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My method for creating highlights is similar to the
shadows. At this point, I will create a new layer
above all of the other layers. It will be a simple
transparent layer set on normal. Because it does not
contain any line art, it will not work the same way as the
shadows by changing the colors beneath it. Instead,
whatever I put on this layer will simply sit on top of the
art beneath it.
I use white as my highlight color. Selecting the
"Overlay 1" layer, I use the magic wand tool to
select a fill area. Then I select the highlight layer
and use the brush tool with settings 50% opacity 1%
flow. Then I do exactly what I did with the shadows,
brushing on highlights. I try to make them subtle
for the most part. I use the eraser tool on 100%
opacity and 1% flow to thin my highlights in the same way
as I used the white brush tool for shadows.
Alternating between my brush and eraser, I get the
highlights the way I want them.
On some very shiny surfaces, I will turn the opacity up to
100% on the brush tool. For example, Diana's hair
and choker are extra shiny and I don't have to be as
subtle. But I find that, for the most part, too many
or too bold highlights make the comic look terrible. They are
mainly there to add contrast to the shadows and complete
the three dimensional appearance.
For some items, such as Diana's necklace, I will drop in a
gradient layer rather than shading by hand.
The highlight layer, if you were to look at it by itself
against a black background, would look like this:

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