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Usually the webcam window has a maximize icon on the top right and if you click on it,it becomes full screen. Can you give me more details about which chat software you are using so that i can give you more details about this.
You need to find a video chat program that you are comfortable with. Most of the major Instant Messenger programs have been adding video chat to their features over the last couple of years.
Check this link for a good summary of current products and some excellent advice and reviews.
They favour windows live messenger - just be sure that whichever program you choose will support your camera, and will work on your PC.
If you need help using the software, please ask again once you have decided which to use and we can try to help, but the majority of them are reasonably easy to set up and use.
Hope this helps :)