Crystallization and Quantification of Crystalline and Non-Crystalline Phases in Kaolin-Based Cordierites.

Kaolin is most often used as traditional raw material in ceramic industry. The purpose of the study was to obtain understanding of the structural and chemical variability of cordierite ceramics influenced by chemical and mineralogical properties of six raw kaolins taken from different localities when they are applied in ceramics mixtures with vermiculite and sintered up to 1300 °C. The X-ray diffraction and simultaneous thermogravimetric and differential thermal analysis were used to identify and characterize crystalline mineral phases and the course of reactions during the heating. The percentages of the crystalline and non-crystalline phases were newly determined by recalculation of the bulk chemical analyses of kaolins and cordierite ceramics using Chemical Quantitative Mineral Analysis (CQMA) method. Varying amounts of minerals in kaolins: kaolinite from 73.3 to 85.0, muscovite from 4.2 to 9.9, and quartz from 6.0 to 19.5 (mass %) affected amount of cordierite/indialite from 75.2 to 85.1, enstatite from 5.8 to 8.9 (when are calculated as their maximal possible percentages), and non-crystalline phases from 8.8 to 15.1 (mass %) in cordierite ceramics. Regression analysis predicted high relationship between quantity of: (a) kaolinite in kaolins and crystalline cordierite and (b) quartz in kaolins and non-crystalline phases in the ceramics. The migration of potassium from muscovite into the cordierite structure, melting point and crystallization of cordierite/indialite phases and pore size variability in relation to impurity of kaolins are documented and discussed.

Effect of CaO on retention of S, Cl, Br, As, Mn, V, Cr, Ni, Cu, Zn, W and Pb in bottom ashes from fluidized-bed coal combustion power station.

This work was conducted to evaluate whether Ca-bearing additives used during coal combustion can also help with the retention of some other elements. This work was focused on the evaluation of bottom ashes collected during four full-scale combustion tests at an operating thermal fluidized-bed power station. Bottom ashes were preferred to fly ashes for the study to avoid interference from condensation processes usually occurring in the post-combustion zone. This work focused on the behaviors of S, Cl, Br, As, Mn, V, Cr, Ni, Cu, Zn, W, and Pb. Strong positive correlations with CaO content in bottom ashes were observed (for all four combustion tests) for S, As, Cl and Br (R=0.917-0.999). Strong inverse proportionality was calculated between the contents of Pb, Zn, Ni, Cr and Mn and CaO, so these elements showed association to materials other than Ca-bearing compounds (e.g., to aluminosilicates, organic matter, etc.). Somewhat unclear behaviors were observed for W, Cu, and V. Their correlation coefficients were evaluated as statistically "not significant", i.e., these elements were not thought to be significantly associated with CaO. It was also discovered that major enrichment of CaO in the finest bottom ash fractions could be advantageously used for simple separation of elements strongly associated with these fractions, mainly S and As, but also Cl or Br. Removal of 5% of the finest ash particles brings about a decrease in As concentration down to 77%-80% of its original bulk ash content, which can be conveniently used e.g., when high As content complicates further ash utilization.

Effect of unburned carbon content in fly ash on the retention of 12 elements out of coal-combustion flue gas.

The aim of this study was to evaluate whether unburned carbon particles present in fly ash can help in the retention of S, Cl, Br, As, Se, Cu, Ni, Zn, Ga, Ge, Rb, and Pb out of flue gas during the coal combustion at fluidised-bed power station where the coal was combusted along with limestone. The competitive influence of 10%-25% CaO in fly ashes on the distribution of studied elements was studied as well to be clear which factor governs behaviour of studied elements. Except of S (with significant association with CaO) and Rb and Pb (with major affinity to Al2O3) the statistically significant and positive correlation coefficients were calculated for the relations between unburned carbon content and Br (0.959), Cl (0.957), Cu (0.916), Se (0.898), Ni (0.866), As (0.861), Zn (0.742), Ge (0.717), and Ga (0.588) content. The results suggest that the unburned carbon is promising material in terms of flue gas cleaning even if contained in highly calcareous fly ashes.

Molecular modeling of surface modification of Wyoming and Cheto montmorillonite by methylene blue.

