HQ-TEA -- A shelf-stable customizable lith developer part A

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grainyvision

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So I was really unhappy with the state of homebrew lith developers, especially since Easylith isn't cheap and most others contain formaldehyde. I wanted a lith developer part A that contains little sulfite, is minimally acidic (ie, doesn't require a lot of part B to neutralize), and is shelf stable for at least several months, even if tray life isn't great. I stumbled into mixing hydroquinone with triethanolamine in order to make an ideal lith developer that is shelf stable, and contains literally nothing else and thus completely open for customizing with different ratios of sulfite etc.

My recipe is super simple:

* TEA - 300ml
* HQ - 60g

Heat to at least 170F/76C and mix to combine, 190F/88C makes mixing easier. Keep in mind that TEA is flammable. The autoignition temperature is ~250C but I see no need to bring the temperature above 100C. The HQ may reduce the temperature and require more heating. There may be air bubbles which resemble crystals, but if they try to float to the top with no stirring then you know it's just air. Note that this will increase the volume of the solution to around 350ml. If using an exact bottle size, keep this in mind. Final solution will progress from a bright yellow to a slightly darker orangeish-yellow.

More HQ could be dissolved in the TEA, but at that point it gets kinda difficult to measure with a graduate. Anyway, so this is literally just HQ in an alkaline syrup. No water is present and in theory it should last practically forever despite containing no preservatives, similar to HC-110. Using a lith developer like this requires several more "parts" because HQ and alkali alone are not stable once you introduce water.

I recommend keeping on hand:

* 10% solution of sodium sulfite
* 10% solution of potassium bromide
* 10% solution of potassium/sodium carbonate OR 1% solution of sodium hydroxide
* 1% solution of citric acid (acetic acid or some other stable acid should work too, I just prefer non-smelly)
* syringe capable of measuring less than 10ml
* graduate for measuring 5-50ml

A starting point mix is the following:

* 1L of water
* 15ml of HQ-TEA
* 10-30ml of 10% sulfite
* 5-20ml of 10% bromide

This should work and may be a bit fast depending on paper choice. TEA has a pH of around 10-11.2 depending on dilution, so add some acid if the activity is too high as if you had added too much part B with standard lith developers. If using yellow technical grade TEA, it can have a pH of up to 12, so a starting point mix would probably require something to bring down the pH.

General notes:

* Some papers show excessive snowball type effects in shadows and blacks, increase sulfite for this.
* Some papers *may* (unconfirmed) react with even a weak solution of TEA+bromide and cause fogging and/or degredation of dmax and speed. This is learned from my research of "PFS-4", but unsure it applies with developing agents and sulfite present.
* If the developer has a distinct red film on it especially near tray edges, do NOT attempt to process anything else until adding enough sulfite to dissolve the red film and 2-6ml more sulfite so that it keeps working for each print, usually around 6ml total. If you live on the edge with this developer always being almost dead, plan on adding 2-10ml of sulfite after each print, especially if a lot of blacks are present in the image being printed.
* you can print with no sulfite present, but the results will be terrible, low contrast, and with no infectious development. Some amount of sulfite is required and consumed by infectious development.
* When the developer is right on the edge of dying and you can see a film moving around on the print in development under safelights, you can move the print to a water tray, add some sulfite to the developer, mix it up, and put the print back in
* If there is not enough sulfite, along with slower development action, you can get fogging on edges that looks like blur/out of focus, and will get low contrast without proper infectious developed blacks.
* This will work fine with no additional alkali in my experience and TEA seems to be a much more stable pH buffer than carbonate/hydroxide. If you prefer less color or faster times, you can add some alkali though.
* If using minimal sulfite your developer will die.. a lot. It can be revived with sulfite usually, but it does seem to easily just get overloaded with restrainers from printing after ~15 prints. The developer isn't truly dead until it's brown and sulfite does nothing to the color.
* I've tried replenishment (HQ-TEA+sulfite) after true developer death, but it didn't go well. Needs more testing probably
* This seems to be a cooler tone lith developer than most other lith developers. One paper type (Kodabrome) which typically prints out to peach and warm orange tones, printed out to green shadows and peach highlights. Another paper type (Polymax) which typically prints out neutral instead printed out with with cool blacks and subtle lilac highlights. This is probably due to both TEA having some side-effect, and the lack of formaldehyde and relatively low sulfite content.
 
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grainyvision

grainyvision

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Would be great to see some prints from your recipe.
G.

