Evidence for access of molecules the size of acetone or pyridine to the intracrystalline tunnels of nanofibre clay (sepiolite) has indicated formation of a new type of organic-inorganic nanocomposites. However, the introduction of larger molecules has been a recurring problem. It is now agreed that for indigo, the molecules are located on the external surface and at the ends of the fibres, thus blocking access to internal tunnels. We claim, however, that it is possible for indigo molecules to access the internal channels of sepiolite. FTIR and XRD analyses have provided evidence for folding of the sepiolite structure preheated at high temperature (above 350 degrees C). By comparison, we have shown that for indigo/sepiolite mixtures treated in the same conditions, no change in the crystalline structure of the sepiolite is observed, and that blue samples, related to Maya blue, with indigo molecules incorporated deeply enough into sepiolite to prevent folding of the tunnels, can be obtained. NMR, FTIR and thermal analysis confirm the interaction of indigo with the water coordinated to magnesium(II) and located inside the internal and external channels of sepiolite. Two other hypotheses are excluded; we show both that zeolitic water is not blocked in the tunnels by indigo, and that if thermal decomposition products of indigo can be formed, they are in a minority.

Having first studied the loss of water in sepiolite via TGA, we then observed through FTIR the evolution of the indigo/sepiolite chemical bonds during the Maya blue formation process. Three stages, corresponding to three different temperature domains, were observed. They explain the peculiar properties of this pigment.

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