Old Paper, Old Chemistry

[Camerashy]

Interesting if you have Old chemicals and paper. You can improve how your paper behaves by adding incremental amounts of a benzotriazole solution to your paper developer or by bleaching the finished print.
Does paper developer lend itself to replenishment?

 

[jhotopf]

Great to see Derek here. He's on a couple of my discords.

 

[thronobulax]

Does paper developer lend itself to replenishment?

Not really but it is possible to make paper developer with a very long shelf/use life and high capacity.

If you can find a source of raw chemicals, and particularly Glycin, you can make your own Ansco 130 - the formula is well known. The working solution at 1+1 will handle about 50 8x10s/liter and lasts for months when stored in a glass bottle. I used to use Kodak Dektol at 1+2 and throw it out each session, until I discovered the Ansco 130 alternative. Now I make up new working strength developer every 2-3 months (and I print a lot).

 

[Ian Grant]

Does paper developer lend itself to replenishment?

In a home darkroom in theory you could replenish developer and also fixer, in practice though it's not done.

On another Forum some say Ilford ID-78, the warm-tone developer I use, has a long life, a few days once mixed, stored in a bottle between sessions. In practice that's not what I've observed finding the results after a day are poorer. However as I almost exclusively use FB papers the volume of developer left at the end of a session has greatly reduced due to the paper base absorption & carry over.

With RC papers it's different, there's just a little carry over, and in addition many RC papers have a developer accelerator, this may help with a used or older developer solution. It's also why RC papers develop faster and generally have shorter suggested development times.

Ilford make RT developers & fixer for Roller Transport machines, these generally use top-up replenishment.

The most economic way of fixing, particularly with FB paper, is two bath fixing.

Ian

 

[HowLarge]

Nova dip tanks advise some replenish regime , I have never used them , but it makes sense with the right developer
and the Xtol replenish regime seems to work for those who use it.
Ian is the expert here , I think it depends on your volume and frequency of use and the note about FB paper being a sponge is
important if you are new to it otherwise you could be looking for a pinhole in your tray..

 

[Camerashy]

I've found that an alkaline fix has a long shelf life , I use separate bottles of fix for film and paper.

 

[thronobulax]

I've found that an alkaline fix has a long shelf life , I use separate bottles of fix for film and paper.

That's a wise move. I would point out that if you are going into an alkaline paper fixer, you want to avoid an acid stop bad, or at least rinse the print when moving from stop to fix. You don't want to carry the acidity of the stop bath into the alkalinity of the fixer.

 

[Ian Grant]

Nova dip tanks advise some replenish regime , I have never used them , but it makes sense with the right developer
and the Xtol replenish regime seems to work for those who use it.
Ian is the expert here , I think it depends on your volume and frequency of use and the note about FB paper being a sponge is
important if you are new to it otherwise you could be looking for a pinhole in your tray..

I have a 16"x12" Nova 3 slot tank which I used for RA-4 prints, with Tetenal mini-lab chemistry and top-up replenishment. I could use it for B&W but I prefer tray processing.

With films I began using replenished Microphen (ID-68) around late 1968, I was at school shooting on HP3/4, I was using brown 2.5 litre bottles, and it was a bleed system. I also shot FP3/4 in various developers. At the time Microphen was available to make 600ml, 2,5 litres, and 13.5 & 22.5 litres (for deep ranks), replenisher was 2.5 litres.

By 1976 I was using ID-11 replenished in deep tanks, but also Microphen/ID-68 for push processing (I was shooting theater, bust mostly rock concerts), until XP1 was released. I pushed that and XP2 on C41 chemistry.

At some point in the early 1980s I switched to Adox Borax MQ, again replenished, slightly finer grain than ID-11/D76, sharper, and about a half stop better film speed, a bit cleaner working less base fog caused by the 25% higher level of Sulphite in ID-11/D76, so better shadow details. Adox Borax MQ (Fotokemia FR 2) is very close to Agfa 44/Agfa Ansco17, all three where once commercially available, with replenishers.

I found 2.5 litres of stock was ideal for replenishment, I would typically replenish after every 5 films, typically I process a number of films.or sheets at the same time. I switched to Xtol when it was released, it's the easiest of all as it is replenished by fresh Xtol, so I would mix a 5 litre pack then split it into 2.5 litres of stock and the other 2.5 litres for replenishment. Results were always very consistent with all the replenished developers I've used.

Ian

 

[Nas]

I've used Kodak D-96 film developer replenished. I mix 5L from powder bought from the Film Photography Project and store in 1L bottles. Replenishing 70ml per roll (probably overkill) in the 1L of working solution I've got very consistent results with Eastman Double X motion picture film. The developer shelf-life has exceeded 6 months for me which was the limit I found for XTOL.

