Two kinds of xerogels were prepared by the slow and rapid hydrolyses of tetraethoxysilane and aluminum nitrate nonahydrate dissolved in ethanol. Xerogels prepared by slow hydrolysis crystallized mullite directly from the amorphous state on firing whereas those formed by rapid hydrolysis crystallized a spinel phase before mullite formation. The composition of the spinel phase was characterized by various methods to be near SiO2·6Al2O3. The process of mullite formation is discussed in relation to the structures of the starting materials.

Characterization of the Spinel Phase from SiO2-Al2O3 Xerogels and the Formation Process of Mullite

Sediments exposed to high temperatures: reconstructing pyrotechnological processes in Late Bronze and Iron Age Strata at Tel Dor (Israel)

The 27Al and 29Si magic-angle spinning nuclear magnetic resonance (MAS-NMR) study of the kaolinite-mullite transformation has shown the presence of Al in tetra- and pentacoordination in dehydroxylated kaolinite. The 29Si NMR signal analysis of samples heated above 400°C demonstrates that the tetrahedral sheet of kaolinite begins to break down near 600°C and continues to do so to 900°C. From the 27Al NMR signal evolution, it can be deduced that the exothermic peak at 980°C in DTA curves is associated with the modification of the coordination of Al, which changes from the tetra- or pentacoordination to the more stable octahedral coordination. Heating the sample at 880°C for 36 h produces the same transformation in the coordination of Al ions and the elimination of the exothermic peak at 980°C in the DTA diagram. After this transformation, all spectra show two tetrahedral lines characteristic of mullite, indicating that nuclei of mullite with low crystallinity are generated during the exothermic process which are not detected by XRD. At higher temperatures tetrahedral NMR peaks increase in intensity, yielding, at 1200°C, the 3:2 mullite NMR spectrum.

Aluminum-27 and Silicon-29 Magic-Angle Spinning Nuclear Magnetic Resonance Study of the Kaolinite-Mullite Transformation

Thermal transformations of kaolinite of different degree of crystallinity have been monitored by 27Al and 29Si high-resolution NMR with magic-angle spinning (MAS NMR), X-ray diffraction, Fourier transform infrared, atomic absorption spectrophotometry and thermogravimetric analysis. NMR shows differences in the dehydroxylation process of kaolinites with different degree of crystallinity and reveals the presence of short-range order in metakaolinite. 29Si NMR spectra acquired with a 30 s recycle delay of poorly and highly crystalline samples heated at 480 and 500° C, respectively, contain three distinct signals; we discuss their assignment in the light of experiments involving leaching of the samples with aqueous KOH. Ca. 40% of Si sites retain their original Q
3 symmetry just above the onset of dehydroxylation and the Q
4 environment is present showing that a small amount of amorphous silica has already segregated. The spectrum of samples treated at 1000° C contains a signal at -110ppm (from Q
4 silicons) and a faint resonance, from mullite, at ca. -87 ppm. 29Si NMR also shows that cristobalite germs are already present at 950–1000° C. The 27Al MAS NMR spectra of metakaolinite reveal the presence of 4-, 5-and 6-coordinated Al. Changes in the three Al populations as a function of temperature have been monitored quantitatively. Below 800° C, 4-and 5-coordinated Al appears at the expense of 6-coordinated Al, but above 800° C the amount of 6-coordinated Al increases again. We suggest a dehydroxylation scheme which accounts for the presence of 4-and 5 coordinated Al. Above 900–950° C the latter signal is no longer present in the 27Al NMR spectra and new 4-and 6-coordinated Al species (mullite and γ-alumina) appear. We propose new ideas for the structure of metakaolinite.

29 Si and 27 Al magic-angle-spinning NMR studies of the thermal transformation of kaolinite

With the use of differential thermal analysis, X-ray diffraction, and transmission electron microscopic techniques, we showed that γ-Al2O3 type spinel phase is solely responsible for the 980°C exotherm in the kaolinite-to-mullite reaction series. Transmission electron microscopic characterization indicated that the spinel formation is preceded by a phase separation in the amorphous dehydroxylated kaolinite matrix. Chemical analysis of the spinel phase by energy dispersive X-ray spectroscopy revealed a nearly pure Al3O2 composition.

Spinel Phase Formation During the 980°C Exothermic Reaction in the Kaolinite‐to‐Mullite Reaction Series

The phases in the kaolinite-mullite reaction sequence were reexamined by ir absorption spectrophotometry. Particular attention was paid to the controversial intermediate Al-containing phases. Amorphous materials were leached from fired kaolinite samples with NaOH to help identify crystalline phases. Metakaolinite partially decomposes, releasing amorphous γ-Al2O3 and SiO2, before the “950°C” exothermic reaction in which metakaolinite is completely decomposed. The resulting spinel-type phase, which is associated with amorphous SiO2 and some poorly crystalline “primary” mullite, is γ-Al203 (crystalline) rather than an Al-Si spinel. There is some evidence, however, that a fraction of the γ-Al2O3, may be an Al-Si spinel. At ≥1100°C secondary mullite therefore forms primarily from the γ-Al2O3/amorphous SiO2 reaction and the recrystallization of primary mullite, whereas excess amorphous SiO2 eventually crystallizes as cristobalite.

H. J. Percival

Papers

Interpretation of the Kaolinite-Mullite Reaction Sequence from Infrared Absorption Spectra

Interpretation of the kaolinite-mullite reaction sequence from infrared absorption spectra