VISA transmits data in HEX format, so for each kind of data you send (ASCII, BInary, HEX, etc), VISA will converted it to its HEX value and send over through VISA. What you can do is right click on the String Control where your command is written and choose "HEX Display" so the HEX values of your ASCII commands will be displayed in HEX--this does not change how the values are sent over VISA.
For example, if you use the HEX display, and send FF, the serial port will transmit the value of 11111111(binary). If you are using Normal Display and send FF,it will have a HEX value of 4646 and being transmitted as a totally different binary number. You can check the following KnowledgeBase for more info:
http://digital.ni.com/public.nsf/websearch/77C8F61D36F5A23086256634005ACB38?OpenDocument