la035361h_si_001.ppt (4.5 MB)
Thermally Induced Phase Transitions and Morphological Changes in Organoclays
presentation
posted on 2004-04-27, 00:00 authored by M. Gelfer, C. Burger, A. Fadeev, I. Sics, B. Chu, B. S. Hsiao, A. Heintz, K. Kojo, S-L. Hsu, M. Si, M. RafailovichThermal transitions and morphological changes in Cloisite organoclays were investigated by differential
scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR)
spectroscopy, and in situ simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction
(WAXD) over the temperature range of 30−260 °C. On the basis of DSC and FTIR results, the surfactant
component in organoclays was found to undergo a melting-like order−disorder transition between 35 and
50 °C. The transition temperatures of the DSC peaks (Ttr) in the organoclays varied slightly with the
surfactant content; however, they were significantly lower than the melting temperature of the free surfactant
(dimethyldihydrotallowammonium chloride; Tm = 70 °C). FTIR results indicated that within the vicinity
of Ttr, the gauche content increased significantly in the conformation of surfactant molecules, while WAXD
results did not show any change in three-dimensional ordering. Multiple scattering peaks were observed
in SAXS profiles. In the SAXS data acquired below Ttr, the second scattering peak was found to occur at
an angle lower than twice that of the first peak position (i.e., nonequidistant scattering maxima). In the
data acquired above Ttr, the second peak was found to shift toward the equidistant position (the most
drastic shift was seen in the system with the highest surfactant content). Using a novel SAXS modeling
technique, we suggest that the appearance of nonequidistant SAXS maxima could result from a bimodal
layer thickness distribution of the organic layers in organoclays. The occurrence of the equidistant scattering
profile above Ttr could be explained by the conversion of the bimodal distribution to the unimodal distribution,
indicating a redistribution of the surfactant that is nonbounded to the clay surface. At temperatures above
190 °C, the scattering maxima gradually broadened and became nonequidistant again but having the
second peak shifted toward a scattering angle higher than twice the first peak position. The changes in
SAXS patterns above 190 °C could be attributed to the collapse of organic layers due to desorption and/or
degradation of surfactant component, which was supported by the TGA data.