@dougal - re: samples - if you look at some companies they specifically allow for samples for education/students/ even hobbies sometimes. I rarely get samples, because I always have a DigiKey or Mouser order going in (why Digikey/Mouser, see below) - but even when I hadn't made more than 1 of anything ever, I took the honest approach on the follow up email/call (more often email these days) - I'm making this thing, if it is a success I hope to sell it - some of the chip companies I use are used because they responded well to that. TI and Maxim come to mind as having very liberal sample policies to support development with their chips in all realms.
I thought it might be interesting to post my list, similar to dougal's, of chip supplier experiences:
Mouser.com: Good shopping experience. Medium selection. One of the cheapest. Fast shipping. Never had any mistakes. Over $50k ordered.
Arrow.com: OK shopping experience. Small selection. No bulk pricing, sometimes no price at all until you make an account. Medium pricing. Slow to ship. About $5k ordered.
AVnet.com: OK site. Big selection. Medium to low price. Good fast cheap shipping. About $25k ordered.
DigiKey.com: Something about their site make me so annoyed, but that is because I use it so much. THis is the site I am most likely to use to explore parts for a given application. Mouser's site is better for this, but their selection is limited compared to Digikey. Best selection, one of the cheapest if you order in 10+ Qty. Lots of shipping options, including first class for like $4. Super SUPER fast shipping - like order at midnight on Sunday and it ships at 3am and gets to me by Tuesday for $6 priority postage. Small orders tend to have mistakes more frequently than other sites, but they are quick to resolve. They are my go to 1) for selection, 2) for price, 3) because they take getting it to you fast, VERY seriously. I don't want to know how much I spent here - probably about $150k
Newark.com (element14): Difficult to use site (sometimes the same search comes up empty, and then doesn't). The most horrible experiences with customer service - delays for credit card verification that are then forgotten, tax added on tax exempt orders (2 months for a refund), rude customer service, things backordered when you get the order that weren't when you paid, management does not respond to anything, even issues that cause the cancellation of $10k orders. Slow to ship, but cheap 2 day shipping. About $25k ordered.
futureelectronics.com - OK site, Good prices, small selection, good shipping. ~$5k ordered
Verical.com - A "market place" - slow order process, bad customer serivce, $15 order fee, sometimes great prices - HORRIBLE FLASH SITE! - about $5k ordered
That's all I can think of for now