Research in progress (February 2022)

Hi, just wanted to give a small update to make sure I’m not being too silent on here.

I’ve been doing a series of fairly deep dives into technical research and experimentation lately. The results of this tend to be boring and difficult to discuss much of, but I’ll give a small summary of each project.

1. I’m working on lith developer formulation and going into a wild new direction. I’m trying to find a suitable sulfite sequestering agent to replace formaldehyde. This has been a rather intense challenge thus far. Acetone DOES work, but the amount required is prohibitive due to the obnoxious odor. I’ve been testing other aldehydes and ketones and combinations to try to increase the potency of acetone, but the ability for these to self-react in alkali has made this a difficult topic to really get a firm grasp on.

2. I’m also working on general lith developer additives. I have 2 potential additives thus far, both non-toxic and not difficult to source. One is a potential activity increaser and/or sulfite sequestering agent which is not an aldehyde or ketone. The other is a “coloring agent”, specifically it can cause lith developer to produce unique red and pink tones. It does not have this effect in non-lith developers tested. The biggest issue is that there is almost no research of using this chemical in any developer, and it has a tendency to produce fog on many but not all papers and seems to be a potent silver solvent and “displacer”.

3. Finally, I’m doing a little bit of research on ECN-2 processing technique and alternate processings. I’m wanting to make sure I have a reliable way to remove remjet before shooting anymore ECN-2 film than I already have backlogged. I also would like to create a “hybrid” processing method for ECN-2 which is aimed to produce increased speed, low color saturation, and excellent ability to push develop. Alt processing results thus far has shown some potential, but contrast was too high and color balance was too wonky.

I’m preparing for an extended trip to California later this month where I’ll finally start getting back into real “high effort” photography again. So there won’t be another update on any of this anytime soon, but just know I’m continuing to work and research. I am tossing around the idea of commercialization for some very select formulas, especially GVM1. I’ve also been doing some research of how to go about actually doing that. Unregulated shipping I think I can manage for GVM1, but for many other formulas seems much less clear. How to mix in a more bulk style is not something I’m geared up for, but can likely tackle for prototype runs like what I’m envisioning right now. Later I’ll post and send out a survey for interested parties to be able to express interest and request a sample of some formulas which are known to not be shipping hazards. Keep an eye out for that, but for this month I expect things will be slow on the chemistry front.

BasicLith, a dead simple lith developer formula for modern papers

BasicLith, also known as GVLith #6, is a formula which I created which will from the basis of a series of densitometry measurements in lith printing developer formulations. However, it is likely useful to the general public as well. I specifically designed it for this aim:

• Work well with Ilford MGV RC and Fomatone RC papers

• Simple to mix with minimal safety concerns, no heating required of flammable solvents

• Avoid DMSO because the smell is annoying

• A shelf life of at least 1 month (unknown if this developer meets this, but its simple enough to mix that it’s not a problem if not) and tray life of at least 1 hour

• As minimal as possible while accomplishing the above goals

Tray life is not great, expect 1-2 hours typically. To make this formula more controllable for vintage lithable papers, add 0.3-2g of bromide per 10ml of developer parts. This developer may produce fog, pepper fog, or uneven development when heated, and is also much less stable. It is fast enough that heating should not be required. Induction period time with Ilford MGV RC at 74F and 10+10+400 is about 50s, with infectious development starting around 4m30s.

Formula

Part A:

• Distilled water, room temperature 40ml

• Sodium Metabisulfite 6.6g (note: small amount of SO2 gas released. Don't hold your head over the beaker)

• Sodium Bicarbonate (baking soda) 0.7g (add this as soon as the metabisulfite is mostly dissolved. It will bubble quite a bit)

• (Optional) PEG-3350, MiraLAX 0.2g

• Propylene Glycol 40ml (warmed using a water bath preferably, but not a requirement)

• Hydroquinone 11.1g

• Top the solution to 100ml using propylene glycol.

• Water is avoided for longer shelf life and because glycol is a better solvent for hydroquinone. It is ok if the solution has some very small particles or a tiny amount of "fiber" looking crystals floating around. It should be mostly transparent though and slightly yellow. The remainder will dissolve upon standing for a few hours.

