A combined analytical approach applied to Medieval wall paintings from Puglia (Italy): The study of painting techniques and its conservation state

A combined analytical approach has been applied to the wall paintings, dated from 10th to 14th centuries, of the Santi Stefani crypt at Vaste (Lecce, Southern Italy). These paintings are a precious testimony of Medieval art in Southern Italy. However, the church shows problems of damp as well as clear evidences of flora, fungi and mold presence, and there is little knowledge of the pictorial methodologies used. Raman spectroscopy allowed to determine the palette and to reconstruct the worksite and the chronological sequence of the various paint layers. Kaolinite, calcite, carbon black, hematite, massicot, goethite, indigo and azurite were identified as pigments along with synthetic pigments, like phthalocyanine blue and chrome yellow. Attenuated total reflectance‐Fourier transform infrared spectroscopy suggested the presence of egg as a binder in some pictorial layers. The conservation state of the crypt is poor, and detachments of pigmented layers are frequent because of the presence of subflorescence and efflorescence: nitrate, sulfate and chloride salts have been identified spectroscopically and quantified by ion chromatography. The extensive use of kaolinite in Santi Stefani, actually not uncommon in Medieval art, is observed for the first time in a crypt of Puglia: its use to stabilize some pigments and to improve their adhesion on substrate is proposed. Copyright © 2015 John Wiley & Sons, Ltd.     

Interaction of humic and fulvic acids with nanoclusters of aluminum hydroxo cations on the surface of kaolinite according to IR spectroscopy data

We chemically modified the surface of kaolinite with nanoclusters of aluminum hydroxo cations. We have determined their composition and sizes. We have used IR spectroscopy to establish the interaction between the carbonyl and -diketone groups of fulvic and humic acids with the Lewis acid sites: coordination unsaturated Al³⁺ cations of the Al₁₃ nanoclusters. We have obtained spectral evidence for hydrogen bond formation between the carboxyl groups of fulvic acid and the hydroxyl groups of the aluminum hydroxo cations.__________Translated from Teoreticheskaya i Éksperimentalnaya Khimiya, Vol. 41, No. 1, pp. 45–49, January–February, 2005.     

An integrated spectroscopic approach to investigate pigments and engobes on pre‐Roman pottery

Painted Canosa ceramics were examined to identify the nature of the pigments employed and their manufacturing technology. A multi‐technique approach was used, comprising Raman microspectroscopy and laser ablation hyphenated to inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS). The analysed samples were mainly produced for burial in tombs and were not intended for everyday use. They belong to the period between the end of the mid‐7th century and the first half of the 4th century BC, and were excavated from the Toppicelli archaeological district near the suburbs of Canosa (Puglia, Italy). Forty‐eight pottery fragments were available for this study. No handling of the samples was required for the Raman study, and it was possible to excise the pigmented layer in such a way that the lacunae were not distinguishable to the naked eye due to the micrometric size of the laser spot as far as LA‐ICP‐MS is concerned. Their combination turned out to be quite useful for the investigation of these archaeological materials: the chemical nature of the white, red, brown and black pigments employed in the pottery manufacture was investigated. Iron and manganese compounds were identified as the red and brown/black main colouring substances, respectively; on the other hand, whites and engobes (whitish slips) were based on kaolinite. This set of colouring substances is of importance, as it enabled the artisan to obtain in one oxidising firing cycle brown, black and red paints. Finally, the finding of manganese black in these Canosa potsherds confirms that Canosa was an important centre connecting the near East to central Italy and Europe since the pre‐Roman age. Copyright © 2010 John Wiley & Sons, Ltd.     

Preparation,characterization, mechanical and barrier properties investigation of chitosan-kaolinite nanocomposite

The purpose of this study was to prepare a novel Clay Bio-Polymer Nanocomposite (CBPN) films by mixing polymer (chitosan, C) with exfoliated nanoclay (kaolinite, k). DRX has shown that the mechano-chemical treatment of kaolinite allows its exfoliation and the significant reduction of its particles size. Physicochemical properties namely thickness, water solubility, color, light transmission and transparency of the films were studied. Fourier transform infrared analysis (FTIR) was to study the interaction between chitosan and kaolinite. Differential scanning calorimetry (DSC) scans showed that the transition temperature (Tg) of films depends on the film's composition. The surface morphology of the films was also studied by scanning electron microscopy (SEM). Results showed that water solubility (Ws) decrease with the increase of the amount of clay. In addition, the presence of clay in the said films increases the mechanical strength. All prepared films were tested for their antimicrobial activities against gram-positive and gram-negative bacteria (strain). It was found that all CBPN films showed good inhibitory activity against all the tested bacteria. The above analysis suggested that the CBPN films could be used as potential candidates for therapeutic application.     

Thermo-infrared-spectroscopy analysis of dimethylsulfoxide-kaolinite intercalation complexes

Dimethylsulfoxide (DMSO) kaolinite complexes of low-and high-defect kaolinites were studied by thermo-IR-spectroscopy analysis. Samples were gradually heated up to 170°C, three hours at each temperature. After cooling to room temperature, they were pressed into KBr disks and their spectra were recorded. From the spectra two types of complexes were identified. In the spectrum of type I complex two bands were attributed to asymmetric and symmetric H-O-H stretching vibrations of intercalated water, bridging between DMSO and the clay-O-planes. As a result of H-bonds between intercalated water molecules and the O-planes, Si-O vibrations of the clay framework were perturbed, in the low-defect kaolinite more than in the high-defect. Type II complex was obtained by the thermal escape of the intercalated water. Consequently, the H-O-H bands were absent from the spectrum of type II complex and the Si-O bands were not perturbed. Type I complex was present up to 120°C whereas type II between 130 and 150°C. The presence of intercalated DMSO was proved from the appearance of methyl bands. These bands decreased with temperature due to the thermal evolution of DMSO but disappeared only in spectra of samples heated at 160°C. Intercalated DMSO was H-bonded to the inner-surface hydroxyls and vibrations associated with this group were perturbed. Due to the thermal evolution of DMSO the intensities of the perturbed bands decreased with the temperature. They disappeared at 160°C together with the methyl bands.     

