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All things Chiba and Dichromate alternatives.

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imgprojts

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I had the day off today, so I spent some time experimenting with carrageenan and reading about the success of the fish glue Chiba process. That got me thinking it might be worth starting a post dedicated entirely to Chiba methods. There’s a lot to explore, especially about avoiding dichromates and finding alternative materials that respond to other sensitizers. I had AI format this to make it more readable, I am an engineer and a horrible writer.

Here’s a list of materials I’ve tried that can form images in a gum-like process. For all of these, I’ve used safe sensitizers such as ferric ammonium citrate and ferric ammonium oxalate.
PVA SBQ seems to behave most like gum. SBQ is pricey, but you don’t need much of it, and it’s not carcinogenic. The SBQ process is chemically different from Chiba, though.

Processes that need thermal control during hydrogen peroxide development​

  • Fish glue – Has produced some impressive images. I haven't tried it
  • Rabbit glue
  • Gelatin – Your house will smell like dead animal and you'll have this hint of dead animal with you at work if you don't use gloves. I love jello and I expected so much better.
  • CMC (carboxymethyl cellulose) – Must stay above 20 °C at all times per Habib Saidane, which is easy in warm climates but tricky here in Washington State for most of the year.
  • Iota carrageenan + gelatin – Worked when mixed and exposed in cold as well as warm water. Several papers suggest that lambda and kappa carrageenans also respond to UV with Fe³⁺ salt

Processes that develop at room temperature (near 20–25 °C)​

  • PVA – Works well, you add citric acid and keep the temperature below 40 °C. Produces consistent images, though tonal range is limited. Cyanotype also develops nicely in it.
  • PVA + CMC – Same as above: add citric acid and stay below 40 °C or all of it will harden and you'll get no image.
  • PVA + Sodium Benzoate and citric acid forms a white precipitate gel that is great for mixing and paintting using a brush. Cyanotype also develops nicely in it.
  • PVA + dilute boric acid – This follows the classic slime formula. A 10–20% boric acid solution in water works; higher concentrations cause precipitation.
  • Iota carrageenan + gelatin – Works when mixed and exposed in cold or warm water.
  • PVA mixed into carrageenan gelatin – Foams heavily and the foam doesn’t dissipate quickly (or ever). I lack the patience for that, but once dry it does form an image.

Things that don’t work​


  • Ferric ammonium oxalate + gelatin, causes problems such as separating from the pigment.
  • Heating PVA+Citric acid crosslinks PVA so you can't try it with a heat gun or develop it in hot water.
  • Developing in water only. My water is alkaline and usually just washes off images on command.
  • Gelatin and PVA don’t mix well, also separate from the pigment.
  • PVA + CMC doesn’t hold pigments in suspension. The pigments settle in the pits of cold press paper after a few minutes. But it is good as a sizing because it doesn't dissolve very easily.

I recently found a great paper source: the Prudiut Store on Amazon sells 300-sheet packs of A4 300 GSM 100% cotton paper for about $58. It doesn’t need acidification for cyanotype or Chiba. It just works. They ship cheaply, so expect some corner damage (mine arrived fine, though). The box even came with a bonus bag of air, which I found amusing. like the packer thought, “You look like you could use this balloon!”

For all these processes, you need to size your paper and apply a clear coat after each layer. Otherwise, the layer underneath can re-dissolve. I use the same PVA or PVA–CMC mix for both sizing and overcoating. These aren’t sensitized; just let them dry and apply the next layer quickly. Be gentle during washing, too much agitation will destroy the image. I’ve found it best to lay the paper face-down in water after peroxide treatment and leave it still. PVA, once hardened properly, can take ages to dissolve, so you can rinse it with hot water or even under the faucet without damage. The resulting image has a rubbery feel wet and a chalky mat feel when dry. You can even spray with boric acid after development and heat it to lock the image more permanently.


Other notes​


  • At 365 nm and lower wavelengths, sodium benzoate works as a photoinitiator. At longer wavelengths, it doesn’t do much.
  • Ammonium persulfate behaves similarly and has some effects that I have not explored yet. Its supposed to develop the image as it is exposed, needing only water afterwards but that was not the case when I tried.
  • I also tried a TEOA + riboflavin dye mix with little success.
  • You can mix any of the gels above with small amounts of clear water-based 3D printer resin and get an image, but I wouldn’t recommend it. The chemicals are carcinogenic, which defeats the purpose of finding safer alternatives to dichromates. Additionally they smell.

