Making a photosensitive powder

[PeterH]

6 hours ago, jsmoove said:

...I think iron oxide can only be used as a toner or dusting on method in a photographic process, probably not part of a photosensitive emulsion itself, but I don't know for sure. ...

I cannot think of any reason why iron oxide cannot be used as the "pigment" in gum-dichromatic style processes.  Or any other photographic process with a wash-away binder carrying a pigment. Wouldn't keep banging on about it otherwise.

[Or ceramic stains with or without a  binder; eg frit or "Gerstley borate"].

PS

Just trying to make the point that if you are using a photographic process involving a pigment and wash-away binder you can to some extent decouple your experiments on pigment-selection and photographic delivery.

... of course if your pigment need to be fired it's an open question how well any pigment will adhere to a 3D shape during the firing process. (I doubt that you will find a heat-tolerant adhesive.)

Edited August 7, 2021 by PeterH
ps

[Callie Beller Diesel]

11 hours ago, jsmoove said:

that would require research and extensive testing." 

 

“We don’t know. Test it and find out.”   Everyone’s *favourite* answer!

I mean, it seems like it’s plausible. Try it!

I didn’t mention to my glassblowing friend where I thought you were in Canada, I just asked if it was available in the country. So you might be looking at mail order anyways.

[blackthorn]

8 hours ago, PeterH said:

I cannot think of any reason why iron oxide cannot be used as the "pigment" in gum-dichromatic style processes.  Or any other photographic process with a wash-away binder carrying a pigment. Wouldn't keep banging on about it otherwise.

[Or ceramic stains with or without a  binder; eg frit or "Gerstley borate"].

 

Absolutely Peter.  Iron, Cobalt, Manganese all can be and are used as pigment in gelatin or gum dichro printing. 

The ONLY thing one has to watch out for it the amount used.  I can attest to the fact that if too much of any of these is used then the emulsion becomes to opaque, like parts of the negative and blocks the exposure.  So much of the emulsion simply washes away after exposure.  Less is more with both oxides and Mason Stains and interestingly enough, that includes Mason Stain White, which I've used with film positives on dark clay bodies, instead of a film negative.

But, @jsmoove, your point about testing is, of course, correct.  I'm still doing that.  I've found many ways how not to make these processes work.

I have no experience with glass work but admire the process.  There are only so many hours for me and that's another rabbit hole in which I could easily get lost.

Edited August 7, 2021 by blackthorn

[jsmoove]

Thanks everyone. I'm not sure what I'll go with, but I'm down to experiment.  The heat resistant adhesive seems to be the main issue for a liquid emulsion.  

I don't have any experience with dichromates, where do you get them?  (pyrofoto was a dichromate) and I've read it  "is more for high-contrast line drawings or images, not continuous tone" so would any dichromate be the same? I guess thats what I'm wondering about. The decals look great, but yeah....no go for wrapping complex 3D surfaces.  

@Callie Beller Diesel The cost is certainly high to find out if it works, (would need that glass crusher too) im hoping to eventually hear from the lady who wrote the phd (contacted her on linkedin) 

Edited August 7, 2021 by jsmoove

[jsmoove]

Apparently Spruce Pine batch carried a photosensitive concentrate in 2003: 

http://warmglass.com/phpBB3/viewtopic.php?f=2&t=692&p=4784&hilit=photosensitive#p4784  

[blackthorn]

I purchased my supply of Potassium Dichromate from Bostick and Sullivan but a quick Google search will turn a dozen more places, like another of my favorites: The Photographer's Formulary.  Here's a link to Bostick and Sullivan:

https://www.bostick-sullivan.com/cart/3/109/

Yes, it's toxic. Maybe more so than Cobalt and perhaps Barium but handle with good and sensible care and you'll be ok.

ps.  Some low fire glazes actually call for Potassium Dichro.   Just saying.

Edited August 7, 2021 by blackthorn

[PeterH]

5 hours ago, jsmoove said:

Thanks everyone. I'm not sure what I'll go with, but I'm down to experiment.  The heat resistant adhesive seems to be the main issue for a liquid emulsion.  

I don't have any experience with dichromates, where do you get them?  (pyrofoto was a dichromate) and I've read it  "is more for high-contrast line drawings or images, not continuous tone" so would any dichromate be the same? I guess thats what I'm wondering about. The decals look great, but yeah....no go for wrapping complex 3D surfaces.  

@Callie Beller Diesel The cost is certainly high to find out if it works, (would need that glass crusher too) im hoping to eventually hear from the lady who wrote the phd (contacted her on linkedin) 

I'm old enough to have made potassium dichromate based indoor fireworks, but that was another time.

