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Matte varnish relies on the matting agent, a chalky additive to what is otherwise gloss varnish, settling unevenly on the surface of the model and producing a rough texture.
If you brush on a thick coat, the matting agent has time to settle and smooth out, with the gaps between the particles of matting agent filled in by the body of the varnish. So matte varnish works much better in a spray application (either rattlecan or airbrush), where it can be applied in very thin, even layers that dry quickly.
The only matte varnishes I've personally found to work well in brush-on form are AK Interactive's matte and ultra matte varnishes, but with those you need to be careful to avoid pooling or it gets a 'frosted' appearance where the varnish pools.
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