Here are some, had to wait for them to dry completely:

Kodabrome:
hqtea-kodabrome_2.jpg

Polymax: (notice snowballing type effect in second image)
hqtea-polymax_1.jpg

hqtea-polymax2_1.jpg

Fomatone MG WT (unsure if this is even a lithable paper, first time using it)

hqtea-fomatone_1.jpg
 
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grainyvision

grainyvision

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Finally got the kind of results I'm looking for:

hqtea-test.jpg

Also, bonus video of infectious development in action:



Recipe (approximation, 3 prints previously done and some chemical adjustments in between)

* 1.1L water
* 10ml HQ-TEA (1:5 HQ+TEA)
* 5ml 10% bromide
* 0.6ml 10% sulfite
* 2.5ml 10% citric acid
* temperature controlled to ~100F
Paper: Fomatone 133 FB "velvet"

Definitely got really nice color and lots of infectious development. This paper develops in this combo unlike anything else I've seen. It will show borders within 30s, show a faint image at 3m, and finally show a low contrast version of the image at ~6m. Then.. nothing happens for 1-2m and then suddenly a streak of black will begin to appear and all the blacks suddenly start to explode with infectious development that you can readily see under safelights.

The biggest problem is that infectious development will literally infect the image beyond blacks. I found extremely gentle agitation at this point and even just letting it sit for 1-2m with no agitation helps to constrain it, but it's definitely not perfect. With normal agitation it will eventually fog the entire image. I'm unsure how to reduce this effect nor why it happens in this way. Might just be an oddity of the paper. Has anyone seen anything like this before?

General developer mix notes:

* Although adding sulfite to this developer once its red will "revive" it, the sulfite and/or byproducts do accumulate and change the developer characteristics. After a few rounds of revival you'll find it very difficult to get proper infectious development even by adding additional HQ-TEA or alkali
* By neutralizing the HQ-TEA with quite a bit of citric acid while keeping sulfite content very low, the tray life of this run was a lot better, lasting about 1-1.5 hours with no chemical changes.
* Keeping the sulfite content low makes the developer speed somewhat faster despite being a low pH developer
* It appears that the developer will exhaust more quickly from infectious development (ie, blacks) than from oxidation by air. In fact, leaving the mix alone for 20 minutes in a heated open tray didn't seem to change color/activity at all.
* This mix will be perfectly clear when first mixed (unlike standard pale yellow of most lith developers) and grow slightly pale yellow as it is used. When exhausted it will quite suddenly turn a reddish brown. More sulfite will return it to a darker pale yellow color
* Unsure if its the paper or the mix, but had to use surprisingly low exposure levels to get the right amount of contrast, With a lot of exposure or big area of blacks/greys uneven development is still pretty likely to happen it seems, but reducing the pH seems to help that considerably compared to without any acid
 
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grainyvision

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Did you use any of the seasoned developer as Old Brown for a new mix? I like the Kodabrom results.

No I haven't been using any old brown. Because of the strict way I'm controlling and replenishing sulfite and acid, I prefer to substitute bromide for old brown and make a fresh mix each time with known components. I'm sure the general 20% old brown guideline would work well, but I'm focused on consistency at the moment. I'm eventually gearing up to formulate a proper "part B" for this which contains ideal ratios of bromide+acid+sulfite for 1:1 mixing with part A for good consistent results.
 
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grainyvision

grainyvision

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Sounds exciting, are you a chemist by training.?

Definitely not, and it's definitely what is holding me back. For instance, found a very interesting patent which claims to allow minimal sulfite use in a lith developer while tripling tray life. Problem is that it's all in notation I don't understand, and even if I did I have no idea how to go about formulating any of the compounds needed.

Anyway, another set of updates and trials... Lots of failures, so many.

Got some pH test strips so I can at least have some judgement of what level my developer is at. I almost definitely don't need to add citric acid ever and should instead do something else. Nominal pH on previous developer mix is ~10, basically right at the bottom line of a viable pH for infectious development


I Did many many many tests wasting MGV and Ilford cooltone paper. It's impossible. Tests include using thiocyanate instead of bromide, extremely alkaline, extremely not alkaline, tons of HQ, very little HQ, tons of sulfite, very little sulfite, bleach prebaths, bleach before exposure, peroxide prebath, PFS-4 prebath, carbonate prebath, 10% hydroxide prebath, and probably several others I'm forgetting. I'm giving up on that pipe dream for now, aside from for second-pass lith anyway. In all cases it either developed normally (ie, linear), gave black fogging, or gave a very low contrast image before doing absolutely nothing and never developing proper blacks