Maybe @blackthorn can suggest safer/greener sensitisers/processes. These are just a couple of google hits.

Gum Diazo Printing v1.4 https://www.alternativephotography.com/gum-diazo-printing-v1-4/

The present paper aims to be a reference guide to anyone in the EU willing to go on printing with pigmented gum while being fully compliant with the actual safety regulations regarding chemical substances (i.e. avoid the use of dichromate, illegal as of September 2017 in the EU).

Although many people may have some leftovers of the sensitizing agent still in their cabinets, it’s hard to imagine that anyone would go on using illegal substances even in small quantities, also because health concerns have more than solid background and vast scientific literature is available documenting how hazardous the hexavalent chromium compounds can be.

Also A non-toxic alternative to gum dichromate https://www.jstage.jst.go.jp/article/photogrst1964/70/Suppliment/70_Suppliment_74/_pdf/-char/en

[jsmoove]

I had mentioned diazidostilbene earlier: https://www.phototypie.fr/en/reactifs-photosensibles/14-diazidostilbene.html  which is green. As for heating it, the msds is in french and says that its explosive. But maybe its ok?  No idea.  

Checking out your links!

Edited August 7, 2021 by jsmoove

[PeterH]

7 hours ago, jsmoove said:

I had mentioned diazidostilbene earlier: https://www.phototypie.fr/en/reactifs-photosensibles/14-diazidostilbene.html  which is green. As for heating it, the msds is in french and says that its explosive. But maybe its ok?  No idea.  

Checking out your links!

As you are aware your link gives an article about using this product and a picture of it.

On the picture you can see that it's CAS number is 2718-90-3.

Aside: A CAS Registry Number, also referred to as CAS RN or informally CAS Number, is a unique numerical identifier assigned by the Chemical Abstracts Service (CAS) to every chemical substance described in the open scientific literature.

There is an MSDS for 2718-90-3 (4,4'-Diazido-2,2'-Stilbenedisulfonic Acid, Disodium Salt) at https://fscimage.fishersci.com/msds/67032.htm

There is an MSDS for 7778-50-9 (Potassium bichromate) at https://www.fishersci.com/msds?productName=AC197760050

----------------

PS Anybody know a way of finding MSDSs in a uniform format, the disparate styles don't help comparison.

PPS Google translates the warning you mention in the French-language MSDS as:
Risk of explosion in case of fire. Fight fire remotely due to the risk of explosion. Be careful as it can decompose on combustion or at high temperatures and generate toxic vapors.

My personal suspicion is that this is intended as guidance to fire brigades attending factory fires where there might be drums of the stuff lying about. If this is the case the warning may have little relevance to the owner of a 25/50g bottle. Although I definitely wouldn't throw it on the fire, and take due care disposing of it.

[jsmoove]

@PeterHI was not aware! So I guess the decomposition point of both would be too low for firing?  I wonder if there is a way to search "light sensitive" with high decomposition points for materials through fishersci msds's?  

Going back to old territory....for cyanotype: what is the reason it can be fired to ceramic but not to glass?  When the iron is left over? The leftover iron's decomposition point is quite high right? What temperature would the iron decompose for cyanotype?

"Although it's main light sensitive constituent is iron, the iron is fugitive at higher temps.  I've not yet tested it's high limit but at bisque it comes off a nice toasty brown."

@blackthorn

Edited August 8, 2021 by jsmoove

[PeterH]

14 hours ago, jsmoove said:

@PeterHI was not aware! So I guess the decomposition point of both would be too low for firing.  I wonder if there is a way to search "light sensitive" with high decomposition points for materials through fishersci msds's?  

Going back to old territory....for cyanotype: what is the reason it can be fired to ceramic but not to glass?  When the iron is left over? The leftover iron's decomposition point is quite high right? What temperature would the iron decompose for cyanotype?

@blackthorn

There seems to be a degree of mutual confusion. I'll explain my thoughts.

Decomposition temperatures

1) If you use a method like pigment-loaded gum-dichromate (or gum-DAS) after exposure and development you finish up with an image consisting of varying thickness of pigment-loaded "gum".

2) Essentially you have created a "transfer" in-situ. Either sitting on top of a glass/glaze or within the top layers of a porous ceramic.

3) At this point the dichromate/DAS has served its purpose, and can be burned-out with the gum during the firing.

4) Hopefully the pigment will stay in sufficiently close proximity to the surface to be fused/incorporated into it during the firing.

There is absolutely no need to look for light-sensitive materials with a high decomposition temperature for this process.

