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When I wrote How do I use elemental effects in Borderlands 2? to the best of my knowledge Explosive guns couldn't critical; I've tested this with "grenade" Assault Rifles, Gyrojet Tourge Assault Rifles and rocket launchers, none of which are able to score a critical (that I ever saw). When using a Tourge explosive Shotgun today, I started getting Criticals just like normal for a shotgun.

Which explosive weapons can cause critical hits? Is there some reason some do and some seem not to?

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Explosive shotguns fire pellets like all the other shotguns. Upon hitting the target, the pellet applies the explosive element at the point of contact between pellet and enemy. This means that if the pellet hit a critical part, it cause the explosive damage to be critical.

Grenade assault rifles and rocket launchers won't get critical hits bacause it's firing a projectile that explodes upon contact with the enemy. Even if you aim for the weak spot on a huge enemy (crystalisks), it won't apply the critical hit.

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If this is indeed true, you may want to look into editing the explosive section of the answer to this question –  Kecoey Oct 5 '12 at 0:27
    
@Kecoey it seems true from what I've seen –  Prinny Brocka Oct 5 '12 at 0:45
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In Borderlands 2, Torgue weapons have two different firing traits.

  • If the weapon spawns with a barrel component of Torgue manufacture, it will shoot folding fin rockets. This rockets cause very high damage, but have high spread and low velocity. They also cannot score critical hits and each rocket cost multiple units of ammunition. In this case, the explosive damage is included in the damage stated in the weapon card, and calculated by the game as a single hit.

  • The other firing trait is present when the barrel component is from any other manufacturer. In this case Torgue weapons will shoot Gyrojet projectiles. These projectiles have low initial speed, but accelerate as they travel forwards, and are faster than the folding fin rockets. They also deal additional explosive area-of-effect damage on impact and can score critical hits. The game calculates the bullet impact and the explosive effect separately (card only shows projectile damage), and the blast can hit enemies near to the point of impact.

Source: Borderlands wiki, "Torgue" article (emphasis mine)
Note that the above does not apply to some Unique, Seraph or Legendary Weapons.

Unique/Seraph/Legendary weapons

Some notable explosive Unique/Seraph/Legendary weapons that can score critical hits: 12 Pounder (Manufacturer and Barrel: Torgue), Cobra (Manufacturer: Jakobs; Barrel: Dahl), Ogre (Manufacturer: Torgue; Barrel: Vladof), Unkempt Harold (Manufacturer and Barrel: Torgue).

Some notable explosive Unique/Seraph/Legendary weapons that can not score critical hits: KerBlaster (Manufacturer and Barrel: Torgue), Seeker (Manufacturer: Torgue; Barrel: Vladof).

Assault Rifles

The Assault Rifles titled: Cannon (Manufacturer: Jakobs, Barrel: Torgue) and Grenadier (Manufacturer: Dahl, Barrel: Torgue) shoot grenades, instead of folding fin rockets or Gyrojet projectiles. They act like folding fin rockets, in that they cannot score critical hits too.

Oddities

The 12 Pounder, a unique rocket launcher, is the only rocket launcher that can score critical hits. Weapon special effect description: "Nec Pluribus Impar, Bitches. – Increased damage, reduced magazine size, and fast reload speed. Fires arcing cannonballs that explode if they directly hit an enemy or bounce with parabolic trajectory if they hit an inert surface before exploding. Cannonballs are capable of scoring Critical hits".

The Seraph Assault Rifle, Seeker, despite being manufactured and having the barrel made by Torgue, can not score critical hits. Weapon special effect description: "Oh, yeah, that's fair... – Shots fired home in on enemies. Each shot consumes 2 ammo."

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Every explosive pistol i have used has been able to land criticals. Same for shotguns. Never yet found a rocket launcher or explosive assault rifle that could land a critical.

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The 12 Pounder rocket launcher can land a critical hit. Torgue Assault rifles titled: Rifle, Root, Lance and Spitter can land critical hits. –  galacticninja Jul 3 '13 at 5:02
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