F. Franco

Factors influencing the intercalation degree (‘reactivity’) of kaolin minerals with potassium acetate, formamide, dimethylsulphoxide and hydrazine

Abstract Factors influencing the degree of intercalation (‘reactivity’) of kaolinite group minerals have been investigated using six kaolin minerals, with variable crystallinity and particle size. Tests were performed to measure the degree of intercalation with potassium acetate, formamide, dimethylsulphoxide and hydrazine. These experiments indicate that intercalation degree depends on a number of factors, including particle size, degree of ordering, type of guest molecules, method of intercalation, and presence and types of impurities. Anew method for determination of the degree of intercalation is proposed, which is not dependent on the intensity of complex reflections. The results indicate that formamide is the most sensitive reagent to distinguish differently ordered kaolin minerals whereas hydrazine appears as the most appropriate reagent to differentiate kaolin minerals from other 7 Å phases.

THERMAL BEHAVIOR OF THE KAOLINITE-HYDRAZINE INTERCALATION COMPLEX

The intercalation complex of a low-defect (“well-crystallized”) kaolinite from Cornwall, England, with hydrazine was studied by high-temperature X-ray diffraction (HTXRD), differential thermal analysis (DTA), and thermogravimetry (TG). The X-ray pattern at room temperature indicated that intercalation of hydrazine into kaolinite causes an increase of the basal spacing from 7.14 to 10.4 A, as previously reported. Heating between 25-200°C produces a structural rearrangement of the complex, which initially causes a contraction of the basal spacing from 10.4 to 9.6 A. In a second stage, the basal spacing reduces to 8.5 A. Finally, in a third stage, a reduction in spacing occurs through a set of intermediate phases, interpreted as interstratifications of intercalated and non-intercalated 1:1 layers. Evidence for these changes was observed by DTA, where three endothermic reactions are observed at low temperature. This behavior suggests that intercalated molecules occupy several well-defined sites in the in-terlayer of the kaolinite complex. The intercalated molecules deintercalate in an ordered fashion, which explains the successive and discontinuous contraction of the basal spacing of the complex. Heating between 200-400°C caused a limited increase in stacking order of the kaolinite structure, whereas dehy-droxylation of kaolinite and the disappearance of its X-ray reflections occurred between 450-640°C.

Thermal behaviour of dickite-dimethylsulfoxide intercalation complex

The thermal behaviour of the intercalation complex of a dickite from Tarifa, Spain, with dimethylsulfoxide was studied by high-temperature X-ray diffraction, differential thermal analysis and thermogravimetry, and attenuated total reflectance infrared spectroscopy. The ATR-FTIR study indicated that the heating between room temperature and 75°C produced the elimination of adsorbed molecules. Above this temperature the elimination of intercalated molecules occurs through several stages. Loss of 6.5% of the intercalated DMSO first causes a slight contraction of the basal spacing at 90şC due to a rearrangement of the DMSO molecules in the interlayers positions. This contraction is followed by the formation of a single layer complex and the restoring of the dickite structure, at 300°C, when the loss of intercalated species have been completed.

BHIGH-TEMPERATURE X-RAY DIFFRACTION, DIFFERENTIAL THERMAL ANALYSIS AND THERMOGRAVIMETRY OF THE KAOLINITE-DIMETHYLSULFOXIDE INTERCALATION COMPLEX

The intercalation complex of a kaolinite from Cornwall, UK, with dimethylsulfoxide (DMSO) was studied by high-temperature X-ray diffraction (HTXRD), differential thermal analysis (DTA) and thermogravimetry (TG). The X-ray pattern obtained at room temperature indicated that intercalation of DMSO into kaolinite caused an increase of the basal spacing of kaolinite from 7.14 to 11.19 Å. Heating between 25 and 300°C caused the removal of the DMSO, which occurred over several stages. In a first stage (25–125°C), an expansion (from 11.19 to 11.28 Å) followed by a contraction (from 11.28 to 11.19 Å) is observed, at the same time as the intensity of the basal reflection decreased and was replaced by a broad band extending from ~11 to ~7 Å. In a second stage (125–200°C), the loss of DMSO did not lead to changes in the HTXRD patterns; and finally, in a third stage, the loss of DMSO caused an important increase in intensity and sharpening of the basal reflections of the kaolinite. These stages were also shown by the DTA-TG curves for the complex. The TG curve indicated that the loss of ~15% of the intercalated DMSO occurs below 150°C, and caused the disruption of the structure. The remaining molecules, forming stronger bonds with the kaolinite surfaces, were lost between 150 and 300°C.

