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It's certainly possible, but it's not really done for several reasons, the most obvious of which is general lack of access to a kiln. Beyond that, there are practical working issues. 40k-style models have lots of layers of armor, tubing, clothes, bling, etc. that could be a pain to sculpt as a single mass. By using a medium that can be added and worked over an already cured surface, we have a much easier time working on individual elements that make up the whole. There's also a reduced risk of mucking up completed sections while working on a new one.
2-part epoxy putties and polymer or air-dry clays are also frequently sanded, filed, and drilled during the sculpting process (especially on larger scale projects) to refine shapes and ensure a smooth finish. Clay could be moistened and smoothed, but unless that surface is the topmost layer, it's likely to be marred by subsequent applications.
Think of a SM's shoulder pad - getting the surface perfectly smooth while still being able to add the trim, especially with rivet or filigree detailing, would be a serious pain. Instead, you could mold the basic shape and sand it smooth, then layer on the trim, then add fine detailing. By working in layers, each element can be fully worked and refined without regard for the others, since they've already cured. Using epoxy putties also means that the layers are self-adhesive, too, allowing you to build the model in parts without worrying about how to attach them and keep their shape (can you imagine trying to sculpt trim separately, fire it, then glue it to a complex curve? nightmarish).
Of course, the larger the sculpt, the easier using clay would be. I just don't see any benefit over the more commonly used mediums, all of which boast at least some benefits over the clay.
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