Part B:

• 70ml water

• Potassium Carbonate 13g

• Sodium Hydroxide 7.3g (note: make sure your crystals do not appear "wet" or clumpy, this amount is quite precise)

• Potassium Bromide 2.7g

• Top to 100ml with water

• Note: Solution will heat up considerably when adding the carbonate and hydroxide and will be very caustic. Use care and appropriate gloves when handling

Revision: The original version of this formula said to add PEG-3350 to part B. However, this is not possible PEG is practically insoluble in such a concentrated alkaline solution. Instead, it should be mixed into the part A instead. Note that in the part A, it may take a while to dissolve and/or require gentle (water bath style) heating

Usage

Use 10-40ml of each part for 1L of working solution developer, preferably at room temperature. I have only tested equal amounts of each part at a time.

Not an absolute requirement, but I highly recommend making a 1% solution of PEG-3350. PEG-3350 is also called polyethylene glycol of molecular weight 3,350. It is a surprisingly easy to find chemical. It is sold in most countries as a laxative. In the US it is sold under the brand name MiraLax. Use 1-7ml of this 1% solution per 10ml of developer parts for increased contrast and "linearity" of infectious development if not included in part B of the developer. This will increase the linearity of shadow development of the lith developer and gives a general increase in contrast. Certain negatives call for more and some for less, so it may be preferable to keep this as a separate solution for more control.

Spoilers

This is a bit of spoilers and the results still need to be double confirmed, but here is some interesting densitometric measurements using BasicLith without PEG at 10+10+400:

ModernLithC1 Progress

Hi everyone. I’ve delayed any real timeline I had for shipping ModernLithC1 kits due to the coronavirus… However, due to this I’ve been doing a lot more testing. I was initially planning to keep the formula a secret but as I do more and more testing, “proprietary” additions can produce good results but compromise in various ways. The formula I continue to get great results with on almost all papers is basically just the original ModernLith formula with very minor adjustments, specifically more carbonate and a tiny bit more sulfite and bromide. The formulation thus far is a 3 part A+B+C kit. The specific names are Developer, Activator, and Stabilizer, respectively. This seems to allow for the most control and the most flexibility with different dilutions. I also had a lith printing survey and got a good number of data points. I’ll eventually write a full blog of the results, but the basic summary is the following:

• Fiber based papers are much more desired for lith printing than RC papers, even when modern RC papers could be easily used for ideal results. I believe this is due to the archivability and uniqueness of FB prints compared to RC. Specifically, many people think that RC paper feels too similar to inkjet prints, and “plasticy”. FB papers also allow for some unique textures not available for RC papers. The pain and process required for FB processing seems to be of fairly small concern.

• Quite a number of people want to mix the formula from scratch, around 40% surprisingly. Despite how much I enjoy it, I believe many people want a basic set of stock solutions that can produce reliable results. This also has driven me to publish the final ModernLith C1 formula.

• Most people don’t care about my other potential products. The only one with any interest in “EXK” an attempt at a neutral tone print developer that is long lived and environmentally friendly (ascorbic acid based).

• Most people use a heated setup, ~70%, and of those, most use a “setup” of simply starting with hot water. I tend to do this myself so that the first couple of prints are significantly faster without needing to drag out my sous vide setup (which can also only handle 8x10 trays really)

• The biggest concern people have in lith printing is being limited to very few modern “lithable” papers and formaldehyde being harmful to handle.

So, the progress on ModernLithC1 has been dedicated primarily to trying to fix a few issues:

1. Eliminate fog that develops when using hot developer on Ilford papers

2. Eliminate snowballing that happens when using cold developer on many FB papers

3. Keep an interesting spectrum of colors in the final result

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Ilford MG FB in ModernLithC1 with sodium chloride and old brown addition (in room temp developer)

Various restrainers were tried for reducing the tendency of fogging in hot developer. Both potassium iodide and sodium chloride. Although iodide works well, it requires a rather huge amount to completely prevent and has a lot of undesirable effects. Some papers really exhibit some weird problems such as mottling and uneven development with very much iodide. This amount of iodide being present also affects the fixer. Specifically, it requires at least double the amount of fixing time and exhausts the fixer significantly faster. It is still something worthwhile to play with as it can produce some interesting tonality and color, but should only be used in tiny amounts and not as a complete fog prevention solution.