 

[thronobulax]

I've used Kodak D-96 film developer replenished. I mix 5L from powder bought from the Film Photography Project and store in 1L bottles. Replenishing 70ml per roll (probably overkill) in the 1L of working solution I've got very consistent results with Eastman Double X motion picture film. The developer shelf-life has exceeded 6 months for me which was the limit I found for XTOL.

Yes, many classic film developers can be replenished. Though, at today's rate of consumption, I wonder how useful that really is when you can gin up so many very inexpensive single-shot developers like Pyrocat, D-23 et al.

But the OP's question was about replenishing paper developers. In theory, this could be done, but I have never seen it in the wild.

As I noted in #3 above, I solved the paper developer exhaustion/oxidation problem by moving to Ansco 130. This developer has very good working strength capacity and a shelf life measured in months (if not more) when stored properly. Frankly I mostly have to replace it well before it hits full capacity utilization because of the fibre paper carryover reduces the total working developer volume noticeably.

The challenge is sourcing Glycin to make it (the other components are quite standard). So far as I know, there is only one place in the US that has it (Photographer's Formulary). I have no idea what the situation might be in the UK or EU though Merck/Sigma-Aldrich UK is claimed to have it. I don't know if they sell to individuals. There might be an opportunity for a concern like Nic And Trick to make pre-measured kits

 

[David M]

Surely, tray development exposes any print developer to fairly rapid oxidation. The Nova type of slot processor might avoid this.

 

[Camerashy]

Surely, tray development exposes any print developer to fairly rapid oxidation. The Nova type of slot processor might avoid this.

I do use a Nova slot print processor, I place cling film on top of the processor push it into the slots with the plastic tubes, then press the cling film around the sides of the processor. Not sure how much it stops oxidisation but it seems to be OK for at least 2 evenings in the darkroom using Ilford PQ Universal. After that I test how much time it takes to achieve satisfactory development.

 

[Ian Grant]

When comparing replenishing paper developers compared to film developers there are other factors to consider.

While film emulsions have a higher silver content per square metre, they are not developed to achieve D max. With MQ film developers the limiting factor with replenishment is Bromide build which begins to inhibit Metol activity as levels rise. To overcome this bleed replenishment has too be used, a volume of working solution is removed and replaced with replenisher.

In the 1950s Ilford realised switching from Metol to Phenidone overcame the Bromide build up issue. They worked on a PQ version of ID-11/D76 accurately measuring the actual depletion of the developer components with use, and were able to formulate a replenisher for top-up use. The developer was released as Autophen in the late 1950s. it was used for large scale photofinishing film processing machines. Unlike OD-11/D76 it did not collapse anfer many months of use, and just kept going. There's a series of 1950's BLP Almanac articles on the evolution of Autophen.

With paper developers development is to achieve Dmax, not to completion as some write. The capacity per litre depends on two factors choice of developer type, and paper base.

As with film developers thelimiting factor with developers llike Dekto/D72, D163, is being MQ developers their capacity is limited by Bromide build up, and the developer suddenly collapses.. Switching to a similar PQ developer very subtantially improves capacity at 3 or 4x.

Ilford's main paper developer used to be ID-20, an MQ formula, in the late 1950s this was replaced by ID-20PQ, identical excect the Metol was replaced by Phenidone. There were compalains that with the greater capacity as Bromide built up image colour was shifting warmer. Ilford refirmulated ID-20PQ as ID-62 halving the Bromide and adding Benzotriazole, which inhibits the colour shift.

ID-62 was never sold commercially, instead it was reformulated as a liquid concentrate, PQ Unuversal. The Sodium Carbonate was replaced by Potassium Carbonate and a small volume of Sodium Hydroxide to overcome solubility issues with the concentrate.

Ilford give the capacity of PQ Universal as 70 10x8 RC prints per litre, and FP prints 45, the difference is mostly the absorption of developer in the FB base. They also say a working tray life of approx 24 hours.

I use ID-78 a warmtone developer (once sold in powder form), essentially a variant of ID-62, a slight increase in Bromide and Carbonate, I mix as a concentrate (it was sold as Harman Warmtone developer). Typically I mix 1.5 litres of working solution, and process around 30 16"x12" FB prints in a session, which is close to PQ Universal capacity. The volume of developer left will have dropped quite noticeably.

Surely, tray development exposes any print developer to fairly rapid oxidation. The Nova type of slot processor might avoid this.

As @Camerashy says a couple of days in a Nova tank sounds about right.

Ilford used to make and sell Phenprint, and a replenisher, this was designed like Autophen, for a long life in roller transport paper process machines. I'm not sure how it differed from PQ Universal to improve it's working life and counter oxidation, it might be increase Sodium Sulphite. Ilford 2000RT Developer is the current equivalent but comes with hazard warnings.

