Dawns piplup gets mad with picachu because he lives to go to isshu region so piplup runs away and stuff.O brock leaves to. Its the second time that brock leaves the series so it will be awesome at 12 September to episodes of isshu region will be played
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at episode 5 of Pokemon diamond and pearl
The name of the 3rd Episode in Diamond and Pearl was called "When Pokémon Worlds Collide!"
on youtube
If you are talking about the games, Piplup was introduced in Pokemon Diamond and Pearl... Piplup was introduced in the anime Pokemon Diamond and Pearl episode 1, titled "Following a Maiden's Voyage!"
http://www.animecrazy.net/category/more-running-anime/pokemon-diamond-and-pearl/ try this site in a few days