Cyanotype

You state that cyanotype "can be fired to ceramic but not to glass", a reference for this would aid the discussion. But here we go:

1) The cyanotype process precipitates out a strongly coloured iron compound, which forms a strong image. If fired this will decompose to a paler iron oxide. Here are some pix of the unfired image. I've yet to see any pix of fired image. https://tinyurl.com/8ubba93x

2) Legalistic quibble. The initial cyanotype process was a liquid process and relied on the backing material (paper,cloth, etc) to hold the precipitated compound in place. This carries over naturally to porous ceramic but not to water-proof glass/glaze.

3) A long-standing solution to this problem is the precipitate the iron compound into a layer of gelatin or similar. https://tinyurl.com/ynhzneer

4) If you want a fired-on image from such cyanotype I would just try firing them. The situation is not that different from transfers or gum-DAS images so the chances of it working are promising.

5) Do we know anybody who has tried this? How successful was the attempt?

Finally photo-sensitive glass

This presents a completely different and formidable set of challenges.  Which I'll comment on in a separate posting.

Edited August 9, 2021 by PeterH
added url

[jsmoove]

@PeterHThanks for breaking this down. I think im confused about the pigment part (#4) How do we know what pigments survive the heat?  

I think my question for the cyanotype is, at what point/temp would the iron actually be fused to glass? I think you're saying it's more trial and error correct?  What is the ballpark? 

I'm mostly confused about the fusing process, if I'm after an image that is completely permanent on glass that will never come off, is fusing materials what im after?  

And #5, I am also curious to know if anyone has tried it...mostly since I don't own a kiln, so I want to understand what would be the most foolproof technique before an attempt.  

Curious to hear your second post on the photosensitive glass too...to me it seems the least toxic to work with, but the most challenging as you say.  Unfortunately not much literature on this.  

Edited August 9, 2021 by jsmoove

[blackthorn]

2 minutes ago, jsmoove said:

I think im confused about the pigment part.   How do we know what pigments survive the heat?  

 

Reading just about any book on Ceramics will provide info on pigments that are used, and the better ones will describe the behavior of most at varying temperatures.

Since we know that:

"Glass melting is performed at temperatures between 700°C and 800 °C which correspond to an optimized value of the viscosity for glass refining and shaping",

we can surmise that firing an exposed and processed sheet of glass will begin to flux at temps nearing that.   Experimentation would be essential to see   1) How high is high enough to completely bond with the surface image;  2) How high is too high, which would result in partial or complete distortion of the image, ala Salvador Dali;  3) If it's even possible to sufficiently melt the glass without it bonding to whatever  cookie or shelving it's resting on during the firing.

 

[blackthorn]

9 hours ago, PeterH said:

1) The cyanotype process precipitates out a strongly coloured iron compound, which forms a strong image. If fired this will decompose to a paler iron oxide. Here are some pix of the unfired image. I've yet to see any pix of fired image. https://tinyurl.com/8ubba93x

2) Legalistic quibble. The initial cyanotype process was a liquid process and relied on the backing material (paper,cloth, etc) to hold the precipitated compound in place. This carries over naturally to porous ceramic but not to water-proof glass/glaze.

3) A long-standing solution to this problem is the precipitate the iron compound into a layer of gelatin or similar. https://tinyurl.com/ynhzneer

4) If you want a fired-on image from such cyanotype I would just try firing them. The situation is not that different from transfers or gum-DAS images so the chances of it working are promising.

5) Do we know anybody who has tried this? How successful was the attempt?

@PeterH To your points 1 and 5 - I posted images of some of my recent tests earlier in this thread.  To your point 2 - I've found this to be true of fully vitrified stoneware and porcelain, so I coated it with a combination of equal parts of Whiting, Gesso and water.  It remains stable long enough to allow for exposure, processing and firing if it done within a day or two.  I haven't tried it yet but I'm also going to spray paint flat white, sand and repeat a few times, on a fully fired slab to see if it allows cyanotype to not bead up.  Gum or gelatin will bond to the painted and sanded surface. 

[PeterH]

43 minutes ago, jsmoove said:

@PeterHThanks for breaking this down. I think im confused about the pigment part (#4) How do we know what pigments survive the heat?  

I think my question for the cyanotype is, at what point/temp would the iron actually be fused to glass? I think you're saying it's more trial and error correct?  What is the ballpark? 

I'm mostly confused about the fusing process, if I'm after an image that is completely permanent on glass that will never come off, is fusing materials what im after?  

And #5, I am also curious to know if anyone has tried it...mostly since I don't own a kiln, so I want to understand what would be the most foolproof technique before an attempt.  

Curious to hear your second post on the photosensitive glass too...to me it seems the least toxic to work with, but the most challenging as you say.  Unfortunately not much literature on this.  

