene-b-ethylethylene) (CEEE)/CEEE, poly(styreneb- isoprene-b-ethylene oxide) (SIO)/ISO (Macromolecules 2001, 34, 6994-7008;Macromolecules 2002, 35, 7007-7017), and poly(styrene-b-isoprene-b-dimethylsiloxane) (SID)/ISD (Macromolecules 2002, 35, 3189- 3197). The RPA calculation provides the mean-field static structure factor for a disordered block copolymer melt, which can be used to anticipate the scattering behavior and spinodal stability limit temperature (Ts); in the context of mean-field theory, the spinodal should lie near the order-disorder-transition temperature (TODT). We find that the …
Thermodynamic Behavior Of Poly(Cyclohexylethylene) In Polyolefin Diblock Copolymers, Eric W. Cochran, Frank S. Bates
Thermodynamic Behavior Of Poly(Cyclohexylethylene) In Polyolefin Diblock Copolymers, Eric W. Cochran, Frank S. Bates
Eric W. Cochran
We report the temperature dependence of the Flory-Huggins interaction parameter for three symmetric diblock copolymer systems containing poly(cyclohexylethylene) (PCHE): poly(cyclohexylethylene-b-ethylene) (CE), poly(cyclohexylethylene-b-ethylethylene) (CEE), and poly(cyclohexylethylene-b-ethylenepropylene) (CP). Order-disorder transition temperatures (TODT) were determined using dynamic mechanical spectroscopy and interpreted with mean-field theory, (χN)ODT = 10.5, leading to well-defined expressions for χ(T). These results have been analyzed in the context of solubility parameter (δ) theory resulting in a unique parameter δC that describes the interactions in CE, CP, and CEE, where δC < δEE < δP < δE with (δE - δC) ≈ 1.6 MPa1/2 at 500 K. In contrast to the predictions of group contribution theory, this indicates that δC is in surprisingly close proximity to the solubility parameter for poly(dimethylsiloxane).