not going to change his career direction
If you are not willing to change your career direction, then your first choice would be the languages that are currently at the top or are quickly on the rise in your field. For the market you specified that would be Java or .Net (C# ahead of VB.Net), but you have those. There are not any other languages that appear to be posed to threaten those except in niche markets.
So that leaves learning a language not because you will use that language in your profession, but to stretch your overall knowledge and skills. As everyone else has stated, C would be the obvious answer. After that you could pick up any number of languages. To pick the right one, decide which areas you could use the most growth in currently. Then choose the language that will focus on that area the most.