You can order free samples at http://www.microchip.com/samples/default.aspx - up to 6 chips can be ordered at one time (max of 2 types of parts, 3 parts each). They let you place 10 orders within a 40 day period.
Microchip used to offer free shipping, but they have now added a $7.50 "processing fee" which is reasonable considering they will send you up to $60 worth of parts per order.
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