William R. Rodgers

Interaction of supercritical CO2 with alkyl-ammonium organoclays : Changes in morphology

This paper investigates the influence of supercritical carbon dioxide on the morphology and surface chemistry of three organic modified montmorillonite species. Alkyl based quaternary ammonium surfactants with differing numbers of chains attached, were chosen to vary the degree of CO(2)-philicity exhibited by the organoclay. In a high pressure batch vessel, the different organoclays were suspended in the supercritical solvent at temperatures of 50 and 200 degrees C and pressures of 7.6 and 9.6 MPa and then removed after de-pressurization at 0.2 or 4.8 MPa/s. The structures of these treated clays were characterized by X-ray diffraction (XRD), differential scanning microscopy (DSC), and thermogravimetric analysis (TGA), and their chemical properties were analyzed by various methods including atomic absorption spectroscopy, and water uptake measurement. Solute-solvent interactions plasticized the organic medium while suspended in the supercritical fluid, which resulted in greater chain mobility and further cation exchange. The results indicate that intercalated surfactants exhibiting a paraffin complex arrangement were most likely to experience significant basal expansion, provided the tilt angle was not already close to being perpendicular to the silicate surface. At the lower processing temperature condition, the chemistry of the clay surface was notably altered by the CO(2) associations with the Lewis acid/base sites, which significantly reduced the moisture adsorption capacity of the material. For those organoclays demonstrating basal expansion, it was noted that the resulting particle size was increased due to enhanced porosity.

Transmission electron microscopy based direct mathematical quantifiers for dispersion in nanocomposites

A rigorous mathematical foundation and a procedure for quantifying three-dimensional exfoliation and dispersion of clay particles in polymer-clay nanocomposites from their two-dimensional transmission electron microscopy micrographs have been developed. Two independent parameters, exfoliation number and interparticle distance, have been proposed. The exfoliation number gives the percentage of exfoliation achieved, whereas the interparticle distance is a measure of spatial separation between particles. The quantitative description of the nanocomposite microstructure would enable the establishment of synthesis/processing-structure-property linkages in nanocomposites and provide a benchmark for other indirect characterization techniques, such as x-ray diffraction, rheology, etc.

Spotting of Automotive Finishes from the Interactions Between Dry Deposition of Crustal Material and Wet Deposition of Sulfate

During the summer of 1988, General Motors Research Laboratories operated a mobile atmospheric research laboratory in Jacksonville, Florida to determine the cause of environmentally- related damage that occurs on automotive finishes In many parts of the U.S. The damage occurs as circular, elliptical, or irregular spots that appear as deposits or precipitates. The results of the present study show that a wetting event (rain or dew) is a prerequisite for damage to occur. Sulfuric acid contained in the rain or dew reacts on surfaces with drydeposited calcium which Is a common constituent of soli. As the droplets evaporate, a calcium sulfate precipitate forms on horizontal surfaces around the perimeter of the droplet. Subsequent washing of the surface may remove the precipitate, but on clearcoats, where the calcium sulfate was present, scars remain.

In situ x-ray diffraction studies of alkyl quaternary ammonium montmorillonite in a CO2 environment

An in situ study was conducted using an x-ray diffractometer and a specially designed high pressure cell to examine the effects of carbon dioxide at different pressures and temperatures on three different modified montmorillonite species. These organoclays possessed organic pillars of quaternary ammonium surfactant with either one, two, or three long (C(16)-C(18)) alkyl chains attached to expand the galleries of the clay mineral. The three clay species were tested between 50 degrees C and 200 degrees C with carbon dioxide pressures between 0.1 and 8.4 MPa. Under these conditions, the three organoclays exhibited marked differences in their basal spacing depending on the surfactant used. The physical state of the intercalated surfactant was found to be of critical importance, with no changes in basal spacing noted until the organic component began to melt, in spite of CO(2) being present. A pressure effect was also noted which delayed melting of the surfactants as the pressure of the system increased. In all cases, further cation exchange with residual sodium cation present in the galleries was observed in the presence of CO(2) and above the melting state of the surfactant. The study included examination of the effect of rapid depressurization on the clay structure, which produced only a small change in basal spacing.