Compilation of Luffy's unaware CoA:
Luffy used Armament against Kuma and BB unintentionally
Luffy sent Ace and Smoker flying
Luffy against Lucci and Blueno's Tekkai's
https://www.youtube.com/watch?v=SAerl1wEnfY&ab_channel=Sogovegeta
Observation vs Mihawk when he thought about losing his arms to him (later he tried to cut them to be free from BM prison), he used Armament against Crocodile and Aokiji unintentionally (cause Crocodile blade should've cut Luffy hand when he did the storm technique, and sent Aokiji flying by kicking him in the abdomen before he'd try to beat him same way he did to Crocodile which is by storm, and against Don Accino to defy hotness and Gasparde too to still launch him flying), and he used Conqueror later in Sabody (against a bull), Amazon Lily (on Boa sisters), Impel Down (on wolves trying to kill Mr. 2) and Marineford (to stop Mr. 3 Lol and his fellow executioner from executing Ace and KO'd some Marines and fellow WB pirates unintentionally) Arcs unintentionally as well
Zoro used unaware CoA against Kuma and Daz Bones, these were his 2 most powerful Lion's song ever of pre-timeskip
Zoro CoC
https://www.youtube.com/watch?v=hKFbKGP2TjY&ab_channel=OnePieceMoments
Zoro unaware CoO and CoA against Daz Bones!!!! (Used unaware Armament to cut Daz's steel and his strongest attack Atomic Sprut)
https://www.youtube.com/watch?v=_2G04XDFTI0&ab_channel=AnimeMoments
Sanji unaware CoA vs Jabra
https://www.youtube.com/watch?v=Jc2pjvGi5Zc&ab_channel=KurokkasuAnime
What other Straw hats I didn't mention that used haki pre-timeskip and what other times I didn't mention?
Edit: I wanna also mention that the times Luffy didn't shrink after Gear 3 was also the times he used haki like when he did Giant rifle against that Giant in Marineford.
Luffy used Armament against Kuma and BB unintentionally
Luffy sent Ace and Smoker flying
Luffy against Lucci and Blueno's Tekkai's
https://www.youtube.com/watch?v=SAerl1wEnfY&ab_channel=Sogovegeta
Observation vs Mihawk when he thought about losing his arms to him (later he tried to cut them to be free from BM prison), he used Armament against Crocodile and Aokiji unintentionally (cause Crocodile blade should've cut Luffy hand when he did the storm technique, and sent Aokiji flying by kicking him in the abdomen before he'd try to beat him same way he did to Crocodile which is by storm, and against Don Accino to defy hotness and Gasparde too to still launch him flying), and he used Conqueror later in Sabody (against a bull), Amazon Lily (on Boa sisters), Impel Down (on wolves trying to kill Mr. 2) and Marineford (to stop Mr. 3 Lol and his fellow executioner from executing Ace and KO'd some Marines and fellow WB pirates unintentionally) Arcs unintentionally as well
Zoro used unaware CoA against Kuma and Daz Bones, these were his 2 most powerful Lion's song ever of pre-timeskip
Zoro CoC
https://www.youtube.com/watch?v=hKFbKGP2TjY&ab_channel=OnePieceMoments
Zoro unaware CoO and CoA against Daz Bones!!!! (Used unaware Armament to cut Daz's steel and his strongest attack Atomic Sprut)
https://www.youtube.com/watch?v=_2G04XDFTI0&ab_channel=AnimeMoments
Sanji unaware CoA vs Jabra
https://www.youtube.com/watch?v=Jc2pjvGi5Zc&ab_channel=KurokkasuAnime
What other Straw hats I didn't mention that used haki pre-timeskip and what other times I didn't mention?
Edit: I wanna also mention that the times Luffy didn't shrink after Gear 3 was also the times he used haki like when he did Giant rifle against that Giant in Marineford.