"...and he gives you a color which he makes from well-ground copper filings;" -Cennini (Dover translation p. 111)
"Take copper that has been beaten thin and burn it in a small iron pan, until it has all fallen into a powder. Then take pieces of green glass and Byzantine blue glass and grind them separately between porphyry stones. Mix these three together in such a waythat there is one third of [copper] powder, one third of green, and one third of blue. Then grind them on the same stone very carefully with wine or urine, put them in an iron or lead pot, and with the greatest care paint the glass following the lines on the board." - Theophilus (Dover translation, p, 63)
Since I've made all but one of the period silver stain formulas I have found, I've decided to try and make vitreous paint. I started by building a frit smasher; it's not the period way to grind glass but it is infinitely easier for some initial tests.
Vasari seems to suggest you just paint with metal dust. Cennini is less specific, but doesn't contradict that. Theophilus clarifies a mixture of metal filings and glass, one part to two..
Just as with my silver stain tests, where I started off with purchased silver salts, I used my frit smasher (aka a frit piston) to smash pieces of scrap clear glass from my scrap buckets. I originally thought that this would require making paints from the same glass you are going to paint on, but nothing in the primary sources suggests that. I've seen reference that say modern vitreous paints are more "glass fluxes" and oxides, rather than actual glass; the latter would seem to be more akin to an enamel as we define it modernly. In this case I specifically sought out pieces from at least two different original sheets to avoid accidentally lining up CoEs.
Scrap glass pieces. I ended up using about twice this. My left hand for scale.
After just a few minutes work, with occasionally shaking of the pile to mix it up for better smashing
For those who don't do much with warm or hot glass, the Coefficient of Expansion relates to how quickly the warming or cooling glass expands or contracts. If you try to use two pieces of glass with incompatible CoEs, they will separate, usually fatally and sometimes explosively. I've generally seen a safe range being only one point in either direction (the common CoEs are 90 and 96 for fusible glass, with 103 also being common to lampworkers making beads. Borosilicate glass/Pyrex used by some lampworkers is CoE 33.) The bulbs I use for my ornaments class are COE 89; we use CoE 90 frit with them with no problem, but 96 is right out.
I rather expected the CoE would be a problem, and would spall or destroy the test chip. I used my frit smasher and generated a mess of pebbles and dust. Lacking anything more specific for filtering, I rolled the material in a piece of cheesecloth to get a grainy powder into a bowl.
Do not inhale this!
I ended up with a wooden bowl of rough clear glass powder. I turned to two purchased bags of metal filings, one iron and one copper. Bother are already a very very fine powder. I scooped a little of each into small wooden bowls using a palette knife, and added a similar amount of glass powder. As I stirred I worried there wouldn't be enough glass to "bind" the metal, and I added more of my clear powder. I ended up, accidentally, with approximately the ratio Theophilus called for. I did some cursory grinding on the palette, but it really didn't help. Testing it with a sable brush showed poor adhesion to the hairs, and the paint that left the brush was fairly poor, very weak with the copper-based batch. The iron batch was much better. As both metals are finely powdered I think I found a better portion of the powder bowl to draw from by luck.
Next go around, I will try to grind them up on porphyry, as period sources call for. I have been confused from time to time on what that means. Over Facebook THL Ian the Green gave me some clearer details from C&I pigment creation. He referenced this video, suggesting the technique at 6:29 and after 8:00 would be helpful. I will try and follow these next.
I placed them on some of my standard test chips, cut to size a binder full of test chips. Because it is glass powder and metal, I suspected that it would require a fairly high temperature to fire these paints; period sources definitely don't have the precise control we have, and in theory this strikes me as much more akin to glass fusing than normal paint firing. I used my standard cycle (which reaches 1250) and waited. And waited. And WAAAAITED.
The chips actually worked quite well. They didn't fire to the smooth and glossy shine of my modern Resuche paints, but they were opaque and well-adhered. I suspected, still, that they would be poorly fixed so I took the chips to my lightbox and hit them with a skewer I use for cleanup work. None of it scratched off.
The iron chip is "psychologically black" rather than optically black; When you see it, you know it's black. Your brain would remember it as black. It's actually fairly grey. The copper based pigment is a pretty color, but I would best describe it as somewhat like dried blood; It's lighter than bistre brown (which reminds me of old tree bark, it's a very dark color but not enough to be perceived as black) and it's a bit darker and more true than tracing brown, which to me has a reddish hint.
Overall, it was incredibly exciting to get working results with these very first attempts. I'm going to pursue more period steps immediately.
As an afterthought, I want to document something Master Avery shared on Facebook. I was totally unaware that you can reverse rust back into iron. The physical structure is destroyed, but the iron is recoverable. This is one way to get good, fine, filings; By using an oxidizer (and I will edit in what he offered, bleach I think) you can get the iron to rust. Then you can easily grind the rust. Putting it in charcoal and heating it appropriately will reverse the oxidation and leave iron. Very, very neat.
Lessons Learned/New Questions:
Holy cow, this worked.
It would work better if ground up more finely
Use commercial powder/better sieved home made powder?
Try the porphyry method
Does da Pisa have a recipe? Mappae Clavicula? The Bolognese manuscript? Have to check them...
I did very tiny batches, next time use my sandblasting mask to avoid any invisible dust inhalation.
How is color modulated? How is my modern tracing black so much darker? More iron? Or a darker mineral?
What will hematite look like? Pinkish, for sure, but...
What is Byzantine blue glass? A color, or a specific formula of glass? Byzantium is a purple...