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It has a wider temperature range, ie. it will go from molten to solid in a few seconds once the joint has been made, whereas 63/37 tin/lead solder solidifies quicker, meaning you have to be really really quick with the soldering iron.
If you prefer to go lead-free, then use the lead free with added silver, not the standard lead free you get from the DIY shop.
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Thanks very much for the pointers chaps!