The tiles on the Shuttle are basically rigid substances laid on the surface of an aluminum airframe that, like all airframes, flexes and expands in use. A series of small tiles with elastic spacing materials between them allows movement without tiles breaking or popping off.

There may be a way to do this by "overlapping" the tiles, but it would not be worth it, and the drag and additional heating created by such a "scaley" surface would probably not be good.

Applying tiles to the Shuttle is not an easy business.

Some work has been done on using high-temperature metals, even a long time ago. The X-20 "Dyna Soar" was to made of Rene 41 super alloy, with molybdenum and graphite used in some parts. Super alloy technology has improved since then.