Paper developer with long shelf life

[faberryman]

I had an hour today so I tested a clip of expired Tri-X that has been in the freezer (Arista Premium 400). Looks like time is going to be about the same as XTOL, actually, but will wait until it's dry and I can check density and also scan it to post. I tested on film leader first, to get a sense of Dmax and adjusted upward to the full 7 mins before developing.

I use Ilford Multigrade. I mix up what I need for a session and throw it out when I am done. I get a new bottle when I run out. If it goes bad before I finish a bottle, I throw it out and get a new bottle. Not the least expensive way to go, but in the grand scheme of things, the cost is negligible, and I always have fresh chemicals.

 

[snusmumriken]

I use Ilford Multigrade. I mix up what I need for a session and throw it out when I am done. I get a new bottle when I run out. If it goes bad before I finish a bottle, I throw it out and get a new bottle. Not the least expensive way to go, but in the grand scheme of things, the cost is negligible, and I always have fresh chemicals.

I thought you had said your Multigrade never went bad, and I was going to ask if you live high in the Andes, or some other oxygen-deprived region. But then I blinked and saw that you hadn’t said that. Ever.

 

[GregY]

Yes, developing agents last a long time in propylene glycol, as Gainer found. I have had a batch of PC-Glycol last 3 years in a partially filled bottle with some small exposure all that time to ultraviolet as well. It works well! I like the freezer idea you used with Mocon and will be doing that from now on.

How does this relate to the topic under discussion of "paper developers w long shelf life" ?

 

[albada]

How does this relate to the topic under discussion of "paper developers w long shelf life" ?

It verifies that developers dissolved in propylene glycol last a long time, especially when stored cool, and thus that a paper developer mixed and stored that way will also be long-lasting.

 

[GregY]

It verifies that developers dissolved in propylene glycol last a long time, especially when stored cool, and thus that a paper developer mixed and stored that way will also be long-lasting.

Albada, which paper developer have you mixed that way? I typically use LPD or Formulary Ansco 130. Are you suggesting they be mixed w polypropylene glycol? Or have I missed something here?
* As aside, I also keep some Ilford Multigrade developer on hand as it's the only paper developer locally available. I buy the 5 litre container and even after it darkens with age, I've never had it go bad.

 

[relistan]

Albada, which paper developer have you mixed that way? I typically use LPD or Formulary Ansco 130. Are you suggesting they be mixed w polypropylene glycol? Or have I missed something here?
* As aside, I also keep some Ilford Multigrade developer on hand as it's the only paper developer locally available. I buy the 5 litre container and even after it darkens with age, I've never had it go bad.

This was also in this thread: https://www.photrio.com/forum/threa...th-long-shelf-life.195427/page-3#post-2613920 . This was the post I was replying to.

 

[albada]

Albada, which paper developer have you mixed that way? I typically use LPD or Formulary Ansco 130. Are you suggesting they be mixed w polypropylene glycol? Or have I missed something here?
* As aside, I also keep some Ilford Multigrade developer on hand as it's the only paper developer locally available. I buy the 5 litre container and even after it darkens with age, I've never had it go bad.

None yet. I was stating that film developers can be stored in glycol, so it should work for paper developers too.
As @relistan pointed out above, I want to try this with ID-62, but have not done so yet.

Usually, only some chemicals in a developer will dissolve in glycol, forcing us to keep the developer in *two* stock solutions: One water-based, and the other glycol-based. This approach only works for folks mixing chemicals from scratch. LPD and 130 come pre-mixed, so they cannot be dissolved in glycol.

 

[Paul Howell]

I ran an experiment on this with dektol, 1 liter in a tray covered with plastic wrap between sessions. The experiment went for four sessions over two weeks, end of each session printed a wedge at the same fstop and intensity. Because I was basically doing this anyway, just not the wedge. Well it was a waste of time. I saw no difference on day 1 vs. day 13 or 14. What I learned is, dektol developer is pretty hard to wear out. This was a 1+2 mix.

When in the Air Force we used Dektol or GAF version with floating lids, lasted day after day, depending on the work load sometimes longer.

