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Here I am puting some basic color down. In both Photoshop and Painter, the way you do this is to create a separate layer for your color and your lines. The best way to do this is to have your linework on a layer above your color. In Photoshop, you just select your lines (which are probably on your background layer) and tell it to create a duplicate layer. After that is done you can erase the background layer. In Painter, you will have to select everything by pressing Ctrl + A or using the lasso tool and copy it. When you paste it, paste it on a new layer. In both programs, you will now need to make it possible to see through the white of the paper so that only the dark lines remain visible. To do this, you select the lines layer and look for something on the layer box that should say "normal". When you click on it, there should be a list of options. For our purposes, we want to select "multiply". This behaves as if you burn the darker colors down into the lower layers, letting you see through light colors. Now you are free to color on the background layer, or on another layer you create BENEATH the line layer and still see the lines.
I continue to play with the colors and try to find a more unified color pallette. I want a very blue image to convey coldness and sadness. You will notice an arrow that I painted in the upper righthand corner. This is just a reminder for me for the direction of my main lightsource.
Using that arrow as a guide, I paint in most of the general highlights and shadows in their approximate colors. I try not to be too concerned with little details at this point. However, I am very tempted to work on the heads. I tend to flesh out heads before anything else.

And here I go, bringing the details of the head out. Now, for this image, I choose not to have the linework show at the end. To do this, I created another layer ABOVE the line layer. I then paint what I believe to be the final colors on that layer, covering the preliminary sketch and the rough colors. I was not really sure how a brain looked like so I looked through an anatomy book and used that as refference. If you don't know what something looks like, find out. Don't try to fake it or it will show.

For the glass effect, I used yet another layer over the layer with the skin and brain and just painted over it with very transparent strokes, building up strokes to get the stronger highlights. To do this, just adjust the opacity of your brush.

Here I jumped right over to begin working on the goddess's face. Notice that I am trying to use a different set of skin colors for her flesh. I am using more warm and saturated colors to show that she is more alive and less cold than the male figure.

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