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I W Hamley

Publications and source records attributed to I W Hamley.

10 recordsLinked to original sources

Small-angle x-ray scattering study of flow alignment of a thermotropic liquid crystal in the nematic and smectic phases.

The capillary flow alignment of the thermotropic liquid crystal 4-n-octyl-4'-cyanobiphenyl in the nematic and smectic phases is investigated using time-resolved synchrotron small-angle x-ray scattering. Samples were cooled from the isotropic phase to erase prior orientation. Upon cooling through the nematic phase under Poiseuille flow in a circular capillary, a transition from the alignment of mesogens along the flow direction to the alignment of layers along the flow direction (mesogens perpendicular to flow) appears to occur continuously at the cooling rate applied. The transition is centered on a temperature at which the Leslie viscosity coefficient alpha3 changes sign. The configuration with layers aligned along the flow direction is also observed in the smectic phase. The transition in the nematic phase on cooling has previously been ascribed to an aligning-nonaligning or tumbling transition. At high flow rates there is evidence for tumbling around an average alignment of layers along the flow direction. At lower flow rates this orientation is more clearly defined. The layer alignment is ascribed to surface-induced ordering propagating into the bulk of the capillary, an observation supported by the parallel alignment of layers observed for a static sample at low temperatures in the nematic phase.

Journal Article↗

Spontaneous condensation in DNA-polystyrene- b-poly(l-lysine) polyelectrolyte block copolymer mixtures.

We investigated the condensation of calf thymus DNA by amphiphilic polystyrene(m)-b-poly(l-lysine)(n) block copolymers ( PS(m)-b- PLys(n), m, n = degree of polymerization), using small-angle X-ray scattering, polarized optical microscopy and laser scanning confocal microscopy. Microscopy studies showed that the DNA condenses in the form of fibrillar precipitates, with an irregular structure, due to electrostatic interactions between PLys and DNA. This is not modified by the presence of hydrophobic PS block. Scattering experiments show that the structure of the polyplexes corresponds to a local order of DNA rods which becomes more compact upon increasing n. It can be concluded that for DNA/ PS(m)-b- PLys(n) polyplexes, the balance between the PLys block length and the excess charge in the system plays an essential role in the formation of a liquid crystalline phase.

Binding Sites↗

Ellipsometric study of adsorption on nanopatterned block copolymer substrates.

We report ellipsometrically obtained adsorption isotherms for a carefully chosen test liquid on block copolymer films of Kraton G1650, compared with adsorption isotherms on homogeneous films of the constituent polymers. Standard atomic force microscopy images imply the outer surface of Kraton G1650 is chemically patterned on the nanoscale, but this could instead be a reflection of structure buried beneath a 10 nm layer of the lower energy component. Our test liquid was chosen on the basis that it did not dissolve in either component and in addition that it was nonwetting on the lower energy polymer while forming thick adsorbed films on pure substrates of the higher energy component. Our ellipsometry data for Kraton G1650 rule out the presence of segregation by the lower energy constituent to the outer surface, implying a mixed surface consistent with Cassie's law. We discuss implications of our findings and related work for the outer surface structures of block copolymer films.

Journal Article↗

Dynamic light scattering study of the dynamics of a gelled polymeric micellar system.

The dynamics of the E(92)B(18)/water system are studied by dynamic light scattering (DLS) in the liquid, soft gel, and hard gel phases. Both the liquid and the soft gel phases are micellar phases, although the structural order is higher in the soft gel phase than in the liquid phase. The hard gel phase corresponds to a face-centered cubic arrangement of micelles. DLS results show that the dilute liquid phase is characterized by a single characteristic time tau(1) associated with the diffusion of the micelles. In addition, a second characteristic time tau(2) associated with the presence of micellar clusters in the system is identified in the concentrated liquid and in the soft gel phases. According to these results, DLS suggests that the structure of the soft gel phase comprises micellar clusters coexisting with micellar fluid, in good agreement with hypotheses from our previous work. The dynamics of the system slows down as the hard gel phase is approached and a plateau is observed in the DLS correlation function. The structure of the hard gel is "softened" upon increasing temperature and/or decreasing concentration.

