Can I volunteer my time for free at my current job to gain extra experience?

Question Details: I work 40 hours a week for a town as a water plant treatment operator. I am interested in cross training to maintenance to gain extra experience but the town won't pay me overtime to do that. I was wondering if I can legally volunteer my time to work maintenance without getting paid, and freeing up the town any liability if I were to get injured. Not sure if there is a special form I would need to sign like an affidavit. I want to be able to work on my off days in maintenance to gain that experience and want to know if there is a legal avenue to make that happen.

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