 

[GregY]

None yet. I was stating that film developers can be stored in glycol, so it should work for paper developers too.
As @relistan pointed out above, I want to try this with ID-62, but have not done so yet.

Usually, only some chemicals in a developer will dissolve in glycol, forcing us to keep the developer in *two* stock solutions: One water-based, and the other glycol-based. This approach only works for folks mixing chemicals from scratch. LPD and 130 come pre-mixed, so they cannot be dissolved in glycol.

i have LPD in powder & some liquid jugs as well. It seems like two issues. I thought the OP was talking about leaving mixed developer in trays. I've never had paper developers (LPD, Neutol, Ansco 130, or Ilford Multigrade) go bad. With the cost of paper I don't care to reuse, replenish and worry about exhausted or contaminated developer. So at the risk of looking at it simplistically, it seems to be a solution to a problem that doesn't exist.
As far as film developers, Pyrocat HD in glycol is my standard developer.

 

[Ian Grant]

None yet. I was stating that film developers can be stored in glycol, so it should work for paper developers too.
As @relistan pointed out above, I want to try this with ID-62, but have not done so yet.

Usually, only some chemicals in a developer will dissolve in glycol, forcing us to keep the developer in *two* stock solutions: One water-based, and the other glycol-based. This approach only works for folks mixing chemicals from scratch. LPD and 130 come pre-mixed, so they cannot be dissolved in glycol.

Developers like ID-62 or ID-78 jeep well anyway if mixed as a concentrate, but unlike the film developers mixed in Propylene Glycol their Sulphite and Carbonate levels are too high which rules out Glycol. It's also worth noting that ID-62 and ID-78 which use Phenidone, have a longer shelf life once opened than their commercial equivalents PQ Universal & Harman Warmtone, which use Dimezone.

Ian

 

[albada]

It's also worth noting that ID-62 and ID-78 which use Phenidone, have a longer shelf life once opened than their commercial equivalents PQ Universal & Harman Warmtone, which use Dimezone.

That's strange! I've read that Phenidone is subject to hydrolysis, making its storage life shorter than Dimezone. Do you know why the opposite would be true?

 

[john_s]

That's strange! I've read that Phenidone is subject to hydrolysis, making its storage life shorter than Dimezone. Do you know why the opposite would be true?

I also have wondered about that statement. I have read that more Dimezone-S needs to be used to be equivalent to phenidone, more than equimolar according to some people, but I have also read that it exists because it keeps better in solution. I use it in my ID-78 but haven't done a test alongside a phenidone batch.

 

[Ian Grant]

That's strange! I've read that Phenidone is subject to hydrolysis, making its storage life shorter than Dimezone. Do you know why the opposite would be true?

I don't, but my observations are based on experience of using Phenidone (as a raw chemical) since 1976, and using Ilford's products. One comment would be that I've found that the concentrated version of ID-78 I mix keeps far better than the published formula. It's likely that the high Sulphite content is the key.

The BJP ran a series of articles about Phenidone developer in the mid to late 1950s, they were from Ilford research looking into a PQ variant of D76/ID-11, one article detailed measuring how the developing agents exhausted, levels of bromide etc. The outcome of the research led to the introduction of Autophen, designed for large scale photofinishing, also known as the Axford-Kendall Phenidone-Hydroquinone Fine Grain developer, with two different replenishers, one for topping up, the other bleed replenishment The last article noted that one laboratory had just kept replenishing "A 24-gallon tank was used and a total of 65,000 rolls was put through with topping-up replenishment using the replenisher designed for this purpose".

But again Autophen was a high Sulphite PQ developer, very stable and with a long life, the spin-off was the realisation that dropping the Sulphite level tweaking the P=Q ratio, changing the buffering, gave a speed enhancing fine grain developer. ID-68/Microphen

When deciding to mix a concentrated PQ developer I had found an example developer in an Ilford patent which had strange weights, but when I looked at the ratios it was obviously ID-62 (PQ Universal) but with Potassium Carbonate and some Sodium Hydroxide instead of Sodium Carbonate, so then it was simple to calculate the weights for and equivalent to the commercial products. As I mentioned earlier ID-78 is a warm=tone variant of ID-62.