Did a lot of testing with thiocyanate instead of bromide on the lead of a patent and these from the 70s indicating that heavy iodide emulsions could undergo infectious development with thiocyanate present in equal weight to bromide, whereas often heavy iodide emulsions just flat out don't lith. It does indeed "work", but it's extremely finicky. If pH is at all low (<10) it'll literally eat the silver off the paper. With the exact right amount it behaves like both a selective development accelerator and restrainer, making blacks go infectious quicker and holding back highlights. Thiocyanate is commonly used in reversal developers for 100% dmax blacks, but I haven't seen a single reference other than the thesis and patent of it ever being used in a lith developer. Too little and it seems like nothing happens. Too much and it'll erode blacks and instead of deepen them, along with making development super slow. Either way it's an extremely interesting direction to be testing. I find it's not really a perfect restrainer either way. You can have a ton and development will still runaway too quickly to be even if your developer mix is too strong. A tiny amount of bromide in the initial mix, such as 0.2ml of 10% helps prevent absolute runaway.. It seems almost super additive or something with bromide, causing even a tiny amount of bromide (such as from doing a single print) to drastically slow down development, and making development impractical after just 4 prints due to too much restrainer, despite the HQ still being mostly clear and pH remaining stable. One paper (polymax) which normally gives rather boring and neutral colors I got very bright colors with using this technique, unfortunately they subdued a lot once dry but shifted to a quite obvious cool purple and lilac tonation. At just the right point in the developer lifecycle polymax became an extremely convincing lith paper with shadows truly developing first and quickly becoming infectious before highlights looked to be "done". A print afterwards though went extremely slow with significantly less infectious development in shadows, but still a bit. Normally polymax is just meh, it's barely a real lith paper with full control of contrast.

Tried to figure out some other papers that don't normally lith, which has slightly more promise. Adox MC112 got lith-like (weak, but "proper" infectious blacks) in one test, but it was uneven, leached into highlights, and I couldn't reproduce it in new mixes

An Oriental paper I tested went extremely bright red in the process, with yellow fogged borders (probably because of orange safelight, forgot you need red for it). No real lith effect though. Blacks went a flat grey green and spread across the image but without convincing infectious development type effects. It's definitely a brighter red than I've ever seen a print though, quite incredible.

I think a proper starting point formula for a thiocyanate based lith developer is like so:

* 10ml HQ-TEA
* 6ml sulfite 10%
* 15ml thiocyanate 10%
* 0.5ml bromide 10%
* 25ml hydroxide 4%

Discard after 5 prints, maximum. Best heated to 90F (too hot can be subject to runaway), image will show up in 2-3 minutes on most papers and snatch point at 5-10. Also warning: it smells pretty strongly of ammonia when warm and you're developing (no smell when not developing)

It definitely will produce a different set of colors on known lithable papers, and might be capable of making some non-lithable papers lithable and/or difficult papers easier, but I'm having trouble figuring out if any of my papers are even rich in iodide for testing that theory

Also a small sample of the different mixes tried, though I got lazy and stopped taking generalized notes on the results:

AgEOgqrTj86IwuZj2riwSR3nehdPgoJaEthkXkG_VD_y5frE8dpU83VLXYuqK6R9RxRDiHzq3CUCm_K8Fn0BGSgUTRp0wGX5zxnirkEgehHMVfmx7faM-k-sxm7Nv19WfSmg8oqhqHuhmKf7N0bTAHWweWg3FVlJl78WgJpVVao33nwrAJtilCw5cFWJw-QsgXIQkvBmiurBgiUIT4WHSZbvDGeYl0oXZzVFz09uK6f89gASNYwry9KJPvHEi49Eic5_yjy2v33UZSYYD4-a3EgkSaGIkHeaFd4pX6sh5ccR_W8hp8lswszvmt0PCNut2m_MlkSsazMkUPpFIzNAYFX_Y6YcsxLOX8QZGsGGrejM1TvcTA5wo9TNfwi8Jvk38v2s1t9jjxcrWkpPAVx2Vw1sLKqxsJ4gUYrEgGiJUVN-KheJuJYgCAskSJi6smUrGR27QpvqXJNDa6YRfrIw9_VbTebFJuZuKbMI521q53Y_cv1Sj3-sKnpk8vo_3rGG8s6JmQqjOkZwlJFNdIqNswQ9orQdkIKiJim3hNTnI6jfjEjiHz64lk504h0GmWg2V6GYMjQE0OnebiucEm350CBxywRR940MKGbSABL3h-Hei0LijhrEo4kZW6_XpHBQD3aYTU1o4GHLEBrEdBA78EX9t5cd4enuURFqJNvsSxbXq4x3NU_ULNxL=w1730-h1298-no
 

Dali

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I second Adelorenzo's comment: Great work!
 
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grainyvision

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Ok, so despite me saying lith printing with Ilford RC papers is impossible, I've got a lead. I've made the most lith-like print by experimenting.. a lot with different mixes.

