A three-layer structure, including a columnar layer (CL), a buffer layer, and unaffected intact enamel, was successively formed from the outer to the inner part of artificial enamel lesions (AEL) by topical applications of a high-concentration acidic sodium fluoride solution (10,000 ppm, pH 5.6) in vitro. The AEL was produced in bovine enamel that was decalcified for 5 days in a lactic acid gel system. The morphological observations by using scanning electron microscopy showed that the CL was made of columnar deposits of small globules about 0.5 μm in diameter. It was observed for the first time that small globules filled the demineralized interprismatic regions in the buffer layer. The unaffected intact enamel was protected from further demineralization under the acidic condition. Structure and composition of the CL were investigated by using X-ray diffraction and X-ray photoelectron spectroscopy. In the CL the atomic ratio was Ca:P = 12.6 and Ca:F = 0.75, and the small globules were mainly a mixture of polycrystalline calcium fluoride and hydroxyapatite. For comparison, the sound enamel and the AEL attained by applications of 0 and 100 ppm acidic sodium fluoride solutions (pH 5.6) were also investigated. The formation mechanism of the three-layer structure and the related cariostatic effects are discussed.

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