Ian

 

[Camerashy]

When comparing replenishing paper developers compared to film developers there are other factors to consider.

While film emulsions have a higher silver content per square metre, they are not developed to achieve D max. With MQ film developers the limiting factor with replenishment is Bromide build which begins to inhibit Metol activity as levels rise. To overcome this bleed replenishment has too be used, a volume of working solution is removed and replaced with replenisher.

In the 1950s Ilford realised switching from Metol to Phenidone overcame the Bromide build up issue. They worked on a PQ version of ID-11/D76 accurately measuring the actual depletion of the developer components with use, and were able to formulate a replenisher for top-up use. The developer was released as Autophen in the late 1950s. it was used for large scale photofinishing film processing machines. Unlike OD-11/D76 it did not collapse anfer many months of use, and just kept going. There's a series of 1950's BLP Almanac articles on the evolution of Autophen.

With paper developers development is to achieve Dmax, not to completion as some write. The capacity per litre depends on two factors choice of developer type, and paper base.

As with film developers thelimiting factor with developers llike Dekto/D72, D163, is being MQ developers their capacity is limited by Bromide build up, and the developer suddenly collapses.. Switching to a similar PQ developer very subtantially improves capacity at 3 or 4x.

Ilford's main paper developer used to be ID-20, an MQ formula, in the late 1950s this was replaced by ID-20PQ, identical excect the Metol was replaced by Phenidone. There were compalains that with the greater capacity as Bromide built up image colour was shifting warmer. Ilford refirmulated ID-20PQ as ID-62 halving the Bromide and adding Benzotriazole, which inhibits the colour shift.

ID-62 was never sold commercially, instead it was reformulated as a liquid concentrate, PQ Unuversal. The Sodium Carbonate was replaced by Potassium Carbonate and a small volume of Sodium Hydroxide to overcome solubility issues with the concentrate.

Ilford give the capacity of PQ Universal as 70 10x8 RC prints per litre, and FP prints 45, the difference is mostly the absorption of developer in the FB base. They also say a working tray life of approx 24 hours.

I use ID-78 a warmtone developer (once sold in powder form), essentially a variant of ID-62, a slight increase in Bromide and Carbonate, I mix as a concentrate (it was sold as Harman Warmtone developer). Typically I mix 1.5 litres of working solution, and process around 30 16"x12" FB prints in a session, which is close to PQ Universal capacity. The volume of developer left will have dropped quite noticeably.



As @Camerashy says a couple of days in a Nova tank sounds about right.

Ilford used to make and sell Phenprint, and a replenisher, this was designed like Autophen, for a long life in roller transport paper process machines. I'm not sure how it differed from PQ Universal to improve it's working life and counter oxidation, it might be increase Sodium Sulphite. Ilford 2000RT Developer is the current equivalent but comes with hazard warnings.

Ian

Going off topic , Ian just out of curiosity have you any idea what films and developer would have been used in Europe during WW2 both for press photography and ariel surveillance?

 

[Ian Grant]

Ilford HP2 initially the HP3 in 1941 for fast film, also FP2. Various developers ID-11, IC-6 deep tank developer, Certinal (Ilford's version of Rodinal introduced in 1907. HPS plates were available in 1942 but there were probably special aerial films made for the military

Pan-X, Plus X, Super-XX, and Tri-X, were introduced in 1939, and coated in the US, UK and a newly opened factory in Hungary (owned by Kodak UK), then under Agfa control during WWII, and nationalised as Forte post war

Tri-X was only available as sheet film, there are photographs of US army vans carrying photographic supplies with Tri-X. The main speed sensitiser had come from Germany, all production in the US was requisitioned by the military. It would have been the same here in the UK. Tri-X manufacture cease when the sensitiser ran out, production didn't restart until 1954.

Where chemistry was in short supply the military mixed it's own from raw chemistry if available. In 1941 Kodak Research (Harrow) published a 32 page Formulary, for military use. The Ilford Manual of Photography was substantially re-written in 1942 by James Mitchell in early 1942, a revised 2nd ed later the same yea, a 3rd ed 1944 & two more reprints. These went mostly to the military, I have one with an officers mess sticker somewhere.

I have some WWII AP magazines, dealers were asking for cameras to be donated for military use. Focal Press, set up in 1938, started producing their small user guides for many German cameras, early in the war for these donated cameras. The two Kurt Jacobson books, Developing - May 1940, and Printing, were written primarily for military photo training and still in print 50 years later and multiple editions.

