Short Answer: The tip is oxidized — you've been running it hot without keeping it tinned with fresh solder.
Detailed: A soldering iron tip is copper plated with iron. At high temperatures (350°C+), exposed iron reacts with oxygen to form black iron oxide. Solder won't wet (stick to) oxide.
Prevention:
Always keep a small blob of solder on the tip when idle
Use brass wool (not a wet sponge — thermal shock cracks tips)
Set temperature to 300–330°C for leaded solder, 350–380°C for lead-free
Fix (if not pitted):
Clean with brass sponge
Apply fresh rosin-core solder
Wipe on damp sponge (quickly)
Repeat until solder flows evenly
If tip is pitted or has holes: Replace it. Tips are consumables ($2–10).

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