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More than twenty years have passed since we invented polymer-clay nanocomposites (PCN), in which only a few wt.-% of silicate is randomly and homogeneously dispersed in the polymer matrix. When molded, these nanocomposites show superior properties compared to pristine polymers such as tensile strength, tensile modulus, heat distortion temperature, gas barrier property, and so on. The number of papers on PCN has increased rapidly in recent years, reaching over 500 only in 2005. As the pioneers of the new technology, we will review its history highlighting our works. Epoch-making events of PCN are as follows: In 1985, The first PCN, nylon 6-clay hybrid (NCH), was invented. In 1987, NCH was first presented at the ACS Fall Meetings. In 1989, NCH was presented at the MRS Fall Meetings, firing PCN. In 1989, Toyota launched cars equipped with a NCH part. In 1996, Clay was found to cause a memory effect in liquid crystals.

ϵ-caprolactam was polymerized in the interlayer space of montmorillonite, the clay mineral yielding a nylon-clay hybrid (NCH). X-ray and TEM measurements revealed that each template of the silicate, which was 1 nm thick, was dispersed in the nylon 6 matrix, and that the interlayer distance of clay increased continuously from 1.2 nm for the unintercalated material to 21.4 nm for the intercalated material. Thus, NCH is a polymer-based molecular composite or a nano-composite. NCH contains 1-15 vol% of monolayer clay. Injection-molded NCH showed excellent mechanical properties compared with nylon 6 in terms of tensile strength, tensile modulus and heat resistance. The tensile modulus of NCH was twice that of Nylon 6, and the heat distortion temperature increased from 65°C for nylon 6 to 145°C for the NCH containing only 1.6 vol% of a clay mineral. It was found that such excellent properties of an NCH system was due to the strong ionic interaction between nylon 6 and the silicate layer.