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Spray slow cooker with non-stick cooking spray. Remove the ham from the wrapper and discard glaze packet. Place inside prepared slow cooker.
Rub brown sugar, maple syrup, mustard, and balsamic vinegar all over the ham using your hands. Pour pineapple juice into the bottom of the slow cooker.
Cover tightly either with the lid or aluminum foil and cook on low 4 to 5 hours, basting twice, during the last hour.
Remove from slow cooker and let set 10 minutes. Slice the ham off the bone and serve warm.