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HADING AND HIGHLIGHTING, METHOD #1

Step 1: With your flats done it's time to give the image some depth.
Step 2: What I sometimes like to do is create a new layer to put my palette on. It will have little areas of color for all my shading and highlighting. It's a good way to see how all the colors are going to look next to each other and makes for quick access to the desired colors.
Step 3: To give the drawing some depth so that it seems it could jump out of the computer and gnaw on your elbow you'll need a consistent light source. This step is very commonly overlooked and if it is you can end up with an image that looks flat for a reason you just can't quite put your finger on. For this image I've chosen the top left as the area my light will come from.

Step 4: Set your brush on Normal mode with an Opacity somewhere around 13% (feel free to adjust depending on your personal preference),

pick the color you want to start with, use the dropper tool to select the color you want from your palette, and color away. You'll be making multiple strokes of the color you've chosen. I usually shade first and then highlight. The more strokes of the brush the darker the area will be. If you want to make a harder line increase the opacity, for a softer one decrease it.
Step 5: Once you're done with the shadows move on to the highlights. If along the way you accidentally make a brush stoke that you don't think is soft enough, like the highlights on this arm

all you have to do is use the smudge tool

with an opacity around 22% (once again adjust depending on how strong you want it to be) to smooth out the colors. Move the tool in a zigzag pattern along the area you want to smooth


and you'll have a softer transition between colors.
Step 6: Continue sampling the dark and light colors from the palette you made to go through and add the shadows and highlights to all the colors. If along the way you feel you need to add colors to your original palette don't hesitate to, but I would recommend making sure to add them to the palette layer and not just using them on the layer you're coloring.

Also, if the part of the drawing you're working on is shiny you can add some some white highlights. Do not highlight with only white. This will suck vibrancy from your image.
Step 7: Add any last coloring details, hide or delete the palette layer, and save your finished image.

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