The zeta potential of kaolin suspensions measured by electrophoresis and electroacoustics

The zeta potentials of kaolin dilute and concentrated suspensions were monitored using the techniques of electrophoresis and electroacoustics, respectively. The effect of addition of salt (KCl), a polymer material (Triton X-100), and an anionic surfactant (sodium dodecyl sulphate, SDS) on the suspension properties was investigated by electrophoresis. Electroacoustics was employed for the measurement of zeta potentials for the highest possible kaolin content in suspension and the effect of dilution. The effect of aging of a freshly prepared sample and kaolin isoelectric point was also studied. Using both techniques it was noted that there was no isoelectric point, just a maximum value in the magnitude of the kaolin suspension zeta potential. These maxima were observed also in the presence of Triton X-100 and SDS. An increase of the concentration of KCl and SDS in suspension shifted the maxima towards more acidic values, while in the presence of Triton X-100 the position of the zeta potential maxima remained constant. Electroacoustic techniques revealed that a freshly prepared concentrated suspension requires about six hours to equilibrate to achieve a steady zeta potential. Diluting the concentrated suspensions led to decrease of the zeta potential as ions bound to the surface desorbed and screened the surface charge. The zeta potential maxima remained unchanged even after heating the powder in an oven at 200°C (to remove any organic material) thereby suggesting that the most likely explanation for the maxima is isomorphic substitution.     

某复杂铝土矿中高岭石与一水硬铝石的分离方法问题研究

研究了某低品位复杂铝土矿中高岭石与一水硬铝石矿物相分离的传统选择性溶剂(HF溶液)的不适应性问题。物质组成分析指出,由于此类物料中伴生有含钠(钠长石)和含镁(铁质角闪石)等脉石类矿物,所以在用HF溶液浸取高岭石的反应过程中,与Al 3+同步进入浸出液中的Na+和Mg2+等,又与F-反应,形成NaMgAlF6·xH2O次生沉淀,且其与一水硬铝石矿物相一并留于余渣中,而直接干扰测定。因此,对H2SO4溶液作为选择性溶剂的可替代性问题进行了验证。结果表明:试样于500℃预焙烧后,用H2SO4(12mol/L)溶液沸水浴浸取分离高岭石,于余渣中测定一水硬铝石,可获得比较满意的结果。同时,对钠长石等其它含铝矿物干扰测定的校正方法问题,也进行了探讨。     

利用Taguchi法以高岭土为原料制备高硅NaY分子筛

采用Taguchi试验方法优化出了以高岭土为原料制备高硅NaY分子筛的最佳合成参数,考察了硅溶胶的加入量、反应体系的碱度、加水量以及晶化时间对NaY分子筛硅铝比和结晶度的影响。结果表明,高硅NaY分子筛的最佳合成条件是：反应体系各组分的物质的量比为7.5SiO₂∶1.0Al₂O₃∶2.2Na₂O∶120H₂O,晶化时间为16 h。同时发现,对合成样品性能的影响最为显著的因素是硅溶胶的加入量和碱度。采用X射线衍射、N₂静态容量吸附法和扫描电镜对利用最佳条件所合成样品的硅铝比、比表面积、孔分布以及表观形貌进行了表征。结果显示,以高岭土原料制备的NaY分子筛比参考样品拥有更高的硅铝比和更大的比表面积。     

Density functional theory investigation of carbon monoxide adsorption on the kaolinite(001) surface

Carbon monoxide(CO) is a gaseous pollutant with adverse effects on human health and the environment. Kaolinite is a natural mineral resource that can be used for different applications, including that it can also be used for retention of pollutant gases. The adsorption behavior of carbon monoxide molecules on the(001) surface of kaolinite was studied systematically by using density-functional theory and supercell models for a range coverage from 0.11 to 1.0 monolayers(ML). The CO adsorbed on the three-fold hollow, two-fold bridge, and one-fold top sites of the kaolinite(001) was tilted with respect to the surface. The strongest adsorbed site of carbon monoxide on the kaolinite(001) surface is the hollow site followed by the bridge and top site. The adsorption energy of CO decreased when increasing the coverage, thus indicating the lower stability of surface adsorption due to the repulsion of neighboring CO molecules. In addition to the adsorption structures and energetics, the lattice relaxation, the electronic density of states, and the different charge distribution have been investigated for different surface coverages.     

Benzene–kaolinite interaction properties

In this work, we present a theoretical study of interaction of benzene with kaolinite and an analysis of the vibrational spectra, electrostatic potential maps, and self consistent field (SCF) orbitals. B3LYP and MP2 benzene–kaolinite results indicate a preferential interaction of benzene on kaolinite octahedral surface. Population analysis indicates that the atoms modified their charges when the monoaromatic molecule and clay mineral are close to tetrahedral and octahedral surface of kaolinite, which suggests that the adsorbed molecule becomes slightly positive. Infrared vibrational data show the reduction in the band frequencies related to the kaolinite external hydroxyls, indicating a weak interaction of benzene with clay mineral. It also was verified, from the potential electrostatic maps, a change in electron density in both benzene and kaolinite. Electron localization function analysis was also carried out for this interaction. © 2011 Wiley Periodicals, Inc.