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The fire performance of curable silicone-based coatings containing expandable graphite, organoclay, and calcium carbonate is evaluated in cellulosic fire scenario (standard ISO834) using a lab-scale furnace test. It is shown that the use of organoclay and calcium carbonate allows achieving same insulative performance when compared with organic commercial intumescent coating. The mode of action of these silicone-based coatings is fully investigated using thermal analyses and spectroscopic analyses including X-ray photoelectron spectroscopy. It is shown that the high fire performance of intumescent silicone-based coatings is due to (1) interactions between calcium carbonate and silicone matrix increasing the thermal stability of the resin and (2) the formation of calcium silicate embedding the top of the char and permitting the formation of an additional protective ceramic layer.

The fire performance of two curable-silicone based coatings containing 25% expandable graphite (EG) are evaluated in hydrocarbon fire scenario (standard UL1709) using a lab-scale furnace test. In this paper, the influence of the catalyst on the fire performance are investigated. Two organometallic titanium based- and tin based catalyst are used to make the curable silicone crosslink. When titanium based catalyst is used, the fire performance are higher and the mechanical properties of the char is better than that when tin is used as catalyst. To explain this surprising different fire behavior, the two residues after the furnace test were analyzed by X-ray photospectroscopy. It has been demonstrated that in the case of titanium based catalyst, the char is composed of graphite embedded by crosslinked silicone structure compare to linear silicone structure in the case of tin based catalyst. The two silicone resins were characterized by Fourier Transform Infrared spectroscopy, 29Si NMR, thermogravimetric analyses, EPMA (electron probe microanalyses). It was highlighted that the tin migrates into the surface during the crosslinking of the matrix leading to a low thermal stability and, thus, low fire performances. Whereas, when titanium based catalyst is used, it participates to the silicone network with the formation of Si–O–Ti bounds increasing the thermal stability of the matrix and so enhancing the fire performance of the silicone/EG based coating.