0000000000048597
AUTHOR
George D. Wignall
showing 9 related works from this author
Critical micellization density: A small-angle-scattering structural study of the monomer-aggregate transition of block copolymers in supercriticalCO2
2000
In this paper we report a small-angle neutron-scattering investigation of micelle formation by the fluorocarbon-hydrocarbon block copolymer, polyvinyl acetate-b-poly (1,1,2,2-tetrahydroperfluoro-octyl acrylate) in supercritical CO{sub 2} (scCO{sub 2}) at 313 K. At high pressure the copolymer is in a monomeric state with a random coil structure, while at low pressure the polymer forms spherical aggregates stable in a wide range of thermodynamic conditions. By profiling pressure, a sharp monomer-micelle transition is obtained due to the tuning of the solvating ability of scCO{sub 2}. We confirm the previous finding that this aggregate-monomer transition is driven by the gradual penetration of…
Recent developments in ultra–small angle neutron scattering techniques
1998
Abstract There is growing interest in the (nano−) scale structural analysis of condensed matter to study synthetic and biological polymers, colloids, porous materials, etc. Over the past two decades, small–angle neutron scattering (SANS), based on the availability of high fluxes of cold neutrons (wavelengths 4−20 A), has proven to be one of the most important tools for such investigations. This success is due to a fortuitous combination of several factors of cold neutrons: high bulk penetrating power, the ability to manipulate local scattering amplitudes via isotopic labeling or an appropriate choice of solvent (contrast variation), minimal radiation damage, and small absorption for most el…
X-ray scattering studies of the structure of aqueous hydroxy-propylcellulose solutions
1991
X-ray diffraction studies have been undertaken on aqueous solutions of hydroxy propylcellulose (HPC) over a wide range of the scattering vector Q. The experiments revealed only modest differences in local structure on a distance scale ca. 5–300 A despite the fact that they covered concentrations generally interpreted as ranging from the isotropic (35.1 wt %) to the anisotropic liquid crystalline (LC) phase (53.5 wt %). Several models were used to interpret the small-angle scattering data, and each gave similar structural parameters and extrapolated intensities (Q → 0) for both solutions. Peaks were observed with d-spacings ca. 12–17 A in both materials. Wide-angle x-ray scattering (WAXS) sh…
Design of nonionic surfactants for supercritical carbon dioxide
1996
Interfacially active block copolymer amphiphiles have been synthesized and their self-assembly into micelles in supercritical carbon dioxide (CO 2 ) has been demonstrated with small-angle neutron scattering (SANS). These materials establish the design criteria for molecularly engineered surfactants that can stabilize and disperse otherwise insoluble matter into a CO 2 continuous phase. Polystyrene- b -poly(1,1-dihydroperfluorooctyl acrylate) copolymers self-assembled into polydisperse core-shell-type micelles as a result of the disparate solubility characteristics of the different block segments in CO 2 . These nonionic surfactants for CO 2 were shown by SANS to be capable of emulsifying u…
Structure of isotactic polypropylene–hydrogenated oligo(cyclopentadiene) (iPP–HOCP) blends Part II. HOCP-rich blends
2000
Abstract Blends of isotactic polypropylene (iPP) and hydrogenated oligo(cyclopentadiene) (HOCP) were investigated to gain structural information by means of both SAXS and SANS techniques. The composition range (from 30 to 60% w/w HOCP content) and the temperature range (between 25 and 160°C) were chosen in order to cover the miscibility gap in the phase diagram of the material system. In a previous report, blends lying outside the miscibility gap have been investigated and the corresponding SAXS patterns were interpreted in terms of a pseudo-two phase model. For the SAXS patterns, blends lying inside the miscibility gap are rather hard to be interpreted in terms of such a model. On the othe…
Structure of diblock copolymers in supercritical carbon dioxide and critical micellization pressure
1999
This paper reports a small angle neutron scattering investigation of micelle formation by fluorocarbon-hydrocarbon block copolymers in supercritical ${\mathrm{CO}}_{2}{(\mathrm{s}\mathrm{c}\ensuremath{-}\mathrm{C}\mathrm{O}}_{2})$ at 65 \ifmmode^\circ\else\textdegree\fi{}C. A sharp unimer-micelle transition is obtained due to the tuning of the solvating ability of ${\mathrm{s}\mathrm{c}\ensuremath{-}\mathrm{C}\mathrm{O}}_{2}$ by profiling pressure, so that the block copolymer, in a semidilute solution, finds ${\mathrm{s}\mathrm{c}\ensuremath{-}\mathrm{C}\mathrm{O}}_{2}$ a good solvent at high pressure and a poor solvent at low pressure. At high pressure the copolymer is in a monomeric state…
The morphology of block copolymer micelles in supercritical carbon dioxide by small-angle neutron and x-ray scattering
1997
Above its critical point, carbon dioxide forms a super-critical fluid, which promises to be an environmentally responsible replacement for the organic solvents traditionally used in polymerizations. Many lipophilic polymers such as polystyrene (PS) are insoluble in CO2, though polymerizations may be accomplished via the use of PS-fluoropolymer stabilizers, which act as emulsifying agents. Small-angle neutron and X-ray scattering have been used to show that these molecules form micelles with a CO2-phobic PS core and a CO2-philic fluoropolymer corona. When the PS block was fixed in length and the fluorinated corona block was varied, the number of block copolymer molecules per micelle (six to …
Small angle neutron scattering studies of critical phenomena in a three-component microemulsion
2007
Critical density fluctuations of a ``water-in-oil`` microemulsion consisting of water, benzene, and BHDC (benzyldimethyl-n-hexadecyl ammonium chloride) were observed near the phase boundary by SANS. Observed profiles were well described by product of a form factor of spherical droplets and a structure factor, consisting of a term describing the inter-droplet correlations and also an Ornstein- Zernike component describing the droplet density fluctuations. Allowance was also made fro droplet polydispersity,though the width of the distribution turned out to be very small (1-2%). Observed temperature dependence of osmotic compressibility was fitted using the crossover function proposed by Belya…
Critical Micelle Density for the Self-Assembly of Block Copolymer Surfactants in Supercritical Carbon Dioxide
1999
The parameters which influence the self-assembly of molecules in solution include the temperature and solvent quality, and this study illustrates the use of these variables to regulate the degree of association of block copolymer amphiphiles in highly compressible supercritical carbon dioxide. Small-angle neutron scattering (SANS) has been used to examine the association behavior of a block copolymer containing a CO2-phobic moiety, poly(vinyl acetate), and a CO2-philic block, poly(1,1-dihydroperfluoro-octylacrylate). By adjustment of the density of the medium through pressure and temperature profiling, the self-assembly can be reversibly controlled from unimers to core−shell spherical micel…