Ian

 

[relistan]

None yet. I was stating that film developers can be stored in glycol, so it should work for paper developers too.
As @relistan pointed out above, I want to try this with ID-62, but have not done so yet.

Usually, only some chemicals in a developer will dissolve in glycol, forcing us to keep the developer in *two* stock solutions: One water-based, and the other glycol-based. This approach only works for folks mixing chemicals from scratch. LPD and 130 come pre-mixed, so they cannot be dissolved in glycol.

Definitely will be interested in your results, Mark!

 

[FotoD]

and the Phenidone as a 1% mixture in Isopropyl Alcohol (and measure this with a syringe), which I think is the less stable part in this flow.

I recently came across this test:

"Because of the inherent difficulty of weighing small quantities of phenidone, I had high hopes for the stock solution mixed at the initial interval, and used to measure phenidone in making PC developer at each testing interval. But the activity of this stock solution was significantly poorer than the keeping qualities of PC, PX, or Xtol developer themselves. I wouldn't recommend using it."

https://healthprofessions.udmercy.edu/academics/na/agm/phenvitc.htm

 

[Philippe-Georges]

I recently came across this test:

"Because of the inherent difficulty of weighing small quantities of phenidone, I had high hopes for the stock solution mixed at the initial interval, and used to measure phenidone in making PC developer at each testing interval. But the activity of this stock solution was significantly poorer than the keeping qualities of PC, PX, or Xtol developer themselves. I wouldn't recommend using it."

https://healthprofessions.udmercy.edu/academics/na/agm/phenvitc.htm

I thought having read somewhere about an other way of diluting Phenidone at a 1% quantity in an other medium than Isopropyl Alcohol and having a better keeping quality.
But I can't recall wat was that compound, it could have been Glycol or Glycerol, but I don't know...

 

[Anon Ymous]

I thought having read somewhere about an other way of diluting Phenidone at a 1% quantity in an other medium than Isopropyl Alcohol and having a better keeping quality.
But I can't recall wat was that compound, it could have been Glycol or Glycerol, but I don't know...

Propylene glycol, it does a very good job at preserving phenidone.

 

[FotoD]

Apparently it was phenidone mixed with sodium metabisulfite and H2O that did not make a good stock solution, according to the study above.

Hopefully it works better in either IPA or propylene glycol.

 

[koraks]

Hopefully it works better in either IPA or propylene glycol.

From experience I know that a 1% solution of phenidone in propylene glycol is very stable.

 

[Philippe-Georges]

Propylene glycol, it does a very good job at preserving phenidone.

thank you

 

[albada]

ID-62

Success! ID-62 with a separate PG solution works! I mixed them and tried it, with perfect results on Foma RC. I developed for 2 minutes at room temperature, and blacks are a hint darker than what Liquidol produced: densities were 1.91 vs 1.87.
The hydroquinone and phenidone are dissolved in propylene glycol (PG), and the rest are in the usual stock solution.
If these two solutions are stored in glass or PET bottles, and the PG solution kept refrigerated, I suspect they will last a couple of years (based on my experiences with other concentrates).

Here's what I mixed:

PG Solution

Propylene glycol (hot: 75-80 C) ..... 40 ml​

Hydroquinone ................................ 12 g​

Phenidone ...................................... 0.5 g​

Propylene glycol to make ............... 50 ml​

Stock Solution

Water .............................................. 800 ml​

Na2EDTA ........................................ 4 g (mix this first to avoid precipitates when adding alkalis below)​

Sodium sulfite, anh ......................... 50 g​

Sodium carbonate, anh .................. 60 g​

Potassium bromide ......................... 2 g​

Benzotriazole .................................. 0.2 g​

To Make 400 ml of Working Solution

Stock solution ................................. 100 ml​

PG solution ..................................... 5 ml​

Water to .......................................... 400 ml​

The EDTA is needed only if you'll be using tap water; it's not needed for distilled water.
My chemicals are 8-10 years old, and some are suspect because they were stored in bottles made of HDPE instead of glass or PET. The Phenidone turned light orange when dissolved in PG, making me suspect that my old PG has some water in it. When mixed with stock solution, the orange vanished because the sulfite restored the phenidone.

