Chemical functionalities of high and low sulfur Australian coals : a case study using micro attenuated total reflectance–fourier transform infrared (ATR–FTIR) spectrometry

The macerals in bituminous coals with varying organic sulfur content from the Early Permian Greta Coal Measures at three locations (Southland Colliery, Drayton Colliery and the Cranky Corner Basin), in and around the Sydney Basin (Australia), have been studied using light-element electron microprobe (EMP) analysis and micro-ATR–FTIR. Electron microprobe analysis of individual macerals reveals that the vitrinite in both the Cranky Corner Basin and Drayton Colliery (Puxtrees seam) samples have similar carbon contents (ca. 78% C in telocollinite), suggesting that they are of equivalent rank. However, the Cranky Corner coals have anomalously low vitrinite reflectance (down to 0.45%) vs. the Drayton materials (ca. 0.7%). They also have very high organic S content (3–6.5%) and lower O content (ca. 10%) than the equivalent macerals in the Drayton sample (0.7% S and 15.6% O). A study was carried out to investigate the impacts of the high organic S on the functional groups of the macerals in these two otherwise iso-rank, stratigraphically-equivalent seams. An iso-rank low-S coal from the overlying Wittingham Coal Measures near Muswellbrook and coals of slightly higher rank from the Greta Coal Measures at Southland Colliery near Cessnock were also evaluated using the same techniques to extend the data set. Although the telocollinite in the Drayton and Cranky Corner coals have very similar carbon content (ca.78% C), the ATR–FTIR spectra of the vitrinite and inertinite macerals in these respectively low S and high S coals show some distinct differences in IR absorbance from various aliphatic and aromatic functional groups. The differences in absorbance of the aliphatic stretching bands (2800–3000 cm−1) and the aromatic carbon (CC) peak at 1606 cm−1 are very obvious. Compared to that of the Drayton sample (0.7% S and 15% O), the telocollinite of the Cranky Corner coal (6% S and 10% O) clearly shows: (i) less absorbance from OH groups, represented by a broad region around 3553 cm−1, (ii) much stronger aliphatic C–H absorbance (stretching modes around 3000–2800 cm−1 and bending modes around 1442 cm−1) and (iii) less absorbance from aromatic carbon functional groups (peaking at 1606 cm−1). Evaluation of the iso-rank Drayton and Cranky Corner coals shows that: (i) the aliphatic C–H absorbances decrease with increasing oxygen content but increase with increasing organic S content and (ii) the aromatic H to aliphatic H ratio (Har/Hali) for the telocollinite increases with (organic) O%, but decreases progressively with increasing organic S. The high organic S content in the maceral appears to be accompanied by a greater proportion of aliphatic functional groups, possibly as a result of some of the O within maceral ring structures in the high S coal samples being replaced.

A spectroscopic investigation of pigment and ceramic samples from Copán, Honduras

A combination of micro-Raman spectroscopy, micro-infrared spectroscopy and SEM–EDX was employed to characterize decorative pigments on Classic Maya ceramics from Copán, Honduras. Variation in red paint mixtures was correlated with changing ceramic types and improvements in process and firing techniques. We have confirmed the use of specular hematite on Coner ceramics by the difference in intensities of Raman bands. Different compositions of brown paint were correlated with imported and local wares. The carbon-iron composition of the ceramic type, Surlo Brown, was confirmed. By combining micro-Raman analysis with micro-ATR infrared and SEM–EDX, we have achieved a more comprehensive characterization of the paint mixtures. These spectroscopic techniques can be used non-destructively on raw samples as a rapid confirmation of ceramic type.

Confirmation of the assignment of vibrations of goethite: An ATR and IES study of goethite structure

Transmission electron microscopy (TEM), field emission scanning electron microscopy (FE-SEM/EDS) and X-ray diffraction (XRD) were used to characterize the morphology of synthetic goethite. The behavior of the hydroxyl/water molecular units of goethite and its thermally treated products were characterized using Fourier transform-infrared emission spectroscopy (FT-IES) and attenuated total reflectance–Fourier transform infrared (ATR–FTIR) spectroscopy. The results showed that all the expected vibrational bands between 4000 and 650 cm−1 including the resolved bands (3800–2200 cm−1) were confirmed. A band attributed to a new type of hydroxyl unit was found at 3708 cm−1 and assigned to the FeO–H stretching vibration without hydrogen bonding. This hydroxyl unit was retained up to the thermal treatment temperature of 500 °C. On the whole, seven kinds of hydroxyl units, involving three surface hydroxyls, a bulk hydroxyl, a FeO–H without hydrogen bonding, a nonstoichiometric hydroxyl and a reversed hydroxyl were observed, and three kinds of adsorbed water were found in/on goethite.

