Adam Gaweł

THE EFFECT OF STRUCTURAL ORDER ON NANOTUBES DERIVED FROM KAOLIN-GROUP MINERALS

Kaolin-group clay minerals can be modified to form nanotubular and mesoporous structures with interesting catalytic properties, but knowledge of the best methods for preparing these structures is still incomplete. The objective of this study was to investigate intercalation/deintercalation as a method for the delamination and rolling of kaolinite layers in relation to structural order. To prepare nanotubular material, kaolinites of different crystallinities and halloysite (all from Polish deposits) were chosen. The experimental procedure consisted of four stages: (1) preparation of a dimethyl sulfoxide precursor intercalate; (2) interlayer grafting with 1,3-butanediol; (3) hexylamine intercalation; and (4) deintercalation of amine-intercalated minerals using toluene as the solvent. Structural perturbations and changes in the morphology of the minerals were examined by X-ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry, and transmission electron microscopy (TEM). The number of rolled kaolinite layers depended heavily on the efficiency of the intercalation steps. An increase in the structural disorder and extensive delamination of the minerals subjected to chemical treatment were recorded. Kaolinite particles which exhibited tubular morphology or showed rolling effects were observed using TEM. The nanotubes formed were ∼30 nm in diameter, with their length depending on the particle sizes of the minerals.

SURFACE AREA AND POROSITY OF NANOTUBES OBTAINED FROM KAOLIN MINERALS OF DIFFERENT STRUCTURAL ORDER

Mesoporous materials with pore diameters in the range 2–50 nm forming tubular or fibrous structures are of great interest due to their unique properties. Because they are commonly used as sorbents and catalyst carriers, knowledge of their surface area and porosity is critical. A modified intercalation/deintercalation method was used to increase the efficiency of nanotube formation from kaolin-group minerals which differ in terms of their degree of structural order. Unlike previous experiments, in the procedure adopted in the present study, methanol was used instead of 1,3-butanediol for grafting reactions and octadecylamine intercalation was also performed. The samples were examined using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). The specific surface area and porosity of previously described and newly formed materials were investigated by N2 adsorption/desorption. Compared to results described earlier, the percent yield of nanotubes obtained in the present study was significantly greater only in the case of ‘Maria III’ kaolinite, which has high structural order. This increase was obtained mainly by the grafting reaction with methanol. Highly ordered stacking of kaolinite-methanol intercalates was noticed and, thus, the amine intercalation was more efficient. In particular, the use of long-chain octadecylamine significantly increased the nanotube yield. The grafting reaction with methanol procedure yielded fewer nanotubes, however, when applied to poorly ordered samples (‘Jaroszów’ kaolinite and ‘Dunino’ halloysite). In the case of the ‘Maria III’ kaolinite, the diameter of the rolled layers observed by TEM was ~30 nm and corresponded to average diameters of newly formed pores (DmN) determined using N2 adsorption/desorption, confirming that nanotubes contributed to an increase in surface area and total pore volume. In the case of ‘Jaroszów’ kaolinite and ‘Dunino’ halloysite mainly macropores (DmN > 100 nm) and mesopores (20 nm > DmN > 40 nm) were formed. The pores were attributed to interparticle and interaggregate spaces in the stacks of platy particles and to the small relative number of nanotubes.

Commercial bentonite from the Kopernica deposit (Tertiary, Slovakia): a petrographic and mineralogical approach

Abstract Commercial bentonite from the Kopernica deposit, Slovakia, is currently mined by the CERTECH Company, Poland, to produce materials intended for animal-care applications and other industrial purposes. The present study aimed to assess the mineralogical, petrographic and physicochemical characteristics of three bentonite varieties from Kopernica used by the company. The X-ray diffraction, optical microscopy, field emission scanning electron microscopy (FESEM), nuclear magnetic resonance, thermal analysis, infrared spectroscopy and chemical analyses showed that the main component of the rocks is montmorillonite with the average structural formula Ca0.31K0.08Na0.04(Al3.23Mg0.54Fe0.23)[(Si7.80Al0.20)O20](OH)4. In addition, opal-C/CT, biotite, potassium feldspar and plagioclase, quartz, clinoptilolite and kaolinite are present. Key information about the textural relationships between the mineral components identified was obtained from detailed thin-section petrography and FESEM studies. The rocks studied have fragmented, eutaxitic texture. They are composed of pumice fragments collapsed into lenticular masses (fiamme) which were strongly deformed and altered, though the shard structures were retained. The compressed glass shards were moulded around pyroclastic grains such as crystal fragments of quartz, biotite and zoned plagioclases, and clasts of volcanic rocks. Observations by FESEM showed that the axes of shards and the walls of the flattened vacuoles are outlined by the inward-growing microlites of silica (axiolitic texture), whilst the interiors of shards are altered to clay. Grain-size distribution, textural properties and microscope observations of grain-size fractions reveal that the Kopernica bentonite contains montmorillonite-opal aggregates difficult to disperse in water.

Characteristics and origin of agates from Płóczki Górne (Lower Silesia, Poland): A combined microscopic, micro-Raman, and cathodoluminescence study

Agates from Płóczki Górne hosted by Permian basaltic rocks are predominantly made of length-fast chalcedony, and subordinately megaquartz and quartzine. Moganite occurs in traces mainly in transparent, outer, darker regions of white-grey coloured agates. Silica matrix of agates comprises a wide variety of solid inclusions represented by celadonite, plagioclases, hematite, goethite, barite, calcite, heulandite-clinoptyloite, nontronite-saponite, and Mn-dioxides (ramsdellite). Mineral phases are locally accompanied by black aggregations of carbonaceous matter, which gives a Raman signature of disordered carbon. These organic components were probably deposited from a hydrothermal fluids at low-temperature conditions and originated from sedimentary rocks found in the surrounding area of Płóczki Górne. The abundance of various SiO2 phases, mineral inclusions as well as various micro-textures (colloform, comb, feathery, and jigsaw-puzzle) in agates resulted from physicochemical fluctuations of SiO2-bearing mineralizing solutions at various stages of these gems formation. Agates from Płóczki Górne formed during post-magmatic stage of basaltic host rocks evolution. Not only were the hydrothermal fluids enriched in silica, but also they contained other elements such as Na, Ca, Al, Mg, Mn, Fe, Ba, SO4, and CO2, which were mobilized from host rocks or surrounding area.

Bentonite from the Central Slovakia Volcanic Field – A Prospective Raw Material for Polish Industry

Abstract This paper summarizes information about recently worked bentonite deposits in Slovakia and presents the results of studies on bentonite from the Central Slovakia Volcanic Field (CSVF). The authors compared the mineralogy of commercial bentonites exploited in the Stara Kremnička (Jelšový potok), Kopernica, and Hliník nad Hronom deposits. X-ray diffraction (XRD), chemical analyses and microscopy showed that the main component is montmorillonite (37-88%), followed by opal C/CT (5-25%), clinoptilolite (up to 15%), feldspars (3-12%), quartz (up to 8%), biotite (2-5%), and kaolinite (up to 2%). The microscopic imaging provided information valuable for the technological assessment of bentonites, particularly the evaluation of mineralogy determined by XRD. The low variability of the mineral composition of commercial bentonites exploited in the western CSVF, together with the significant reserves and localization of deposits close to the Polish-Slovak state border prove that this raw material deserves more attention from Polish industry.