Whenever a new customer arrives at store homepage. If enabled, a pop-up asking for customer ZipCode will be displayed automatically as shown in image below.
Once you enter zipcode, you can see your zipcode is checked for COD for delivery are available or not for your entered zipcode on product detail page. After entering zipcode site will not ask zipcode again.
If you need change design of Auto ask ZipCode window then you can change it from Universal ZipCode plug-in view page that is available inside plug-ins → XcellenceIt.ZipCode → Views → ZipCode → ZipCodepop-up.html.