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I want to do something with my cadians to make them unique, and decided that goggles resting atop their helmets would look great, and go with the valkyrie airborne cavalry theme I'm going for. I am quite a green stuff amature, does anyone have any tips?

Use water to help make the greenstuff a lot easier to work with just wet your fingers tips when you use it
As for the goggles I would use the back of a pencil to make the circles
Cut those out and add some extra detail then WHAM you has goggles
Maybe the pencil would be too big try something smaller

Or an idea for not using GS. You can chop up some ink pen tubes. They are pretty much the perfect size for that. You could then use small strips of GS for the straps and such.

PVC tube/piping is cheap at most hobby shops, look for a variety pack, they have a whole bunch of sizes for all sorts of projects as well. Use green stuff for the optics base and trim short pieces for the scopes. Another option is to get the NVGs from Space Marines Scouts. The attachment area works fine without the googlies so your scouts won't look completely silly if you do a good job.

Yeah, I'd use plastic tube for the goggle lenses, just greenstuff the straps. That presumes you want round lenses, of course.

And since you'll need a fair few, making one then making a rubber mould might be a good idea, they'd then be very easy to cast by pressing greenstuff into the mould.

Casting them does seem like the easiest way to do it. There is an article on dakka about it, maybe it was a tutorial, I can't remember. If someone knows where this is please post it up.