"What pigments that survive the heat" is an easy one: use ones in regular use in pottery. Such as "oxide-washes" and "ceramic stains".  @blackthorn mentioned some in one of his earlier posts. Often a little frit or Gertsey borate (or it's modern substitutes) is added to aid the fusion. Temperatures depend strongly on the glaze (or glass) you're fusing onto. Glaze choice constrained by the clay body of your "pot" (must match thermal expansions).

I've no idea if anybody has tried #5. You'll probably need to suck it and see ... or get lucky with literature-search/google. On the other hand if it doesn't work pretty much all avenues to fuse an "alternate photographic techniques" image to glaze/glass are probably doomed.

Parting thoughts

As stated pretty everywhere in these threads: test, test, test. Either it's a thought-experiment or you need to start making & firing at least some test-pieces. Perhaps join a local studio and get a little hands-on experience, and contact with potters at work.

You also will only succeed if you can get all the stages (including exposing the  3d object) working right. A chain is as strong as its weakest link, and all that.

Obviously you need to safely manage any fumes arising during firing.

... and I should have said that mixed-media is a legitimate choice if it satisfies your objectives. So covering an image on a porous pot with some sort of sealer might meet your needs (varnish, brick sealer, clear paint, ...) and would save a lot of hands-on learning pottery 101+. Or act as a stepping stone to greater things.

Edited August 9, 2021 by PeterH

[PeterH]

@Callie Beller Diesel gave an excellent choice for a "pigment" way back. A coloured frit, presumably with the same coefficient of expansion as the glaze/glass and with a softening temperature chosen to facilitate fusion.

 

 

[jsmoove]

I glazed over the ceramic stains and oxide washes part, I think I understand now. Yes, I think I will look now into what is available in my area.  I like the idea of starting with cyanotype as it's easy to obtain and try out.  

And your thoughts on photosensitive glass as a powder? @PeterH

[blackthorn]

From earlier today.

This will bisque to a light toasty brown.  Any higher and it will dissipate completely.

 

[PeterH]

The idea of "off-label" use of ground photochromic glass-blowers glass is a bold one, but has lots of potential pitfalls. The outstanding one was mentioned early on by @Callie Beller Diesel, The differences the COE (coefficient of expansion) between this glass and your likely substrates. A problem potters have a lot of familiarity with (matching body and glass to avoid crazing or shivering).

While exploring the availability of this expensive photochromic glass (and ways to reduce it to a frit of the right grain size) I suggest you make the first steps in testing if such a frit could be "fused on" in a satisfactory fashion -- where the finished article is capable of passing "stress tests". https://digitalfire.com/glossary/thermal+shock

At the moment I've only got one potentially useful idea, and a wild "Hail Mary" suggestion.

The good idea is to find a supplier of a coloured non-photochromic glass frit of similar COE and melting characteristics as your target photochromic glass. Fuse-on using a photochromic-glass "striking" schedule. Experimenting will be a lot easier (it's already ground) and cheaper. If you cannot get this to work , it's not worth going any further. If it does work you're good to go on your next tile: switch to photochromic frit, glue, expose, fire.

My "It's a one in a million chance, but it might just work" idea it to try a sodium silicate glue to fix the frit to the glass/glaze. While details are hard to find sodium silicate has found applications in highish temperature applications (eg auto repairs: leaking cooling systems, fixing damaged exhausts). Not 100% sure of how waterproof the final product would be (clean-up of silicate glues is with hot water), but if it fixes car cooling systems?  IMHO It's worth a few test-tiles.  I doubt if it would solve the COE mismatch though.

PS  Note that sodium silicate is a generic name https://en.wikipedia.org/wiki/Sodium_silicate

... In early tests I would guard against spitting.

PS 1st fact sheet I could find https://tinyurl.com/4p8k6yv3

 

Edited August 10, 2021 by PeterH

[Callie Beller Diesel]

7 hours ago, PeterH said:

matching body and glass to avoid crazing or shivering).

Glass workers tend to have a much better grasp on this idea, as any cracking for them is a major deal breaking flaw. Crazing in pottery is in some instances an encouraged aesthetic. There’s a lot of instances where things that are considered flaws in glass are desirable in glaze. 

Glass materials suppliers will be able to direct you very easily in regards to combining blown glass frit with slumping glass, or even commercially available float glass. From the manufacturer’s specs that I was reading, of all the technical obstacles in this project I don’t think fusing a frit made from that particular brand of  bar stock to float glass will be one of them. Getting it to the right grain/mesh size will probably be the most time consuming/labour involved bit, if that’s the method you want to try.

