Neutron scattering characterization of homopolymers and graft-copolymer micelles in supercritical carbon dioxide
- Palermo Univ. (Italy). Ist. di Chimica Fisica
- North Carolina Univ., Chapel Hill, NC (United States); and others
Supercritical fluids are becoming an attractive alternative to the liquid solvents traditionally used as polymerization media. 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 molecules soluble in CO{sub 2} (e.g. polyfluoro-octyl acrylate or PFOA) and this polymer has previously been shown to exhibit a positive second virial coefficient (A{sub 2}). Other CO{sub 2}-soluble polymers include hexafluoro-polypropylene oxide (HFPPO), which appears to have a second virial coefficient which is close to zero (10{sup 4}A{sub 2} {approx_equal} 0 +{+-} 0.2 cm{sup 3} g{sup -2} mol). Polydimethylsiloxane (PDMS), is soluble on the molecular level only in the limit of dilute solution and seems to form aggregates as the concentration increases (c > 0.01 g cm{sup -3}). Other polymers (e.g. polystyrene) are insoluble in CO{sub 2}, though polymerizations may be accomplished via the use of PS-PFOA blockcopolymer stabilizers, which are also amenable to SANS characterization, and have been shown to form micelles in CO{sub 2}. Other amphiphilic surfactant molecules that form micelles include PFOA-polyethylene oxide (PFOA-PEO) graft copolymers, which swell as the CO{sub 2} medium is saturated with water. These systems have been characterized by SANS, by taking advantage of the different contrast options afforded by substituting D{sub 2}O for H{sub 2}O. This paper illustrates the utility of SANS to measure molecular dimensions, thermodynamic variables, molecular weights, micelle structures etc. in supercritical CO{sub 2}.
- Research Organization:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- DOE Contract Number:
- AC05-84OR21400
- OSTI ID:
- 203969
- Report Number(s):
- CONF-9509328-1; ON: DE96005727
- Resource Relation:
- Conference: Horizons in small-angle scattering from mesosopic systems, Stromboli (Italy), 27-30 Sep 1995; Other Information: PBD: [1995]
- Country of Publication:
- United States
- Language:
- English
Similar Records
Critical micellization density: A small-angle-scattering structural study of the monomer-aggregate transition of block copolymers in supercritical CO{sub 2}
Structural characterization of a polymer substituted fullerene (flagellene) by small angle neutron scattering