Thermal decomposition of a dickite-hydrazine intercalation complex.

The intercalation complex of a low-defect dickite from Tarifa, Spain, with hydrazine was studied by high-temperature X-ray diffraction (HTXRD). differential thermal analysis (DTA), and ther-mogravimetry (TG). The X-ray diffraction (XRD) pattern obtained at room temperature indicated that the intercalation of hydrazine and H2O into dickite caused an increase of the basal spacing from 7.08 to 10.24 A, which is slightly lower than the 10.4-Å spacing commonly observed after intercalation into kaolinite. Heating between 25–50°C produced a structural rearrangement of the complex, which decreased the basal spacing from 10.24 to 9.4 A, and the resulting 9.4-Å complex was stable between 50–90°C. Heating between 90–300°C caused a gradual reduction in spacing, which occurred through a set of intermediate phases. These phases were interpreted to be interstratifications of intercalated and non-intercalated layers. These changes were also observed by DTA and TG. Two main endothermic reactions and two main stages of mass loss, respectively, were indicated in the DTA and the TG curves in the temperature range 25–200°C. This behavior suggests that intercalated molecules, hydrazine and H2O, occupied well-defined sites in the interlayer of the dickite. The intercalated molecules were lost in an ordered fashion as confirmed by the infrared analysis of the decomposition products; H2O was lost in the first stage and ammonia was identified in the second stage. Above 300°C, complete removal of the intercalated molecules restored the basal spacing of the dickite. However, the basal reflections were broadened, the relative intensities were changed, and changes in the dehydroxylation temperature indicated that the intercalation-desorption process induced some stacking disorder in the dickite structure.

Spectroscopic study of the dehydroxylation process of a sonicated antigorite

The effect of sonication on the dehydroxylation process of antigorite has been studied using TG-DTG and FTIR spectroscopy. Sonication process causes important particle-size reductions, while the structure of the antigorite is preserved as shown by XRD and FTIR. This particle size reduction strongly influences the thermal behaviour of antigorite. The dehydroxylation of untreated antigorite occurs mainly through a stage centred at 749°C. On the contrary, the dehydroxylation of the sonicated sample occurs through three differentiated stages. Spectroscopy study shows that the first stage of dehydroxylation exclusively corresponds to the release of outer hydroxyl groups, while the other two stages at high temperatures correspond to the simultaneous evolution of both inner and outer hydroxyls.

Evidence of contrasting low-grade metamorphic conditions from clay mineral assemblages in Triassic Alpujárride-Maláguide transitional units in the Betic Cordilleras, Spain

Abstract Triassic sequences from ‘intermediate units’ between the Alpujárride and the Maláguide complexes (Betic Cordilleras, Spain) of the westernmost part of the Cordilleras (Casares area) occur as four superimposed tectonic units; the uppermost unit shows lithological characteristics similar to those of the Maláguide complex, changing progressively at increasing depth, towards lithologies typical of the Alpujárride complex. The units studied, with a maximum thickness of ~400 m, record important variations in metamorphic pressures, according to the b parameter of white micas: from low-pressure metamorphism (in the upper unit) to high-pressure facies series (in the deepest one). The mean b values range from 8.988 Å in the uppermost unit (Crestellina) to 9.042 Å in the lowermost one (Jubrique). The lowest metamorphic grade is represented by mineral assemblages consisting of phengite + intermediate Na-K white mica ± Fe-chlorite ± sudoite ± pyrophyllite, which record temperatures of ~300°C and pressures of 1.5-3 kbar. At increasing tectonic depth, intermediate Na-K mica and pyrophyllite disappear and the metamorphic assemblages consist of phengite ± paragonite ± margarite + Mg-chlorite ± sudoite, which record minimum pressures of ~7 kbar and temperatures in the order of 400-450°C. These mineral assemblages provide evidence of the passage from collisional to extensional geotectonic settings. The units showing different metamorphic patterns were juxtaposed tectonically, after the development of metamorphic mineral assemblages.