The Grand Master trainer is the only one who provides trainer-taught plans, this ends at 350 skill with Felsteel Whisper Knives.
You can learn additional plans that are sold as limited supply plans or by faction quartermasters (requiring you to have certain a certain rep level with that faction) and you can obtain plans that drop from various mobs.
Vendor Sold (Limited Supply, no reputation requirement)
- Skill 325 Adamantite Plate Bracers
- Skill 325 Adamantite Cleaver
- Skill 325 Adamantite Dagger
- Skill 325 Adamantite Maul
- Skill 335 Adamantite Plate Gloves
- Skill 335 Adamantite Rapier
- Skill 340 Adamantite Breastplate
- Skill 340 Lesser Rune of Shielding
- Skill 350 Adamantite Rod
- Skill 375 Eternium Rod
Vendor Sold (Faction quartermaster; reputation requirement)
- Skill 350 Adamantite Sharpening Stone - Honored with Cenarion Expedition
- Skill 350 Adamantite Weightstone - Honored with Cenarion Expedition
- Skill 350 Flamebane Bracers - Friendly with Aldor
- Skill 350 Greater Rune of Warding - Honored with Cenarion Expedition
- Skill 355 Enchanted Adamantite Belt - Friendly with Scryers
- Skill 355 Enchanted Adamantite Boots - Honored with Scryers
- Skill 360 Enchanted Adamantite Breastplate - Revered with Scryers
- Skill 360 Felsteel Shield Spike - Exalted with Honor Hold
- Skill 360 Flamebane Gloves - Honored with Aldor
- Skill 365 Enchanted Adamantite Leggings - Exalted with Scryers
- Skill 365 Flamebane Breastplate - Revered with Aldor
- Skill 365 Flamebane Helm - Exalted with Aldor
- Skill 375 Iceguard Breastplate - Honored with Violet Eye
- Skill 375 Iceguard Helm - Honored with Violet Eye
- Skill 375 Iceguard Leggings - Revered with Violet Eye
- Skill 375 Wildguard Breastplate - Exalted with Cenarion Expedition
- Skill 375 Wildguard Helm - Revered with Cenarion Expedition
- Skill 375 Wildguard Leggings - Revered with Cenarion Expedition
World drop (get very lucky or buy in AH)
- Skill 365 Black Felsteel Bracers
- Skill 365 Blessed Bracers
- Skill 365 Bracers of the Green Fortress
- Skill 365 Dirge
- Skill 365 Eternium Runed Blade
- Skill 365 Fel Edged Battleaxe
- Skill 365 Fel Hardened Maul
- Skill 365 Felfury Gauntlets
- Skill 365 Felsteel Longblade
- Skill 365 Felsteel Reaper
- Skill 365 Gauntlets of the Iron Tower
- Skill 365 Hand of Eternity
- Skill 365 Helm of the Stalwart Defender
- Skill 365 Khorium Champion
- Skill 365 Oathkeeper's Helm
- Skill 365 Runic Hammer
- Skill 365 Steelgrip Gauntlets
- Skill 365 Storm Helm
World Bind on Pickup drops (soloable, can only be looted by Blacksmith):
- Skill 360 Plans: Khorium Belt from Murkblood Raider at Sunspring Post (Nagrand)
- Skill 360 Plans: Khorium Pants from Deathforge Guardian at The Deathforge (Shadowmoon)
- Skill 365 Plans: Khorium Boots from Disenbodied Protector at Ruins of Enkaat (Netherstorm)
- Skill 365 Plans: Ragesteel Gloves from Boulderfist Warrior near Halaa (Nagrand)
- Skill 365 Plans: Ragesteel Helm from Anger Guard at Force Camp:Anger (Blade's Edge Mountains)
- Skill 375 Plans: Greater Rune of Shielding from Sunfury Bloodwarder at Manaforge B'Naar (Netherstorm)
Instance Bind on Pickup drops (need group, can only be looted by Blacksmith):
- Skill 360 Plans: Felsteel Leggings from Unchained Doombringer in The Arcatraz
- Skill 360 Plans: Felsteel Gloves from Auchenai Monk in Auchenai Crypts
- Skill 365 Plans: Felsteel Helm from Cabal Fanatic in Shadow Labyrinth
- Skill 370 Plans: Swiftsteel Gloves from Nexus Stalker in Mana Tombs
- Skill 370 Plans: Earthpeace Breastplate from High Botanist Freywinn in The Botanica