I think it was a problem with the language as well as how they handle it internally. It was basically the algorithm that dictates how the language works, and consequently there was no way to have one material touch more than one other material. But I might misremember.

Anyway, I'm looking at this from the user's perspective. I wanted to do some physics-based ray-tracing with lenses and pbrt is what I ended up trying. As such, I really needed the multi-material aspect to work correctly. Also, it would be nice to be able to describe surfaces using a z=f(x,y) kind of formulation, or a way to place a hook in the renderer.

It's definitely an architectural problem as well. I do wonder if we could extend that though, without too much trouble for the general architecture - after all, the material does not necessarily need to represent all the outside materials and instead the ray only needs to be able to go from one medium to another. I'm happy to chat about possible extensions in that direction, although to be fair I wont have much time in the next weeks to sit down on anything like this. But, I do really hope that this can become a playground for ray tracing experiments in general!