Chloride was something I really tried out not with the intention of fixing anything, but rather with the goal of producing deep red tones like is possible on the famous Polywarmtone paper. It didn’t produce that, but was interesting regardless. The primary advantage of chloride is that it seems to very weakly affect most RC papers and maybe even accelerates development on RC papers, but also acts to significantly decrease the amount of snowballing on FB papers, making them reasonable to use with room temperature developer. I believe the chloride stands in as a 90% neutral salt that just helps the developer to penetrate more evenly into the FB emulsions, and maybe to penetrate more quickly into RC emulsions. I believe this is why I had fewer problems when I was using massive (and expensive) quantities of oxalate. The actual effects on tonality with chloride are fairly minor, tending to produce more golden and yellow tones rather than peach and making the famously neutral tone Foma emulsions pick up a hint of warmth in the highlights. Chloride wouldn’t be included with any ModernLithC1 kit, as it’s so easy to find locally (literally just kosher salt etc) and the absolutely massive amounts required. For instance, in most tests I start with ~80g per liter of developer. The exact amount is far from critical for chloride due to it’s very weak restraining effect in this type of developer.

ModernLithC1 v10 prototype formulation

Part A, developer:

• Add 100g of hydroquinone to 800ml of heated propylene glycol. Temperature needed is ~140F. Do not boil the glycol and be careful of flammable vapors!

• Top to 1L with glycol

Part B, activator:

• Start with 800ml of room temperature (not hot) water

• Add 350g of anhydrous potassium carbonate. Solution will heat up significantly

• Add 10g of potassium bromide

• Add 25g of potassium oxalate (determined to be optional, but may increase tray life slightly)

• Add 25g of sodium sulfite (use 30g for longer tray life when using old brown)

• Top to 1L with water

Part C, stabilizer:

• Add 40g of ascorbic acid to 400ml of heated propylene glycol. Temperature needed is ~160F and significant stirring is needed. Do not boil the glycol and be careful of flammable vapors!

• Before all the powder is dissolved completely, top to 500ml with heated glycol (solution is very close to solubility limit so the extra glycol makes things go faster)

Part D, bonus:

• Start with 800ml of hot water

• Add 200g of sodium chloride (anything non-iodized such as kosher salt or pickling salt)

• Top to 1L with water

Part C can be substituted with simply adding some ascorbic acid to water to make a % solution. However, the solution will not be stable and will decay within a matter of hours, so only a small amount should be made at a time.

Usage: Start with a dilution of 10ml + 40ml + 10ml per liter for RC papers and 10ml + 40ml + 5ml per liter for FB papers. Stabilizer is optional, but excluding it will cause shorter tray life and poor reactions in some papers. Additional stabilizer tends to slow down infectious development and in some papers trend toward colder brown tones of lower overall contrast. For FB papers especially, add 200ml of part D per liter of developer. This will prevent snowballing and may increase overall development speed. It will also cause some cold and neutral tone papers to give peach highlights and some peachy warmtone papers to give yellow and golden highlights.

Fomatone Warmtone 332 RC, without old brown addition

Fomatone Warmtone 332 RC with ~200ml/L of old brown and same dilution otherwise

Usage of old brown can give nice results, but for consistent results the old brown should be “tracked” and not allowed to “condense” too much. I recommend keeping a “round 1” and “round 2” bottle of old brown. When fresh developer that had no old brown expires, put it into round 1. When the developer expires that used the round 1 old brown expires, put it into the round 2 bottle. When the developer used from round 2 old brown expires, don’t keep it for old brown purposes. Bromide especially will accumulate in old brown as it is condensed more. Because so many modern papers are sensitive to bromide amounts, this can cause poor results where you simply follow “add 200ml of old brown” but end up adding what would be the equivalent of 2L of “uncondensed” old brown worth of bromide. Old brown has a number of effects if used with some caution. The primary components of old brown are additional alkali, additional bromide, and potentially a weak but very stable developing agent called hydroquinone-monosulfonate. In my testing, old brown usage tends to cause more highlight development and thus reducing contrast and to give more colorful highlights in general. Too much old brown can cause the lith “split” to break down, where midtones are too dark but shadows aren’t dark enough. It can also cause blacks to remain fairly brown instead of becoming a properly dark black.

Importantly however for old brown usage, is that it means I can keep ModernLithC1 stock solutions very low bromide, but also not need to provide yet another solution part for the papers that might give better results with additional bromide. So, the ModernLithC1 formula going forward is basically being designed to incorporate old brown into the final working solution.