Pigments tested​

  • Failures:
  • Poster paint (chalk-containing types fail completely)
  • Acrylic paint (no luck)
  • Successes:
  • Graphite powder – very gritty
  • India ink – stains paper if unsized
  • Mica powders – including fluorescent ones (they fog exposure a bit, but look beautiful under UV)
  • Watercolors – best overall results

Always use proper PPE and wear orange or red safety glasses! Studies show blue light is most associated with cataract formation, and UV will damage your eyes too. I tested with 365 nm UV lamps, and with 385nm using a UV projector. For negative exposures printed on inkjet transparency, anything between 365 nm and 400 nm should work. I’ve tried 395 nm and even blue light both are slower, but effective. For projection setups, 385 nm is the sweet spot since it penetrates better than 365 nm while staying within a useful range. My current setup uses a 50 W 385 nm LED (about 10 mm square), and it handles the job nicely.

Overall, this mix of safer sensitizers and alternative binders has opened up a lot of room for experimentation. The Chiba-inspired processes might not replace dichromate-based gum completely, but they’re getting close—and they’re much safer to work with. If anything this has become a passtime with no end in sight. I could probably continue experimenting until my grand kids pry my arthritic body parts off my chemical bottles. I got no grandkids yet.
 
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imgprojts

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Okay here's the gum cunundrum that is hard for me to understand... Why doesnt it just float away?

I use cold press paper because it has a texture to it which then holds the emulsion. Under the emulsion you need something to prevent the inks or pigments from staining the paper. So I use pva or pva mixed with cmc. Both immediately start dissolving in water. But thats ok if your emulsion is hardened over it. Others use gelatine or alum gelatine or gluteraldehide hardened gelatine. So okay I get it, dont let the pigment in.

With that in mind I proceede to get polypropylene synthetic paper /Yupo. I coated it in pva, pva cmc, gelatine, gelatine + boric + ammonium persulfate. Naively thinking that on a very nice flat surface I should get good coatings that easily dissolve. But nope!

When developing, I can see the emulsion harden up and then float away as a very thin pealed skin. The things I tried didnt work to retain the pva image.

Yet somehow the same thing works great on transoarencies using cyanotype formula as the sensitizer for the pva.

The gelatine one appears to work best. The stuff stays stuck and not dissolved. I bet that exposing from the back may result in better images. I dont understand how an image could even form if the light hardening the gelarine is on the surface hardening the material there and working its way down to the paper. Technically the image is only attached where it crosslinked all the way thru. Everywhere else it just hardens and floats away.

1771719588280.jpeg
In this image, the center graphic shows what I mean. If the material is water sokuble, then the hardened layers should just float away if theres nothing to anchor it to the emulsion. So maybe there really isnt a sizing that works and the anchors are just the paper fibers.
 

koraks

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What you're describing above is the exact reason why carbon transfer was invented after Poitevin ran into the same problems as you do, now. The trick behind carbon transfer is that even a thin layer of hardened gelatin on top of the tissue will end up in the print because that is transferred to a new support, where it in fact becomes the bottom layer. We're talking about the period 1859-1864 now.

So this is a fundamental problem of direct pigment processes; i.e. processes where hardening of colloids or other polymers is used as the image-making concept. There are a few workarounds, but they all have their drawbacks:
* use a very thin layer so there's always adherence to the base support. The drawback is that it'll become an extremely high-contrast medium and you get virtually no higher midtones.
* use a support that's sufficiently coarse (like the cold-pressed paper) so that the thickness of the layer is variable and you get at least some adherence here and there. The result is coarse/grainy tonality.
* use a halftone printing approach where you limit the tone that's created to just black and white, and construct intermediate tones by varying dot size (AM) or dot frequency (FM).
* exposing from the back does indeed work as well, but evidently not very well with Yupo as it's virtually opaque; it does work well with transparent media, as long as they are (1) thin and (2) the light is highly collimated. Otherwise you get a very fuzzy image.

So, to answer your question:
Why doesnt it just float away?
It does float away, but the precise thickness of the layer that can survive (Calvin Grier calls this the 'tonal threshold') depends on a multitude of factors. Under favorable conditions, you can get some gradation; this is the twilight zone that classic gum printing exploits. Note that in classic gum printing, it's customary to stack several layers precisely because of this reason; it's virtually impossible to get a full tonal range from dmax to paper white and good tonality in-between in a single layer.
 
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imgprojts

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Its weird because most paper has visible structure that is much larger than pigment so any pigmented gel will just soak an dry on relatively flat paper layers.

See, I thought paper would have "hairs" so the gel would harden around those and via that anchor it would survive the development. But I see no hairs, its mostly just a flat vertical stack of long flat strans of cellulose fiber. So then maybe the gum or gel is hardening a little under the top fiber layers? Definetly without some sort of structure below, the exposed image just floats and you're left with perfectly fine images all wrinkled and wrapped into themselves.

A hairy paper shoul give much better results, right? Maybe?. I gotta search on this.
 
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