The influence of chemical composition to position and intensity of the absorption bands observed in the FTIR spectra of palygorskite has been studied by a detailed comparative study of six samples. Palygorskites studied have high purity and different chemical composition. At one extreme, there are two samples that correspond to Mg-rich palygorskites, at the other extreme a sample with a composition very close to the theoretical formula of this mineral, and there are three further samples whose structural formulae lie between these extremes. The position of the bands identified in the FTIR spectra of the palygorskites studied is similar for all samples, but there are some differences in their intensity, which are significant. Analysing these intensities, valuable information about the distribution of cations along the octahedral sheet has been obtained. Isomorphic substitution in octahedral sheet occurs only in M2 position. AI, and Fe may occupy M2 position whereas Mg can occupy all possible sites: MI, M2 and M3.

Maya blue is an organo‐clay artificial pigment composed of indigo and palygorskite. It was invented and frequently used in Mesoamerica in ancient times (eighth to 16th centuries). We analyse in this paper one of the characteristics of Maya blue that has attracted the attention of scientists since its rediscovery in 1931: its high stability against chemical aggression (acids, alkalis, solvents, etc.) and biodegradation, which has permitted the survival of many works of art for centuries in hostile environments, such as the tropical forest. We have reproduced the different methods proposed to produce a synthetic pigment with the characteristics of the ancient Maya blue. The stability of the pigments produced using either palygorskite or sepiolite has been analysed by performing acid attacks of different intensities. The results are analysed in terms of pigment decolouration and destruction of the clay lattice, revealed by X‐ray diffraction. Palygorskite pigments are much more resistant than sepiolite pigments. It is shown that indigo does not protect the clay lattice against acid aggression. We show that Maya blue is an extremely resistant pigment, but it can be destroyed using very intense acid treatment under reflux.

The heating process (30-200 QC) of a paly gorskite-indigo mixture has been monitored in situ and simultaneously by synchrotron powder diffraction and Raman spectroscopy. During this process, the dye and the clay interact to form Maya blue (MB), a pigment highly resistant to degradation . It is shown that the formation of a very stable pigment occurs in the 70-130 QC interval; i.e., when palygorskite starts to loose zeolitic water, and is accompanied by a reduction of the crystallographic a parameter, as well as by alterations in the C=C and C=O bonds of indigo. Mid-and near-infrared spectroscopic work and rnicroporosity measurements, employed to study the rehydration process after the complex formation, pro vide evidence for the inhibition of the rehydration of l\1B as compared with palygorskite. These results are consistent with the blocking of the palygorskite tunnel entrance by indigo molecules with a possible partial penetration inside the tunnels. The surface silanols of palygorskite are not perturbed by indigo, suggesting that MB is not a surface complex.

Abstract-Many studies of the chemical composition of sepiolite and palygorskite have been carried out using analytical electron microscopy (AEM). According to the literature, a compositional gap exists between sepiolites and palygorskites, but the results presented here show that they may all be intermediate compositions between two extremes. The results of> 1000 AEM analyses and structural formulae have been obtained for the samples studied (22 samples of sepiolite and 21 samples of palygorskite) and indicate that no compositional gap exists between sepiolite and palygorskite. Sepiolite occupies the most magnesic and trioctahedral extreme and palygorskite the most aluminic-magnesic and dioctahedral extreme. Sepiolite and palygorskite with intermediate compositions exist between the two pure extremes:(1) sepiolite with a small proportion of octahedral substitution; (2) palygorskite with a very wide range of substitution (the pure dioctahedral extreme is unusual); and (3)

No abstract