(1) Natalie showed great composure in answering Brian's provocative question.
(2) Natalie showed great composure when answering Brian's provocative question.
(3) Natalie showed great composure when she answered Brian's provocative question.
(4) Natalie showed great composure when she was answering Brian's provocative question.
(5) Natalie showed great composure while she was answering Brian's provocative question.
Question: Which is correct?
Those are all possible.
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Just a small observation:
Typically "while" goes with the continuous form and "when" doesn't, giving these as most typical:
when she answered
while she was answering
It is not wrong, however, to use the reverse pattern.
CJ