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Test 4x5 portrait to a test 11x14 Ilford MGV RC lith print in ModernLithC1 with chloride and old brown (still learning how to take not terrible portraits in this isolation)

And now, for a combo of blooper reels and early success in the formulation, and some notes on things learned.

Ascorbic Acid is a lot more soluble in triethanolamine (TEA) than propylene glycol. It also functions as a chelating agent, keeping the ascorbic acid alive longer in tap water containing iron. I was hoping I could use it in the part C so that it can contain more ascorbic acid and it’d increase tray life stability. However, TEA seems to intensify potential staining and fogging. It also causes some papers to develop unevenly, even in extremely small amounts. In previous testing TEA has seemed to interfere with infectious development and this was doubly confirmed in these recent formulation tests with fairly large amounts of TEA. It didn’t exhibit the same effect when using very small amounts.

Benzotriazole is an interesting addition. It is soluble in propylene glycol, unlike other possible restrainers. While a small amount definitely cools the print image, if a lot more is used it can actually give very warm tones, especially toward browns and even reds. On most papers though a large amount massively slows down development, and require significantly more alkali to get proper infectious development. It does however cure the staining issue I see on some papers with heated developer. I don’t really like the effects it tends to give so it won’t go into any official ModernLith formulation, but feel free to make a 0.1% solution and add between 5ml to 100ml. 100ml is where it will start to give warmer tones, while 5-30ml it’ll give colder tones.

I tried using isopropyl alcohol in the formulation just to see if it would prevent snowballing, and it actually made things incredibly very badly worse. It also is very strong smelling in a tray, caused shorter tray life, and is a hard to find commodity these days with the coronavirus and all.

As a conclusion, I still have a small number of notes to directly apply to improve this formula, as well as ideas still to try. It has been more frustrating than I imagined really to get something I’m 100% happy with, especially when going beyond the great Ilford MGV RC. However, progress is being made, and hopefully after this coronavirus stuff dies down, I can look more seriously at something that can be shipped.

More EXG1 Results

So I’ve now used EXG1 with a stock pile of well preserved but ancient Kodak Plus-X (expiration 1966) that came out with excellent results. I wouldn’t really say it’s an ideal developer for this fogged film due to quite a bit of grain, but I do really enjoy the tonality of it, and the grain isn’t too bad since I’m using it in 6x4.5 format.

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Kodak Plus-X in 6x4.5 developed in EXG1

The Plus-X was developed at 70F for 8m30s. Overall density seemed like it could’ve used just a slight bit less time, and there was some base fogging naturally from the age of the film. However, the base fog was about comparable to a test roll that was processed in D-76.

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Flat (no burn/dodge) 8x8” print on Ilford MGV

Now finally, I also made my first prints from EXG1 processed film. The film used was FP4+ in 35mm processed for 11m in EXG1. Overall wasn’t too difficult to print, but I did have to burn in the sky quite a bit in the high contrast scene on the final print (which I neglected to scan before framing). I used Ilford MGV RC paper developed in Ansco 130 and exposed at f/8 11s with contrast grade 2 filtration.

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Raw film scan of the FP4+ negative

Anyway, so the developer could use a bit more highlight compensation, but other than some clipped highlights I had no problem translating the film onto paper for darkroom printing. It definitely is quite grainy for 35mm FP4+ at box speed, but I tend to like grain anyway and especially like the tonality here. It can be a bit contrasty for portraits, but is great for my other work.

Prototype Update #10 (brown warmtone developer, EXI series)

I’ve been taking a break from lith developers due to general frustration, but I haven’t been giving up on other new interesting paper developer formulas. EXI is a series of experiments with the aim of creating a very warmtone developer that works properly with modern papers. Every warmtone developer formula I’ve tried with modern papers either skews to green/olive, or can’t produce convincing blacks.. or in general looks minimally warmer than Liquidol etc. This developer is being formulated primarily with convincing warmtones on the paper I’ve had a ton of trouble with, Ilford Warmtone RC. There are a few ideas being tried. The theory behind a warmtone print is that the grain size of the prints is fairly small. Grain size correlates with color and from smallest to largest goes: yellow -> red -> green -> brown -> purple -> black… of course with some weirdness and exceptions on different emulsion designs.