[jsmoove]

On 8/7/2021 at 2:41 PM, jsmoove said:

http://warmglass.com/phpBB3/viewtopic.php?f=2&t=692&p=4784&hilit=photosensitive#p4784  

Apparently there was a photosensitive concentrate made by Gaffer discontinued in 2005.  I've learnt that Gaffer is owned by Reichenbach, so maybe there is a chance that they still can make it.  (unlikely, but you never know?)  I'm assuming concentrate means dry materials.  

- So Gaffer's current stock for photosensitive glass is stock that they had before the switchover.  Reichenbach owns the brand now and technically will be making it since they are testing recipes apparently.  Originally Reichenbach did actually carry photosensitive glass, they had the gold, copper and yellow.  This is old info:

https://imgur.com/a/M37Ojbs  

@PeterH I had also come across sodium silicate and wondered if that would be a good binder.  I think im in too deep here without firsthand experience. As you say, to test out fusing frit first. Alot of factors!  (that makes 4 F's)  

 

Edited August 11, 2021 by jsmoove

[PeterH]

14 hours ago, Callie Beller Diesel said:

Glass workers tend to have a much better grasp on this idea, as any cracking for them is a major deal breaking flaw. Crazing in pottery is in some instances an encouraged aesthetic. There’s a lot of instances where things that are considered flaws in glass are desirable in glaze. 

Glass materials suppliers will be able to direct you very easily in regards to combining blown glass frit with slumping glass, or even commercially available float glass. From the manufacturer’s specs that I was reading, of all the technical obstacles in this project I don’t think fusing a frit made from that particular brand of  bar stock to float glass will be one of them. Getting it to the right grain/mesh size will probably be the most time consuming/labour involved bit, if that’s the method you want to try.

Glad somebody is keeping their eye on the ball, I was getting fixated with the "on-glaze" problem.

---------

Do you have any idea if their are any constraints on the thermal treatment of the photochromic ruby glass prior to exposure to UV?

PS Skimming Weyl's "Coloured Glasses" suggests that:
- Pre-exposure the glass is rich in both Cu⁺ and Ce³⁺.
- On exposure the concentrations of Cu⁰ and Ce⁴⁺ increase.
- During the strike firing the Cu⁰ atoms congregate into copper nanoparticles.

Edited August 11, 2021 by PeterH
clarity

[PeterH]

On 7/30/2021 at 1:11 AM, jsmoove said:

The thing is, nowhere is it mentioned in the thesis what type of machine they use to crush the rod into powder.  

 

On 7/30/2021 at 8:31 AM, Callie Beller Diesel said:

For the first: From the couple of classes I took in hot glass, if you’re making your own pate de verre or glass frit, usually you’re pounding it out by hand somehow. At school they had a 4” steel tube with another really heavy capped off steel tube that fit inside it that acted as a very analog piston, or a tube shaped mortar and pestle. If you wanted, you could create powders out of rod or found glass. It’s a LOT of elbow grease. I don’t know if that was a tool specific to the shop I was in, or if they’re commonplace in other hot glass shops.

Might be worth glancing at
DIY To the Rescue: How to Make a Frit Piston
https://www.delphiglass.com/blog/how-to/diy-to-the-rescue-how-to-make-a-frit-piston

Scaling it to a suitable size

[jsmoove]

Regarding liquid light, there appears to be one person who was able to fire it on glass:

"As part of my PhD research I have been using liquid light on cast glass with some success using chemistry from Rockland Colloid.
I have used various varnishes as a sub but found the best results from cleaning the glass properly and applying the emulsion direct. I have done this mainly because I am then firing the glass in a kiln. AG-Plus has a higher silver content and so is ideal for firing but regular liquid light works just fine too."

From: https://www.photo.net/discuss/threads/liquid-light-on-glass.231705/

https://www.photo.net/gallery/592725#//Sort-Newest/All-Categories/All-Time/Page-1

I don't know the temperatures he used though.  This is 2006.

[blackthorn]

From what I found in my research on slumping glass onto ceramic substrates:

Fire the kiln to a temperature between 1200 to 1300°F (648.9 to 704.4°C), keeping an eye on the glass through the peephole.

The glass will begin softening and turn glossy when the temperature nears 1000°F (537.7°C) and start slumping as it nears 1200°F (648.9°C).

Sadly, I think this is much higher that the silver in Liquid Light can endure but have yet to confirm this.  It will likely dissapate above 1000ºF.

It's on my list to test but will require dedicated kiln time at the school and we're in the middle of a term with students scrambling like ferrets to have their work fired.

Still, sounds interesting and I'll pursue it as time permits.