1- Sure Byakuya hasn't gone mad crazy on someone but you don't just look at the way they attack others but also the words they use and their facial expressions. And I believe I have noticed multiple occasions where Byakuya has been surprised. 1) Yoruichi showing up in the Soul Society Arc. 2) Ichigo showing Byakuya his Bankai and parrying all the petals of his initial Bankai state in Soul Society Arc. 3) Ichigo running through the Kuchiki Manor and bursting into Byakuya's room in Soul Society Arc.
2- Shunsui is a very ideal candidate for this, more so than Byakuya. Often carefree, lazy and humorous, Shunsui has mainly shown surprise in the case of Wonderweiss attacking Ukitake. I have rarely seen him surprised in any other occasion. He tries to distract and persuade enemies from combat, instead offering conversation and/or sake. Even when facing Old Man he kept his cool as Ryujinjakka's Shikai was released.
3- Unohana definitely rivals, if not surpasses, Shunsui. The most alarm she has ever shown has been when Isane was about to attack Aizen after he had defeated Hitsugaya and that was in the form of a warning. As said she's soft-spoken, benevolent and well-mannered. Even on the way to Fake Karakura Town with Ichigo she seemed to calmly explain how Ichigo was their trump card against Aizen despite the situation.
4- Mayuri is hardly a candidate for a calm character, because on multiple occasions he let his emotions guide his words. He has been surprised and shown utmost disgust and anger when he's been upstaged. 1) Uryu vs. Mayuri Soul Society arc when Uryu shot his Bankai in half. 2) Bount Arc when he discovered his data had been tampered with. 3) Mayuri was extremely angry when Ichigo and Unohana compared him to Kisuke.
5- On the other hand, Nemu can be a strong candidate too. She's about as soft-spoken as Unohana and shows little emotion that isn't the result of severe pain. She has never been angry nor has she been sad; I can't say I've even seen her express happiness. Anything like surprise, alarm or similar emotions are extremely dulled to the point where there's barely any indication.
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