Yes, with CSS, only round / elliptical borders are available. If you need other shapes, you will need to use an image.
You can get straight diagonals by abusing boundary connections:
<div style="background: gray; height: 100px; width: 200px; position: relative;">
<div style="height: 1px; width: 1px; border-top: solid gray 20px; border-right: solid white 20px; position: absolute; bottom: -1px; right: 0;"></div>
</div>
Not sure if a particularly good idea.
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