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 the son of the sister by breastfeeding considered a mahram in Islam, and is it permissible for a woman to go for Hajj with him?

Everything that is prohibited by lineage is also prohibited by breastfeeding. The son of the sister by breastfeeding is considered a mahram, just like the son of the sister by blood, and it is permissible for him to be her mahram for Hajj and Umrah. And Allah Knows Best.

Is it permissible for the big brother to force his sisters to wear Hijjab (Islamic wear) if their father didn`t do his part in this regard ?

All Perfect Praise is due to Allah, The Lord of The Worlds

The father`s attention should be drawn gently and politely, and the sisters should also be reminded with good words since Allah, The Almighty, Says (What means): "O ye who believe! Save yourselves and your families from a Fire whose fuel is Men and Stones." [Al-Tahreem/6]. And Allah Knows Best.

A pious man proposed to me and my father was hesitant in this regard because he is black, am I sinful if I accepted his proposal?

If the suitor is pious, color isn`t a drawback. However, try talking to your father kindly, so that he approves of your marriage with contentment, and that is better for you.