No, that's not a standard feature. But you could add that through customization:
1. Add a new field called secondaryemail to the Users table.
2. Create a simple screen based on the User's table. It could be as simple as having only a grid with the fields you need, and making sure it supports edit.
3. On the button that emails the work orders, include the secondaryemail for that employee as a CC to the email.
It's Method, so you aren't stuck in a box of only being able to use standard features - you can extend Method to do what you want.
Paul