I don't have a hot plate, so I used a strip of scrap sheet aluminum on the stove.

I turn on only the left burner, at a medium-low setting, and the temperature of the sheet metal ranges from too hot (left) to too cool (right). I slide the beaker to the left or right to maintain correct temperature. I call this arrangement "the poor man's hot plate." I stir with the thermometer, so I can constantly monitor the temperature of the PG solution.

 

[BlueWind]

Very interesting options,

One question concerning commercial powder developers: if I use only part of the package, the part that I use may have different proportions of its componentes, as compared to using the whole package. In other words, the distribution of the componentes (in powder form) may not be homogeneous.

I was advised against using parts of the film developer Kodak D-76 for this reason, dissolving the whole package every time was the right thing to do.

Does this apply also to paper developers ??

Thank you once more

Joao

 

[Doremus Scudder]

Yes! In the 14 years that I've participated in this forum, you are the first to point out the meaning of my name.

Regarding the OP's desire for a "paper developer with long shelf-life":
I'm planning to mix ID-62 (see formula above in post #64), but I want to dissolve the two developers (phenidone and hydroquinone) in propylene glycol (PG). If I keep the PG solution refrigerated or frozen, and the stock solution at room temperature (hot in summer), I'm hoping that both will last over a year.
Has anyone tried this?

BTW, @relistan is putting developers in PG with his new PC-512 developer (here's the link to that thread).

Mark,

I mix ID-62 from scratch fairly regularly and have had no need to use PG at all. I do make a 1% aqueous solution of BTA, simply because it's easier to measure it that way.

FWIW, I use spoon recipes for most of my print developers, so mixing is quite easy and less time-consuming than dragging out the triple-beam balance scale. My dry chemicals are years old and still are as active as ever. Here's my spoon recipe for ID-62:

Note: This is to make 2 liters of working solution. By doubling the ingredients and using only one liter of water, you can make a stock solution that you then dilute 1+3.

Water (hot, ca. 120°F) ------ 1000ml
Sodium sulfite -------------- 1 Tbsp + 1/4 tsp
Hydroquinone -------------- 2 1/8 tsp
Sodium carbonate (mono) - 2 Tbsp
Phenidone ------------------ 1/8 tsp
Potassium bromide --------- rounded 1/8 tsp
Benzotriazole --------------- 10ml of a 1% solution
Water to make -------------- 2000ml

Starting the mix with just one liter and then topping up to two liters with cold water gets the developer closer to working temperature quickly.

By the way, "Kalium" is also German for potassium.

Best,

Doremus

 

[Anon Ymous]

Very interesting options,

One question concerning commercial powder developers: if I use only part of the package, the part that I use may have different proportions of its componentes, as compared to using the whole package. In other words, the distribution of the componentes (in powder form) may not be homogeneous.

I was advised against using parts of the film developer Kodak D-76 for this reason, dissolving the whole package every time was the right thing to do.

Does this apply also to paper developers ??

Thank you once more

Joao

Well, yes, it also applies to paper developers, but any consequences of uneven distribution will only affect a sheet of paper or two, not the precious film you carefully exposed and can't shoot again...

 

[Ian Grant]

Doremus, ID-62 is used 1+3 for normal use, so double strength would be 1+7.

Mark, as an Albada viewfinder user I'm not sure why the need to split a developer that keeps well into two parts, except to show it can be done. There was a time when MQ print developers were two part, and I keep ID-3 on my darkroom shelf as in two parts, it's identical to D165/Selectol Soft (originally a Kodak Ltd developer), Adaptall Soft is tye same.

Well perhaps one reason to split, you could have three different Part B's, one Normal, one for Warm-tones, and one for Cold-tones.

Ian