What is the ruling on performing voluntary prayers during official working hours?
All perfect praise be to Allah, The Lord of The Worlds, and may His Peace and Blessings be upon our Prophet Muhammad and upon all of his family and companions
There is no harm if there was break time during official working hours, but if not then it is impermissible. And Allah Knows Best.
Is it permissible for a person to sever ties with his sister because her husband had quit prayer and done him harm?
A sister is a blood-relative and maintaining blood-relations is obligatory in Islam. As regards her husband, he should be invited to the way of Allah with wisdom and beautiful preaching.
Is it permissible for someone to make a supplication to Allah to marry an already married, or an engaged woman?
No, it isn`t, and the person who does so is sinful before Allah, The Almighty.
How should I be kind to my atheist father?
Allah, The Exalted, has decreed and ordained his slaves to be kind with parents, even if they are polytheists, by honoring and obeying them in all that isn`t sinful, so that they might love Islam and embrace it as a result.