You can add any folder you want from any drive you want, including networked drives, into your libraries. All you have to do then is set whatever one you want as default.
I know that is what I do. To do this just open up a library and look right under the name of it (Documents library for example) and you will see a link to the locations. Just click on that and then point it to some folders you have made on your other drive. Once you have that done then just right click on the new location and set it as default.
Now that said I have found out that even when you do that you will still get some stuff saved in the original place. It seems as if some programs, including windows do not care what you want for a location. But really that is basically only appdata and some things like that. Anything you save to docs/music/videos/etc. would go to the new location that you have specified.
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