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Overflow volumes would have been used in the past when target disks for final output were full, but are pretty much an obsolete feature. No need to use them or worry about their location.
Regarding RAM and processor usage, see this page:"Performance tip: Don't starve your software of RAM". Following the guidelines there for your 12GB computer, you'd leave 2GB for other applications, maybe a couple of GB for the foreground proces to hold RAM preview frames---leaving you with 2GB each for four background rendering processes.
Also, don't be fooled. You 8-core computer is just an 8-core computer as far as After Effects is concerned. The purported doubling of processor cores that hyperthreading creates isn't relevant for Render Multiple Frames Simultaneously multiprocessing.
Regarding overflow volumes, see this page: "Overflow volumes and segment settings"
If you're new, please start here. Pretty please?
thanks, that's exactly the type of link I've been looking for.