How Do You Prepare or Simulate Partially Exhausted Developer?

bvy · Jan 6, 2018

It may sound silly, but I'm looking for a way to manually or chemically exhaust my paper developer in a controlled way. I use Ilford PQ 1+9. In another post I made, I had some success with RA-4 reversal which calls for using a black and white paper developer as a first step. I had started by using some partially exhausted developer I had lying around in an effort just to get in the ballpark with exposure and color balance. And as luck (good and bad) would have it, I produced a near perfect print with that developer. Only now, I can't reproduce that result with fresh developer! I get excessive contrast and mottling. I tried diluting the developer and that improved the contrast, but the mottling is still extreme. Something about the partially exhausted developer I used delivered a good print.

I'd rather not toss good paper into fresh developer. And waiting till I use some developer isn't very reliable. I don't think exhaustion by oxidation is the same as exhaustion by depletion, but maybe it responds the same way? Looking for ideas...

NedL · Jan 6, 2018

Some thoughts, might not be helpful:

I've got a bottle of LPD diluted 1:6 ( it's usually used 1:2 ) that I sometimes use for paper negatives. It depletes faster than normal and needs to be replenished more often. I add a little splash of stock solution when the development times get too long. So if your RA-4 reversal can use a more dilute first developer, it's easier to deplete it. Also, maybe just dilution would help your process?

Another bottle of replenished LPD I was using for reversal after H2O2 bleaching. Even though I was washing the prints before redevelopment, it got weak sooner than I expected from what must have been a tiny amount of H2O2 carryover. After I noticed that, I increased the wash by a lot, and it's not a problem any more. But H2O2 will weaken a developer like crazy. It would probably be hard to figure out how much H2O2 to add to weaken but not kill your developer... probably more effort and testing than you want to do. But maybe you could add very dilute H2O2 drop by drop until a test strip indicates the developer has weakened?

PS RA-4 reversal sounds really neat. Are you enlarging slides? It would be cool to try it in a camera!

Anon Ymous · Jan 6, 2018

You can try adding potassium bromide. Bromide is a byproduct of development. Photographic paper mostly uses silver bromide, although other halogens might be used as well. Adding chloride wouldn't really make any difference, it's far less effective as a restrainer. Iodide on the other hand is a very powerful restrainer and used in minute quantities, such as milligrams. Anyway, see what effect added potassium bromide has, you have not much to lose.

Bill Burk · Jan 6, 2018

Anon Ymous said:
You can try adding potassium bromide. Bromide is a byproduct of development .

Brilliant. This is probably the right answer

Bob Carnie · Jan 6, 2018

bvy said:
It may sound silly, but I'm looking for a way to manually or chemically exhaust my paper developer in a controlled way. I use Ilford PQ 1+9. In another post I made, I had some success with RA-4 reversal which calls for using a black and white paper developer as a first step. I had started by using some partially exhausted developer I had lying around in an effort just to get in the ballpark with exposure and color balance. And as luck (good and bad) would have it, I produced a near perfect print with that developer. Only now, I can't reproduce that result with fresh developer! I get excessive contrast and mottling. I tried diluting the developer and that improved the contrast, but the mottling is still extreme. Something about the partially exhausted developer I used delivered a good print.

I'd rather not toss good paper into fresh developer. And waiting till I use some developer isn't very reliable. I don't think exhaustion by oxidation is the same as exhaustion by depletion, but maybe it responds the same way? Looking for ideas...

I do this for all my lith printing where once the lith is mixed I expose around 10-20 sheets of 8x10 Rc and throw them into the developer, which I believe effectively seasons the batch then I add the Old Brown and start printing.. I am always mixing high concentration high volumnes of chems for printing.

edit the paper is exposed to light and blackens in the dev..

Gerald C Koch · Jan 6, 2018

Run some scrap parer thru it. This was done years ago with film to take the edge off new film developer. It was termed 'seasoning' the developer.

Bob Carnie · Jan 6, 2018

I do this to try to match a mid day printing session where the lith chemicals are aged and giving me the colour and effect I want.. bit of a balancing act and is most useful when doing two or three days of printing for a show.

Bob Carnie · Jan 6, 2018

We also did this to keep the chems active for RA4 printing where at least 10 ft of 30inch paper was exposed and put through the machine.. colour processes need paper going through them and this minimum of paper really helped.

bvy · Jan 6, 2018

NedL said:
PS RA-4 reversal sounds really neat. Are you enlarging slides? It would be cool to try it in a camera!

Yes. Enlarging slides. See this link. I've done some 8x10 stuff in camera too, but not in a while.

The H2O2 idea is interesting. I use it to add contrast in RA4 printing, but something makes me think the clock starts ticking once you add it. I want something that will stabilize, not gradually kill the developer. It should be easy to try however.

