View this collection of Picasso collages. He was a great innovator with materials, form and positive/negative space.
http://www.nytimes.com/slideshow/2011/02/11/arts/design/20110211-picasso.html
http://accidentalmysteries.blogspot.com/2010/07/16-collage-artists.html
really nice visual culture blog + links
Robert Rauschenberg, American Artist, Dies at 82 - New York Times
Robert Rauschenberg was discussed in Digital Studio recently, his hybrid artworks were a brilliant predecessor of the current photoshop layered collage aesthetic. Here is one from 1963...
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No, not digital art, this is silk screen and mixed media.