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There seems to be a great deal of confusion about ammunition, particularly cast iron shot, and 'metal' moulds for casting iron. The situation is a whole lot more complicated and, indeed, a very under-researched area.
 
To start with ammunition. The oft quoted Florentine reference to iron balls does not state what type of iron was being used - ie wrought or cast iron. From our current (very limited) knowledge of the development of cast iron it is much (much) more likely that the balls were hammered, ie wrought, iron. If you want to know how these were made see our old friend Biringuccio - page 321 of the standard translation
 
To very briefly summarise the development of ammunition. Early guns, 1325 - 1375, fired arrows (garros) with a very few isolated references to iron - probably wrought as stated above. These early guns were probably small calibre by the way. Lead shot, plommee, were also used from a very early date. Stone shot appears in the records from the later 14th century, the 1360s or so. These stone shot could be very large - up to several hundred kilograms. It is likely, though difficult to prove, that large stone shot were adopted from contemporary non-gunpowder siege weapons, trebuchets etc.
 
Petrach's reference to 'metal' probably means a copper alloy of some kind. It would be important to see the original to be sure.
 
The introduction of cast iron shot is an exceedingly confused area. The commonly stated date is the early 15th century with cast iron becoming common thereafter. However a thorough survey of the archives of the artillery of the Dukes of Burgundy reveals that cast-iron was very uncommon - almost non-existent. It is not till much later in the 15th century that cast iron shot became common. I must stress though that this period is really not well researched.
 
Intriguingly the Burgundian archives do have the occasional reference to cast-iron guns in the 1420s.
 
Stone shot went on being used well into the 17th century. ALL forms of shot, stone, lead and cast-iron, were in use at the same time - and up to at least the later 16th century.
 
Metal moulds. This is an area even less researched than the above. That cast-iron shot were made in quantities in the 15th century probably means that they had access to this technology. However stone moulds were found on the Mary Rose (sank 1545). There have been several reported wrought-iron tong-like implements for casting shot but their dating is problematic - early to mid 16th century probably.
 
Finally can I make two last pleas:
First do not believe all you read - on the internet as well as in the printed literature - on medieval artillery. The proportion of good to bad is probably in the region of 1% to 99%. It is one of those areas where the same old hoary myths and legends get regurgitated ad nauseam without any critical examination.
Second the early history of cast iron is so under-researched that it is impossible to draw any reliable conclusions. More GOOD PRIMARY research needed please. (Do however see the early 20th century work of people like Rathgen)
 
Sorry for the long rant but we here (that is the Smithbrown partnership) get a bit fed up to see the same stories trotted out endlessly.
 
Regards
 
Bob Smith