Anon Ymous said:
You can try adding potassium bromide. Bromide is a byproduct of development.

I like this idea. It looks easy to get, and I would expect reproducible results with accurate measurements.

Bob Carnie said:
I do this for all my lith printing where once the lith is mixed I expose around 10-20 sheets of 8x10 Rc and throw them into the developer, which I believe effectively seasons the batch then I add the Old Brown and start printing.. I am always mixing high concentration high volumnes of chems for printing.

edit the paper is exposed to light and blackens in the dev..

I'm sure that would work, but it would be as a last resort. It's a little expensive for what I'm doing, since I'm using the developer one shot.

Thanks all...

RPC · Jan 6, 2018

Anon Ymous said:
You can try adding potassium bromide. Bromide is a byproduct of development. Photographic paper mostly uses silver bromide, although other halogens might be used as well. Adding chloride wouldn't really make any difference, it's far less effective as a restrainer. Iodide on the other hand is a very powerful restrainer and used in minute quantities, such as milligrams. Anyway, see what effect added potassium bromide has, you have not much to lose.

RA-4 papers are primarily chloride papers. When I make home brew RA-4 developer, the formula calls for sodium chloride as the restrainer (potassium chloride would also work). Thus I think that would be appropriate here, although bromide could have an affect as well. In fact, when I have experimented with RA-4 reversal, I used home-brew dektol for the first developer with chloride as the restrainer instead of bromide and got better results.

Anon Ymous · Jan 6, 2018

RPC said:
RA-4 papers are primarily chloride papers. When I make home brew RA-4 developer, the formula calls for sodium chloride as the restrainer (potassium chloride would also work). Thus I think that would be appropriate here, although bromide could have an affect as well. In fact, when I have experimented with RA-4 reversal, I used home-brew dektol for the first developer with chloride as the restrainer instead of bromide and got better results.

Yes, RA4 papers might be primarily chloride emulsions, but the typical BW paper is mostly bromide and that's what the OP used when he "partially exhausted" his PQ universal. As a result, this developer has an increased bromide content, apart from somewhat used up developing agents. Even in the case of chlorobromide paper emulsions, the chloride released doesn't make any difference, because bromide is far more powerful as a restrainer. So, I think adding some potassium bromide could help and might actually be the most important factor. In any case, potassium bromide is a key ingredient in developer starters, perhaps along with potassium iodide in much lesser quantities.

RPC · Jan 6, 2018

The RA-4 developer formula I use uses chloride only, and no bromide. Altering the amount of chloride has a large affect on the results, I have found. I would bet there is some chloride in RA-4 starter, perhaps even more than bromide.

The developer used may have given improved results, but I wouldn't limit my experimentation to simply trying to duplicate that.

Bromide may have an affect but I think it is worth experimenting with chloride as well.

bvy · Jan 7, 2018

So what is it that gradually turns a print developer yellow and then brown as it is used? Is it the byproducts of development or oxidation? Or both?

RPC · Jan 7, 2018

I believe it is just oxidation. I don't see how the byproducts could cause it, if you are referring to the halides released. Developer can darken just sitting there, without development having to have taken place.

After reviewing some past threads it seems that some have achieved better results by actually removing bromide from the first developer. It was proposed that the bromide actually puts too much of a brake on development, particularly with the cyan (top) layer.

In my experiments I had very high filtration settings and still unable to get a balanced print so used chloride instead of bromide in my first developer and then the print balanced easier with more normal settings. This is in line with the idea of the cyan layer not developing properly due to the bromide, as it would make the print more reddish and require more filtration. Using the chloride, less powerful than bromide, must have allowed the cyan layer to develop more completely, while still preventing fog.

Although I had solved that problem, I still had the usual issues with high contrast and crossover which I have not been back in the darkroom since to try and conquer. But someday...

Mr Bill · Jan 7, 2018

RPC said:
The RA-4 developer formula I use uses chloride only, and no bromide. Altering the amount of chloride has a large affect on the results, I have found.

The RA-4 paper was originally said to be a chloride paper, so presumably has no (or very little) bromide in it. And one could reasonably presume that RA-4 starter solution also has virtually no bromide (but probably any other type of developer starter does). Since starter solutions are intended to mimic "seasoning" of the developer, one presumes that they use the same chemicals that are byproducts of development.

Regarding developer sensitivity to chloride or bromide, the older EP-2 papers were very sensitive to replenishment rates. When RA-4 came out, we (at the lab where I worked) were amazed how tolerant it was to replenishment errors. Since the actual development agent was the same, we presumed this "insensitivity" was due to the use of chloride rather than bromide; not proven (to us), but a seemingly obvious conclusion.