Journal Article↗

Nanotechnology with soft materials.

Nature exploits self-organization of soft materials in many ways, to produce cell membranes, biopolymer fibers and viruses, to name just three. Mankind is now able to design materials at the nanoscale, whether through atom-by-atom or molecule-by-molecule methods (top-down) or through self-organization (bottom-up). The latter method encompasses soft nanotechnology. Self-organization of soft materials can be exploited to create a panoply of nanostructures for diverse applications. The richness of structures results from the weak ordering because of noncovalent interactions. Thus, thermal energy is important as it enables transitions between phases with differing degrees of order. The power of self-organization may be harnessed most usefully in a number of nanotechnology applications, which include the preparation of nanoparticles, the templating of nanostructures, nanomotor design, the exploitation of biomineralization, and the development of functionalized delivery vectors.

Journal Article↗

Surface energy of ethylene-co-1-butene copolymers determined by contact angle methods.

Wilhelmy plate measurements of contact angles with a series of test liquids are used to calculate the surface energies of two poly(ethylene-co-1-butene) random copolymers. Results from five methods of calculation are reported: one-liquid (Good-Girifalco and Neumann), two-liquid (harmonic mean and geometric mean), and three-liquid (Lifshitz-van der Waals acid-base) methods. We find that all five methods are sensitive to the choice of test liquids used for contact angle measurements, as previously reported, but consistent results are obtained if recommended combinations of liquids are used. The mean results of the three-liquid acid-base method are judged to be the most reliable and informative, leading to surface energies of 30.8 mJ/m2 for poly(ethylene-co-1-butene) copolymer composed of 92 mol% ethylene and 30.2 mJ/m2 for copolymer composed of 88 mol% ethylene.

Journal Article↗

Liquid-solid transition in a model hard sphere system of block copolymer micelles.

The transition between micellar liquid and face-centered-cubic crystalline solid in a solution of an amphiphilic diblock copolymer is investigated by small-angle x-ray scattering and rheology. The system is well described by the hard sphere model and there is no evidence for percolation driven by attractive interactions, in contrast to previous reports. Instead, a coexistence region separates liquid and crystal phases.

Journal Article↗

Cell dynamics simulations of shear-induced alignment and defect annihilation in stripe patterns formed by block copolymers.

The effect of large amplitude oscillatory shear on two-dimensional stripe patterns formed by block copolymers was investigated using cell dynamics simulations. A global orientational order parameter S and a correlation function for stripe normals G(r-r(')) were used to characterize the degree of stripe orientation under shear. The kinetics of stripe alignment, quantified by S, at various shear and quench conditions were studied as a function of strain amplitude, shear frequency, and temperature. The mechanisms of shear alignment and defect annihilation were investigated. A critical shear condition for complete alignment of stripes along the shear direction was also identified.

Diffusion↗

Solution self-assembly of hybrid block copolymers containing poly(ethylene glycol) and amphiphilic beta-strand peptide sequences.

The self-assembly in aqueous solution of hybrid block copolymers consisting of amphiphilic beta-strand peptide sequences flanked by one or two PEG chains was investigated by means of circular dichroism spectroscopy, small-angle X-ray scattering, and transmission electron microscopy. In comparison with the native peptide sequence, it was found that the peptide secondary structure was stabilized against pH variation in the di- and tri-block copolymers with PEG. Small-angle X-ray scattering indicated the presence of fibrillar structures, the dimensions of which are comparable to the estimated width of a beta-strand (with terminal PEG chains in the case of the copolymers). Transmission electron microscopy on selectively stained and dried specimens shows directly the presence of fibrils. It is proposed that these fibrils result from the hierarchical self-assembly of peptide beta-strands into helical tapes, which then stack into fibrils.

Amino Acid Sequence↗