Okay, I have read a whole lot of different techniques for painting eyes. I have also the firm belief that everyone has ways of doing things that they are most comfortable with. Now one of these is painting eyes.
I see that many people like to paint the whole eye black, then do two white dots on either side. This works great if you prime white. I guess. Remember, all of this is based on MY techniques and preferences, and YOU may not agree, especially if you have found a better way. The way I see it, you now have to do two, not one little tiny dots for each eye, thus doubling the chance of error right there.
Now, here is how my way works.... First off, it is common knowledge that 90% of the time I prime black. Armor, face, everything. I have just primed the old Teclis High Elf model, completely black. This is most advantageous for my technique (well, I call it mine but it is most probably not), but you can work around it if you prime white. Since my face is black, I paint the eye "areas" white, or just slightly grey actually. It is a bit messy but with thinned paints it doesn't present too much of a problem. This is cool, because now I know where the eye and surrounding detail such a lids etc. is, so I can take my dark brown inks or washes and touch up all around the eye. That is, you may clean up any white that has gone over the edge of the eyelids by using the ink or wash to cover it up. Once the skin painting begins, carefully avoid painting skin over this area and you will have nicely defined (and outlined) eyes. This leaves just a horrid looking but accurate white eye on each side. If you are doing a blind beggar, then you are done and you can move on to something else ;b However, most of us do not paint many blind beggars.
Now we have a very well defined white eye to work with. I have started using two new things when doing the next steps. Originally, I would paint a vertical stripe down the middle (or sides if the figure is looking out of the corner of it's eyes) with black and say "Bravo, on to the face and skin"! This works if you are not fussy or experienced, but now, use the iris color you want. That is, use blue if you want blue eyes, or crimson if you are painting Elric or whatever.
Now you may need to touch this up again with the wash or ink, but that is fine. Next, I made a most important purchase. I bought a Pigma Micron 0.2mm drafting pen. I will dot the iris with the black pen and voila! You have some beautiful eyes. This will take some practice, and you must ensure that the paint is dry before using the pen on it lest you ruin your pen (they are not the cheapest pens around). Now you can carry on painting your face and with careful edging around the eyes, your definition is already there!
Give it a go and remember, have fun! That is what it is all about!
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