0000000000048596
AUTHOR
James B. Mcclain
Critical micellization density: A small-angle-scattering structural study of the monomer-aggregate transition of block copolymers in supercriticalCO2
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…
Industrial applications of the aggregation of block copolymers in supercritical CO 2 : a SANS study
Industrial applications of supercritical carbon dioxide (scCO2) rely upon the rather selective and easily adjustable solvent ability of CO2. CO2 near the critical point is a poor solvent for high molecular weight (HMW) hydrocarbon polymers, while it is a very good solvent for amorphous fluorinated polymers. By increasing the pressure, CO2 becomes a good solvent even for HMW hydrogenated chains. Specially engineered amphiphilic di-block copolymers, with CO2-philic and CO2-phobic portions, are expected to undergo trough a monomer–aggregate transition when the solvent density of the scCO2 changes. Here small-angle neutron scattering (SANS) results are reported for a block copolymer dissolved i…
Design of nonionic surfactants for supercritical carbon dioxide
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…
QENS from polymer aggregates in supercritical CO2
Abstract We report QENS measurements from PS-b-PFOA aggregates in supercritical CO2. Line shapes are dominated by localized diffusive modes and segmental dynamics of the anchored, finite-length PFOA chains. For Q⩽0.6 A−1, we obtain effective diffusion coefficients of ≅0.8 10−6 cm2/s. At higher Q, a single component is not sufficient as shown by excess intensity on the flanks. For Q⩾1.5 A−1, the wings reflect contributions due to a distribution of faster, more localized chain modes.
Critical Micelle Density for the Self-Assembly of Block Copolymer Surfactants in Supercritical Carbon Dioxide
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…
QENS from polymeric micelles in supercritical CO[sub 2]
We report QENS measurements from PS-b-PFOA aggregates in supercritical CO2. These consist of dense cores of CO2-insoluble polystyrene surrounded by a ‘corona’ of PFOA surfactant molecules whose CO2-philic groups interface with supercritical CO2. Lineshapes are dominated by localized diffusive modes and segmental dynamics of the anchored, finite-length PFOA chains. For Q∼0.6 A−1, we obtain effective diffusion coefficients of ≈0.8×10−6 cm2/sec. At higher Q, a single component is not sufficient as shown by excess intensity on the flanks. For Q>1.5 A−1, the wings reflect contributions due to a distribution of faster, more localized chain modes.
Neutron scattering characterization of homopolymers and graft-copolymer micelles in supercritical carbon dioxide
Abstract Superficial fluids (SCF) are becoming an attractive alternative to the liquid solvents traditionally used as polymerization media [1]. As the synthesis proceeds, a wide range of colloidal aggregates form, but there has hitherto been no way to measure such structures directly. We have applied small-angle neutron scattering (SANS) to characterize such systems, and although SCF polymerizations are carried out at high pressures, the penetrating power of the neutron beam means that typical cell windows are virtually transparent. Systems studied include polymers soluble in CO 2 such as poly(1,1-dihydroperfluorooctyl acrylate) (PFOA), poly(hexafluoropropylene oxide) (PHFPO) and poly(dimet…