You can change the working hours that are used with the calender in OWA by using the following powershell command:
set-MailboxCalendarConfiguration -Identity -WorkingHoursStartTime 08:00:00 -WorkingHoursEndTime 18:00:00
You can do this for the whole organisation by using Get-Mailbox and piping the results to the set-MailboxCalendarConfiguration:
Get-Mailbox | set-MailboxCalendarConfiguration -WorkingHoursStartTime 08:00:00 -WorkingHoursEndTime 18:00:00
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