You could use a combination of cron and iptables to block incoming connections at 10pm and drop the rule again at 8pm. That could then work for whatever service you offer on that machine, not just Samba.
If your server is not always up, use anacron rather than cron.
If other people, such as you as the admin, still need access during off-times, then you need additional rules which could make it a little bit more difficult.
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