Mr Bill · Jan 7, 2018

bvy said:
So what is it that gradually turns a print developer yellow and then brown as it is used? Is it the byproducts of development or oxidation? Or both?

In replenished systems, the developer can take on different colors depending on the specific paper used. I've seen seasoned tank solutions with either a pale yellow OR blue color, depending on the paper, so this is presumably a case of dyes - perhaps filter layer, etc., coming out of the paper. Extremely dark browns are presumably from oxidized developing agent, but it's something I've seldom seen in commercial work (occasionally a processing machine might get a small air leak on the inlet side of a circulation pump; this kills the developer in short order, as well as turning it dark).

bvy · Jan 7, 2018

Thanks. I should clarify that I'm interested in whatever byproducts are produced from developing black and white paper, not color paper, since that's how I produced the partially exhausted developer that I started with. That's what I want to mimic as closely as possible.

RPC · Jan 7, 2018

The byproducts may not be the issue, or only issue, however. Here is a thought:

It is possible that developing agents do not exhaust at the same rate, so with your developer, if the hydroquinone was exhausted but the other developing agent wasn't, then it could have still fully developed a lower contrast image, since hydroquinone is a high contrast developer. Crossover might have been reduced as well because of this. With fresh developer the hydroquinone had full activity.

To me the best answer to improving RA-4 reversal is to formulate a first developer tailored to it, instead of trying to use existing developers.

Mr Bill · Jan 7, 2018

bvy said:
Thanks. I should clarify that I'm interested in whatever byproducts are produced from developing black and white paper, not color paper, since that's how I produced the partially exhausted developer that I started with. That's what I want to mimic as closely as possible.

I'd say to do as Anon says.

To more closely mimic used developer, start by diluting it (this lowers the developing agent concentration) plus add something like KBr. If you want to kill off the preservative you'd want to aerate the developer, but I don't really see much purpose in doing this.

Certainly you can also do this by running exposed paper through it, provided that you have a good supply of it that you are willing to throw away. But the chemical treatment will get you (approximately) there faster, once you have established a recipe.

Mr Bill · Jan 7, 2018

RPC said:
To me the best answer to improving RA-4 reversal is to formulate a first developer tailored to it, instead of trying to use existing developers.

I'd concur with this, if you already sort of know what you're doing and are willing to put some time into a series of methodical tests.

But if you don't want to go that far, and already know that a certain commercial developer, somewhat exhausted, does what you want then this may be preferable to you; I dunno.

darkroommike · Jan 7, 2018

Gerald C Koch said:
Run some scrap parer thru it. This was done years ago with film to take the edge off new film developer. It was termed 'seasoning' the developer.

Gerald said it first, and after the first batch, just save a bit of the old developer for the next round of printing.

iandvaag · Jan 8, 2018

Maybe (to save on paper costs, if you don't have a tonne of scrap lying around) you could throw a couple exposed sheets of paper in the developer, bleach them with a rehalogenating bleach (e.g. K3FeCN6 and KBr), rinse and back into the developer. From there it is literally rinse and repeat! This method would also oxidize the developer in addition to introducing a restrainer (bromide or chloride depending on the rehal bleach composition). I don't know whether the effect would be significantly different to simply adding the restrainer directly. I guess the trade-off would be that there would be some dilution of the developer due to the carryover of the rinse water back into the developer. Squegeeing the prints would reduce this, and it doesn't matter if the paper gets scratched. It would be cheaper than using many fresh sheets.

I hope you are able to reproduce the exhausted PQ developer. Your most recent RA-4 reversal print is stunning, and has inspired me to give it a try. Best of luck.

bvy · Jan 8, 2018

RPC said:
To me the best answer to improving RA-4 reversal is to formulate a first developer tailored to it, instead of trying to use existing developers.

I think, in a roundabout way, that's what I'm doing.

iandvaag said:
I hope you are able to reproduce the exhausted PQ developer. Your most recent RA-4 reversal print is stunning, and has inspired me to give it a try. Best of luck.

Thanks a lot! The results have inspired me to become more methodical about the process in hopes of getting repeatable results. I'll keep the group posted.

peoplemerge · Jan 27, 2018

@RPC So the MSDS for PQ contains:
1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone
Diethylenetriamine Pentaacetic Acid Na5
HYDROQUINONE
Potassium Carbonate

I don't know about how to find the first 2 of those.

iandvaag · Jan 27, 2018

The first one is also known as Dimezone-S. If you can't find Phenidone is quite similar, but you may have to tweak the amount.

The second one is a chelating agent, and I imagine could be omitted if you use softened/distilled water, albeit with some change in pH.

How Do You Prepare or Simulate Partially Exhausted Developer?

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