Important discoveries with Ilford Cooltone RC:

* A halide of some sort is required.. (ie, bromide, iodide, etc). Without one, infectious development will not happen
* The minimum pH for getting proper blacks is 11. Below 11 very little if any infectious development occurs
* TEA appears to be optional and an excess should not be used, but the amount of TEA used in HQ-TEA mixes isn't enough to matter. More TEA can potentially lead to some areas becoming bleached.. maybe
* Bromide and thiocyanate will NOT facilitate infectious development. In fact, either component in any significant quantity will completely prevent infectious development. (<0.1g of bromide, <0.5g thiocyanate per liter)
* It takes a ton of iodide in order to properly slow down lith development enough to not be.. well, a "lith" print with 100% black/white. I had to mix a 10% iodide solution just for the occasion (normally I only have use for 1% or more often 0.1%)
* Initial "lead" tests were done using a ~40C heated solution of 300ml in lab equipment with a magnetic stirrer under daylight and cut up strips of paper. I basically figured I had a lead when the paper didn't go black instantly, and it first went grey and then had "streaky" blacks that spread with time, and used only hydroquinone for the devleoping agent. Adding a tiny amount (probably 0.05g) of phenidone seemed to produce some similar results, but it's too hard to tell with this setup if that is hyperadditivity happening or if it actually helps to make infectious development happen

Ok, so onto the formula for this print:

* 15ml HQ-TEA (formula from above)
* 10ml sodium sulfite 10%
* 10ml potassium iodide 10%(!) -- more would've probably helped, but I ran out
* 40ml potassium carbonate 20%
* 10ml benzotriazol 1% --this was an isolated test (ie, not tested before in anyway) to attempt to slow down development. More testing required to figure out if this was too much or not enough
* measured pH, ~11.25 (pH strips, so I can't give much accuracy)
* Printed f/5.6, 20s -- about 4 stops greater than a normal print
* Print was rinsed well with running warm water before development to eliminate known surface incorporated developers that would've activated at this pH level.

The lifespan of this developer is SHORT. If you need to do an especially long exposure, I recommend premeasuring the carbonate and only dumping it in after the exposure is complete. Adding some additional sulfite can help lifespan, but there is a definitely fine point where adding a tiny bit more sulfite will completely halt infectious development. Even if the HQ in this formula didn't expire extremely quickly, the little bit of bromide released by the development process would quickly eliminate lith results. In a test run I got to 3 prints before completely unsuitable due to lack of blacks from infectious development.

Finally here's the print. Ilford Cooltone RC in first-pass lith:

cooltone success.jpg



Here is a full resolution scan. Note that the black peppering is really on the print, but the white specs are just dust: https://www.dropbox.com/s/yovsl2f9y7aq9n9/cooltone success-full.jpg?dl=0

Now, a number of obvious problems still to be figured out:

* Peppering occurs, as seen here
* The middle of the print is significantly more eager to go into infectious development before the edges. This was my best print. Many prints in other prototype developer mixes had literally just a middle black spot of infectious development.
* As stated above, the developer is extremely unstable both due to the effects of bromide and the extremely high alkalinity required and low sulfite level. I'd really like a way to decrease the alkalinity required
* Extremely sensitive to sulfite levels, more so than a normal lith developer.
* Development is very difficult to keep slow. I typically use hot developer, but for this I used luke warm just so that the snatch point was greater than 1 minute. The fast development also doesn't seem to help the tendency for uneven development

I'm going to visit family for Thanksgiving, so unfortunately won't be able to continue more experiments on this until next weekend, but I'm already extremely excited to get back and mess with this more

edit: One small additional problem, on the print there is some fairly obvious yellow staining to the left side of the print. You can kinda see this in the scan but to a much less extent. This is probably some indication of the cause of the edges not developing properly
 
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grainyvision

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I've written some updates on my blog for experiments with this and basically towards the goal of making a general purpose lith printing formula that works with all papers. Thus far some interesting leads, though some persistent and annoying problems. I can discuss any questions etc here, but otherwise I will keep all updates on my blog with occasional cross posting here.

"lithalike" developer post for a lith-looking developer: https://grainy.vision/blog/magic-lith-prototype-update-2-lithalike-developer-discovery
General boring update of discoveries: https://grainy.vision/blog/magic-lith-prototype-update-3
"EXA" developer series testing for glycin+HQ lith developer: https://grainy.vision/blog/magic-lith-prototype-update-4
 
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grainyvision

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Just as an update to this. TEA might not be an ideal method of storage. I checked on a 5% solution that I mixed about 6 months ago and left at room temp in a half empty bottle and it had changed to a dark brown. It did still work as expected, but I assume the discoloration is due to oxidation of the hydroquinone. Propylene glycol solutions of HQ seem to be more stable and glycol is much less reactive in developer formulas. A 10% solution of HQ in glycol is easily possible
 
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