Actually the time should be replaced with whatever you specify. If you say
UPDATE table SET timefield="000045";
the time should be set to 00:00:45.
If there was any value there before, it should be overwritten.
If you want to add time to a timefield, you'll have to use a the date_add() function:
http://www.mysql.com/doc/D/a/Date_and_time_functions.html
like:
UPDATE table SET timefield=date_add(timefield,20 second);