Thanks to weird ideas and interesting non-photography chemistry papers, I’ve stumbled onto an extraordinary method of lith printing. I call it “Pharoh Lith” as a pun on ferro as in iron in a less common oxidation state. Pharoh Lith is a developer that basically breaks every rule in the book for a developer in order to exploit some exotic chemistry. The formula for EXF1 is as so:
2L of water
Some shreds of steel wool (amount is not important)
3g of hydroquinone (can be in propelyne glycol or TEA. Either work just as well, but TEA may require pH adjustments)
0.8g potassium bromide (8ml of 10%)
1.5g of sodium hydroxide (30ml of 5%) (target pH is between 11.5 and 13)
Preferably waiting 20-30 minutes before using this developer to allow the chemistry magic to happen (otherwise, first 2 or 3 prints will develop too fast and not exhibit good contrast)
Process (recommended)
Rinse print before development (removes incorporated developers and ensures more even development)
Develop. Typically takes 5-15 minutes depending on developer temperature, bromide content, and paper choice. Lithable papers will develop quite quickly
Put into proper acidic stop bath, citric acid or regular indicator stop should be safe for this. Water bath can also be used but must be changed often. If the stop bath becomes alkaline it can cause iron fibers to seem to appear on the print and cause staining
Rinse well under running hot water, at least 30s, to remove any stray fibers etc
Fix in acidic (ie, not TF-4) fixer
Rinse well
Dip into acidic solution “to taste”. Strong solutions of oxalic acid will remove the superimposed iron image and decrease overall density on certain papers, but a short and dilute dip will help clear highlights without affecting other tones. A stronger >1% Citric acid should in theory remove any sludging from highlights with no tonal changes at all, though may be less efficient at clearing sludging and thus also affect archivability. More testing required. This acid dip can be skipped, but permanence will be especially unknown if not fully toned afterwards.
Standard archival rinsing
Tone image in an archival toner (gold or selenium)
When this is mixed the developer will quickly turn “dead developer brown”. This is exactly what you want. Basically the way this developer works is that the HQ quickly dies (forms photo-inactive benzoquinone) both from the iron in solution, and generally fast oxidation in such an alkali solution with no sulfite. However, if you’re patient and wait for the developer to die pretty much completely, an amazing thing happens. It comes back to life as a fairly stable developer. It’ll still be opaque dark brown so inspecting development progress is annoying, but the developer will work with consistent results over several hours, though it does get slower with more time. If you intend to try this prototype, I recommend buying some cheap pH strips. After the 30 minute warm up period, and occasionally with more prints and time sitting, the pH of the solution will decrease. If the pH drops below 11 you’ll get poor results that also develop incredibly slowly. Anyway, so the results of this are rather incredible AND universal. It works on every modern paper tested so far, though less-hardened papers normally capable of lith will require some chemical adjustments to slow down development (probably more restrainer, maybe less initial HQ).
“EXF1D” (before toning), Ilford Cooltone RC in Pharoh Lith from 645 ortho litho negative
The overall properties of the prints produced (of course still depending upon paper choice some)
Fairly even development in most cases with proper agitation, even on hardened modern papers
Somewhat warm-brown (depending on bromide content) shadows and extremely warm highlights and midtones, tilting more toward the red and golden colors rather than green.
Some minor overall staining which will give a subtle peachy tone to the paper base. This can be partially removed with farmers reducer, but it is thus far impossible to remove it completely. Highlights will otherwise be extremely sensitive to both ferricyanide bleaching and farmers reducer
Great amounts of contrast control via exposure over highlights and midtones, and a fair amount over lower midtones and shadows. ie, it feels pretty much 90% like lith printing for contrast control. Blacks will come in first, highlights and midtones won’t move after the induction period like in lith printing… but the shadows can tend to darken somewhat fast compared to how quickly blacks completely darken. With previous experiments though, this effect can probably be controlled some with restrainers like iodide and chloride.
A long lasting and consistent developer. I used it for 3 hours tonight and made 7 prints, and other than making pH adjustments and a bit of iron sludging (easily cured with a quick acid dip) the prints looked nearly identical, but with warmer blacks at the end due to bromide added by printing
An iron image superimposed on the silver image in the shadows and especially blacks. This effect is why the image is so warm, and also why the permanence without toning is in question. The iron is most likely simple iron (Fe3) oxide, but if there is any iron hydroxide or other iron salts, then this can oxidize the silver over time. With selenium or gold toning though, the silver would be protected from oxidation. Gold toning is especially nice for this, producing blue highlights and midtones (if you go far enough) and warm brown shadows, if you don’t go for complete toning. If completely toned the entire image will be rather blue with shadows being closer to neutral. Note however, that this iron image can cause differences for bleaching. Typical ferricyanide bleach will not touch the iron image and any uncleanliness will be revealed by small specs of prussian blue. Ferrocyanide bleaching would convert the iron image to prussian blue, allowing you to potentially shift the dramatic warm colors to insanely cold and blue colors after redevelopment of the silver. Note I haven’t tried that at this point, need to order some ferrocyanide first. The iron image will be rather weak and nowhere near black enough to use with complete bleaching and fixing of the silver
Extremely fine grain at lower pH levels (11.5) and increasing grain in the shadows as pH is increased. Development also goes somewhat quicker and contrast is higher with a higher pH level.
“EXF1G” (before toning), MGV RC in Pharoh Lith, printed from 645 ortho litho negative
Explanation of chemistry:
This is more of a best guess, but this is how I think the chemistry behind this works. According to a paper, the reaction of HQ with metalic Fe goes like so:
Fe is oxidized by HQ, producing Fe2+ and Q (benzoquinone)
Fe2+ ions will reduce Q ions to HQ, ie, it restores the developing ability. Fe2+ ions are converted to Fe3+ in the process
Fe3+ is made insoluble by the alkali solution and converted to Fe3+ oxide and Fe3+ hydroxide. Fe3+ can combine with HQ to once again produce Q.. but it seems like an alkaline solution makes it decompose naturally more quickly than HQ can decompose it.
Fomatone 133 FB in Pharoh Lith from 645 ortho litho negative, strong oxalic acid “bleached”
Basically the iron functions as a “battery” for the HQ. You charge it with HQ in the solution, and it consumes pretty much all of it, then begins to release it but over a much longer time period. The paper referenced claims that HQ will still be in solution over 10 hours later, but at around 1/4 of the level originally put into the solution, and with a great curve when the HQ first begins being produced with it going from about 10% lower than initial amount to 50% lower over 2 hours. The paper only used a pH of 9 however, so using this significantly higher pH and plus introducing silver halides into the mix puts this into mostly uncharted territory. In addition to the Fe2+ regenerating Q into HQ, it also is a reducing agent and I believe will function as a weak developer. With a higher pH however this effect seems to mostly disappear, probably due to Fe2+ being unstable in alkaline solutions. This is why a pH of at least 11.5 is recommended. Below this level you’ll get a more normalized non-lith type of contrast and significantly more staining. The actual staining function of this developer I don’t really understand and can’t find any reference to. There are ancient ferrous based developers which produce a similar effect, but these are typically only ferrous sulfate or ferrous oxalate, and only within an acidic solution. In this process, the Fe2+ has nothing to become a complex/salt with other than the bromide, which I also believe is only possible in acidic solutions.
“EXF1D” partial selenium toned