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EDIT: Apparently they're also on utility protectrons (the ones with the nail guns). That's off Fallout Wiki... I will be back in a while with some location info.
EDIT EDIT: Also just caught this on the wiki:
"Over a hundred spikes can be purchased from Proctor Teagan aboard the Prydwen. "
That's the same for railway rifle. Once you first get it either by railroad or finding it on a specific location. You will find ammo for it by some sort of discovery unlock when you have it. Otherwise add two ranks on scrounger and it should show up random ammo for you to gather.
Interiors
cambridge mass chemical
four leaf fishpacking plant
saugus ironworks
hester's consumer robotics
Base game exteriors
POIJS017 3,7 (north of west everett estates)
POISC20 -6,-14 x2 (2 or 3 pip map squares east of cutler bend) (two bots)
relaytower05ext -13,-3 (southwest of oberland station, I think)
roboticspioneerparkext03 -13,-18
wickedshippingext -21,15
DLC locations
Vim pop factory interior
Nuka World/Vault Tec - Among The Stars (two bots)
I dont believe you can make them with the ammunition plant from the contraptions dlc (just checked the wiki and its says u cant, but wiki's areint always right)