Ian

 

[thronobulax]

Surely, tray development exposes any print developer to fairly rapid oxidation. The Nova type of slot processor might avoid this.

It depends on the developer. For normal MQ developers like Dektol that is certainly the case. But the whole reason I switched to 130 is that is it far less subject to oxidative deterioration. The Glycin seems to be the magic that makes it so and this was well understood many decades ago. (Other than the Glycin, 130 resembles a fairly pedestrian MQ developer.)

 

[Camerashy]

Ilford HP2 initially the HP3 in 1941 for fast film, also FP2. Various developers ID-11, IC-6 deep tank developer, Certinal (Ilford's version of Rodinal introduced in 1907. HPS plates were available in 1942 but there were probably special aerial films made for the military

Pan-X, Plus X, Super-XX, and Tri-X, were introduced in 1939, and coated in the US, UK and a newly opened factory in Hungary (owned by Kodak UK), then under Agfa control during WWII, and nationalised as Forte post war

Tri-X was only available as sheet film, there are photographs of US army vans carrying photographic supplies with Tri-X. The main speed sensitiser had come from Germany, all production in the US was requisitioned by the military. It would have been the same here in the UK. Tri-X manufacture cease when the sensitiser ran out, production didn't restart until 1954.

Where chemistry was in short supply the military mixed it's own from raw chemistry if available. In 1941 Kodak Research (Harrow) published a 32 page Formulary, for military use. The Ilford Manual of Photography was substantially re-written in 1942 by James Mitchell in early 1942, a revised 2nd ed later the same yea, a 3rd ed 1944 & two more reprints. These went mostly to the military, I have one with an officers mess sticker somewhere.

I have some WWII AP magazines, dealers were asking for cameras to be donated for military use. Focal Press, set up in 1938, started producing their small user guides for many German cameras, early in the war for these donated cameras. The two Kurt Jacobson books, Developing - May 1940, and Printing, were written primarily for military photo training and still in print 50 years later and multiple editions.

Ian

Thanks Ian for the very informative answer.

 

[thronobulax]

In my particular case, the working strength (1:1) 130 sits in an open tray for 4-6 hours per session and then rebottled in a brown glasss container, stored in a cool, dark place. It is usable for well beyond 30-60 days and often has to be retired well before it is depleted or hits its capacity utilization (50, 8x10 equivalents per litre) because of the volume lost to carryover.

 

[Ian Grant]

Thanks Ian for the very informative answer.

It's the tip of the iceberg.

I have a wartime How To book "Hints, Tips & Gadgets" somewhere, it tells you how to make all sorts of photographic items, simply, first printed in 194, it's actually a collection of short pieces previously printed in Amateur Photographer. Companies like Gnome engineering had their premises taken over to make military items, it had not long been founded by a German engineer who had fled Germany and his company there.

Almost nothing was available for the amateur market during the war, so DIY was the key. Wartime BJP magazines contained simila ideas, I have some of the ideas in BJP Almanacs. One was to keep your used film developer, and add extra developing agents, adjust the PH by adding more Sodium Carbonate form a print developer.

It's also interesting how much German & others emigres fleeing the Nazis before the war brought to British photography. Andor Kraszna-Krausz had fled Hungary and set up Focal Press in 1938, Kurt I Jacobson and L A M Manheim from Germany became his initial principle authors, and there were others.

Kurt Jacobson had the greatest impact, first as an author, but he had a PhD in photographic science and founded a company that became Pavelle in Epsom. He introduced the Pavelle colour print process, selling paper and chemistry, in partnership with a US corporation. More importantly he designed and built the first Dichroic head colour roll head printers and mad a colour head for Durst LF enlarger. Later his company was bought and became Durst UK, still manufactiring in Epsom.

Ian

 

[Reginald S.]

Since my friend from former Tetenal Co. told me that Dr. Edwin Mutter taught him replenishing paper developer in the manner of tossing 50% of the used dev, and than filling back to 100% with fresh one, I replenish my developer, too. Which works very well and keeps my dev stable for month - if I do the replenishment directly after the printing session instead of before printing.
That's what E.Mutter taught.I forgot the chemical reason but kept the scheme. Which works very well.

The other reason for better longlife are chemical stabilisators, often found in good developers. But, stabilisators being the most important parts of developers doesn't mean that all expensive products have enough of them in their formula.

Finally I'm believing very hard that Propan/Butan sprayed on top of opened bottles is an important key for a good longlife strategy.
Ok, warmtone developers doesn't seem to keep for long times in general. However, I haven't had success in keeping Tetenal Centrabrom longer than 6 month, once opened.

Normal devs has been Rollei RHC and Moersch products here; today I'm exclusively working with Moersch Bromdev and Eco 4812. Have to check his warmtone devs some other day...