The break through I found in keeping the color more toward brown, rather than the more typical black/purple/green spectrum is sodium oxalate (though potassium oxalate should work better). I don’t entirely understand how it works, but it seems to function as a unique restrainer and potential silver solvent. It helps to intensify blacks in some ways and in other ways makes shadows skip from olive green to sepia and brown colors. It seems to have minimal effect on highlight tonation.

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Ilford Warmtone RC in “EXI4” prototype developer

The following is “EXI4”. Note that this is definitely a prototype developer that I’m still optimizing and eventually plan to make a stock solution version so that I don’t go insane

Part A:

• 10ml of Glycin-TEA 10% (can be substituted with 1g of glycin, and 10ml of triethanolamine, added last)

• 1ml of Phenidone-glycol 1% (can be substituted with 0.01g phenidone)

• 30ml of triethanolamine (clear 99% grade)

• 3.1g sodium oxalate (can be mixed into a % water solution, potassium oxalate should also work better as a substitute)

• 8g sodium sulfite

• 0.6g potassium bromide

• to 500ml water

Part B:

• hydroquinone-glycol or TEA 10% can be used (in the future an HQ metabisulfite solution can probably be formulated like Adam’s variant of Ansco 130)

Add up to 5ml of part B to the final solution for deeper blacks and more overall contrast. Without any part B blacks will be rather brown.

The solution lasts in a tray at least a few hours, and should have fairly “normal” tray life otherwise. Develop for 3-5 minutes, 4 minutes is typical. Imagine will come up fairly linearly, image should appear pretty much “done” at 2 minutes under safelight, but blacks will continue to intensify and pulling early can result in some streaking in blacks. Over expose print by 1-2 stops compared to most other developers.

Results are overall brownish warmtone, especially in the shadows. Works best with warmtone papers, but will also give subtle warm brown tones to some neutral papers.

Magic Lith Prototype Update #9 -- EXH Failure

In testing an idea with EXF where I combined ferrous sulfate, hydroquinone, triethanolamine, and carbonate I observed that the developer continued to work for a good amount of time in a beaker, several hours. I wanted to do a control test to see what ferrous sulfate was contributing to the process though. I made the same solution, but with no ferrous sulfate, and ensured that the pH of both solutions was the same. The results were incredibly surprising. The “control” without ferrous sulfate stayed alive for a very long time. Still producing images after 8 hours, though at around 300% slower speed. This seemed promising though, since there in theory was only hydroquinone acting as a developing agent and even if a lot of the hydroquinone oxidized, as long as some was alive infectious development should be possible…

But once again I’m smacked with abrupt failure when trying a similar concoction, EXH1, in a tray with actual paper tests. The developer works for a long time, can develop good blacks, and develops fairly quick at room temperature, but does not exhibit any infectious development. It also requires a lot of bromide to reduce fogging levels. The exact formula is as so:

• 2L water

• Triethanolamine (TEA) 100ml

• Potassium carbonate 12g (6g of 20%)

• Hydroquinone 1g (in propelyne glycol 10%, 10ml)

• 2g of bromide (20ml of 10%)

The very high amount of TEA seems to preserve the hydroquinone quite well though the solution does quickly discolor.. However, a big give away is that there is very little red film present on the developer after a few minutes. It also does not give any infectious development, nor other hallmarks of lith printing like colorful highlights. In this the induction period seems to blur into shadow and black development, meaning that with more development the entire image gets darker and more highlights become present. I tested this on many papers, including Kodabrome which is a very good lith paper in traditional formulas. My hypothesis for the reason behind this failure is that TEA reacts, not with hydroquinone nor benzoquinone, but rather reacts with the radical semiquinone to produce some kind of complex which either is a weak developing agent or is not active. In this respect, a large surplus of TEA reacts in the same way as a surplus of sulfite would, it scavenges oxygen and preserves the hydroquinone, but also scavenges the semiquinone and prevents infectious development. With this in mind, HQ mixed into propelyne glycol would be a better “part A” than HQ mixed into TEA. With a lot of research, I’ve found this is a big subject area with very little or no previous research written about it.. However, TEA with other quinone compounds is known to form complexes with semiquinones and is also an electron donor, meaning it can potentially convert semiquinone back to hydroquinone. It appears to be an imperfect preservative compared to sulfite, since the solution will quickly discolor to brown, but either way the end result is that this is a major dead end into a fair number of ideas I had about this. I’m not really sure what else can be done at this point.