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I always had a libertarian bent, but "America's Great Depression" by Rothbard was the book that made me self-consciously libertarian. Interestingly enough, it didn't do it right away. I read the book in high school on someone's recommendation. Not the kind of thing I normally read...
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I found more on home schooling and critique of the compulsory schooling system:
http://www.youtube.com/watch?v=PP5UU_TbAfU
http://www.johntaylorgatto.com/chapters/index.htm