The surface area of various types of montmorillonites (MMT) with different values of layer charge plays a very important role in surface arrangement of methylene blue cations (MB). Photoluminescence measurements can be strongly or partially influenced by this surface arrangement of cations. For these reasons and on the basis of our previous results, molecular simulations were performed for various types of montmorillonites covered with methylene blue cations. Adsorption of methylene blue cations on Na-Wyoming MMT surface is different from Ca-Cheto MMT. In the case of Wyoming with a lower layer charge, MB cations lie parallel to the silicate layer for all investigated samples. On the other hand, Cheto surface is covered with a higher amount of MB cations. The results obtained from molecular modeling indicate that MB lies parallel to low loading case and become tilted with respect to layer for a higher loading. Moreover, a higher amount of MB cations covering the silicate layer are much less energy-stable. A higher loading of MB cations leads to aggregates but at low loading MB cations degrade to monomers.

Effect of surface and interlayer structure on the fluorescence of rhodamine B-montmorillonite: modeling and experiment.

The surface and interlayer structure of rhodamine B (RhB)-montmorillonite for various guest concentrations has been studied using a combination of X-ray powder diffraction and molecular modeling (molecular mechanics and molecular dynamics) in the Cerius(2) modeling environment. The joint effect of surface and interlayer structure on the fluorescence spectrum has been observed and discussed in relation to the position and orientation of RhB(+) cations with respect to the silicate layer. Structural analysis showed that the surface and interlayer structures are different as to the arrangement of RhB(+) cations, and both of them strongly depend on the guest concentration in the intercalation solution and on the method of preparation. The repeated intercalation of montmorillonite by rhodamine B used in the present work allowed obtaining RhB-montmorillonite in the maximum degree of ion exchange for every sample.

Humic acids from oxidized coals I. Elemental composition, titration curves, heavy metals in HA samples, nuclear magnetic resonance spectra of HAs and infrared spectroscopy.

The formation of humic acids (HAs) from bituminous coal was verified by laboratory oxidation. In a relatively short time the oxidation by air at temperature above 150 degrees C led to the formation of HAs. These HAs were compared with those isolated from oxidized bituminous coal from the vicinity of red bed bodies, from weathered bituminous coal, oxihumolite and lignite. For this the organic and inorganic elemental composition of HAs, apparent dissociation constants, metal-binding capacities, nuclear magnetic resonance and infrared spectra were determined and evaluated. With increasing temperature of laboratory oxidation of bituminous coal the percentage of aromaticity of HAs increases. HAs prepared from coal oxidized at 150 degrees C are characterized by an aromaticity index 78% while for HAs prepared at 250 and 300 degrees C by 95% aromaticity. The same index for HAs isolated from naturally oxidized bituminous coals is of about 87% whereas it is of about 50% for oxihumolite and lignite. The apparent dissociation constants (Kapp) are much higher in HAs isolated from oxihumolite and lignite (pKapp from 3.35 to 3.80) than those from oxidized bituminous coal samples (pKapp from 4.47 to 4.85). There is a good negative correlation between Pb-binding capacity and pKapp of all samples suggesting that metallic ions are bonded to acidic groups of HAs. Also contents of inorganic elements like Fe, Al, Si are much higher in HAs isolated from lignite and oxihumolite than those in HAs from oxidized bituminous coal. Thus, it seems that the temperatures below 150 degrees C and the long oxidation time are necessary conditions for the formation of HAs in oxidative altered bituminous coal deposited deeply under the earth surface.

Structure analysis of montmorillonite intercalated with rhodamine B: modeling and experiment.

The intercalation process and the structure of montmorillonite intercalated with [rhodamine B]+ cations have been investigated using molecular modeling (molecular mechanics and molecular dynamics simulations), X-ray powder diffraction and IR spectroscopy. The structure of the intercalate depends strongly on the concentration of rhodamine B in the intercalation solution. The presence of two phases in the intercalated structure was revealed by modeling and X-ray powder diffraction: (i) phase with basal spacing 18 A and with bilayer arrangement of guests and (ii) phase with average basal spacing 23 A and with monolayer arrangement of guests. In both phases the monomeric and dimeric arrangement can coexist in the interlayer space. Three types of dimers in the interlayer structure have been found by modeling: (i) H-dimer (head-to-head arrangement) present in the 18 A phase, (ii) sandwich type of the head-to-tail arrangement (present in the 23 A phase) and (iii) J-dimer (head-to-tail arrangement) present in the 23 A phase. Figure Montmorillonite intercalated with rhodamine B cations. On the left: phase 18 A, bilayer dimeric arrangement of guests (H-dimers). On the right: phase 23 A, monolayer arrangement of guests prepared using intercalation solution with a low concentration of rhodamine B