Hi. I'm trying to figure out how i can save materials you get in Zbrush on to my highpolys vertexes so i can bake them out in xNormal later. Only thing i seem to find is if you have UV's but i want it straight on my HP object.
In xNormal on the Highpoly tab, make sure 'Ignore per-vertex color' is turned off
In the baking options, turn on the 'Bake highpolys vertex colors' map type
That will bake polypaint to your lowpoly mesh without the sculpt needing UVs. It's not the same as baking the material from zbrush though; those can not be baked to a static texture without a serious sacrifice to visual quality.
Here's a pretty dated tutorial on how to extract your matcap details, but like cryrid said, visual quality will probably not be as good since many ZBrush materials react to lighting in realtime.
You could use zapplink to get different views to paint with. You would just have to load each view in spotlight. Basically pick a matcap, save the views, and paint a version of your mesh with spotlight. Sounds kinda ridiculous, but if you really don't want UVs that's how I'd try and do it.
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That will bake polypaint to your lowpoly mesh without the sculpt needing UVs. It's not the same as baking the material from zbrush though; those can not be baked to a static texture without a serious sacrifice to visual quality.
http://www.zbrushcentral.com/showthread.php?36229-BAKING-MATERIAL-IN-ZBRUSH-tutorial