In situ ATR-FTIR study of H2O and D2O adsorption on TiO2 under UV irradiation

The adsorption of water and deuterium oxide on TiO2 surfaces was investigated in the dark as well as under UV(A) irradiation using in situ ATR-FTIR spectroscopy under oxygen and oxygen free conditions. Adsorption of H2O-D2O mixtures revealed an isotopic exchange reaction occurring onto the surface of TiO2 in the dark. Under UV(A) irradiation, the amount of both OH and OD groups was found to be increased by the presence of molecular oxygen. Furthermore, the photocatalytic formation of hydroperoxide under oxygenated condition has been recorded utilizing Attenuated Total Reflection Fourier Transformed Infrared (ATR-FTIR) spectroscopy which appeared as new band at 3483 cm-1. Different possible mechanisms are discussed in terms of the source of hydroxyl groups formed and/or hydration water on the TiO2 surface for the photocatalytic reaction and photoinduced hydrophilicity.

Uso da palha de carnaúba em revestimento de dutos

In this work, the plant species Copernicia prunifera (Miller) H. E. Moore (carnauba), naturally occurring which prevails in the northeast region of Brazil was the subject of studies aiming its use as external coating of pipelines used in petroleum industry. The part of the plant worked were the leaves, also called straw, which were coated with resinous material. For this purpose, it was necessary to evaluate the effectiveness of the use of acrylic resins in the straw carnauba coating. The properties of the untreated carnauba straw and chemically treated with sodium hydroxide, hexane and carbon tetrachloride were investigated by ATRFTIR, SEM and thermal analysis. The first two techniques showed that treatment with solvents has caused major changes in the straw surface, while the thermal analysis indicated that the sodium hydroxide caused variations in thermal stability of straw constituents. Water absorption measurements showed that treatments have accelerated the absorption process and the reduction of contact angle values for treated samples with solvents indicated higher hidrophilicity of straw. The tensile tests showed lower values of elastic modulus and tensile strength for treated samples. Furthermore, coatings using pure commercial resins A and B as well as the formulations with clay were applied in straw and they were examined once again through thermal analysis, water absorption measurements, contact angle and mechanical tests. To analyze the effect of heat ageing, samples were subjected to tensile tests again in order to assess its resistance. The results showed that the resins/clay formulations increased thermal stability of straw, they promoted a good impermeabilization and caused significant decrease in the values of elastic modulus and tensile strength. Evaluating the ageing effect on the mechanical properties, it has been showed good recovery to the coated straw with the formulations A 60 and A 80% in modulus and tensile strength values and elongation at break values have remained very close. It is thus concluded that the carnauba straw can be used as a coating of pipelines with significant cost savings, since there is no need for pretreatment for its use and shows itself as a viable biotechnology alternative, contributing to the quality of coatings material and environment preservation.

Pathways of the Photocatalytic Reaction of Acetate in H2O and D2O Combined: An EPR and ATR-FTIR Study

The adsorption and photocatalytic degradation of acetate on TiO2 surfaces was investigated in H2O and D2O by ATR-FTIR and EPR Spectroscopy respectively. These studies were carried out in the dark and under UV(A) illumination to gain additional insights into the adsorption behaviour with the identification of paramagnetic species formed during the oxidation of acetate. Isotopic exchange during the adsorption of D2O on TiO2 surface led to different interactions between the adsorbate and OD groups. At different pH levels, several surface complexes of acetate can be formed such as monodentate, or bidentates. Under UV(A) irradiation of TiO2 aqueous suspensions, the formation of hydroxyl and methoxy radicals evidenced as the corresponding spin-adducts, were found to dominate in alkaline and acidic suspensions respectively. Two possible pathways for the oxidation of acetate have been suggested at different pH levels in solution in terms of the source of the spin adduct formed. These proposed pathways were found to be in good agreement with ATR-FTIR and EPR results.