TEA/PG Paper Dev Concentrate Ideas?

I find that I'm in the darkroom more erratically of late. A recent post on Photo.net got me thinking about long shelf life paper developers. Has anyone been experimenting with this? Would it be too difficult to load the concentrate to levels that would leave a sufficiently alkaline developer after dilution or would it likely require some 2 part procedure? I'm stuck in the house with the flu today and the mind tends to wander.....

Craig, I've made and tested 2 TEA based concentrated paper developers.

1. Metol/ascorbic acid /TEA warm tone paper developer

2. Phenidone /ascorbic acid /TEA cold tone paper developer

The formulas are somewhere in the APUG archives - plus reports of activity testing over the last 2+ years, or PM me

I have been using a 2 solution concentrated version of Ilford ID-78 warm tone paper developer for about a year. The Phenidone and Hydroquinone are dissolved in the Propylene Glycol based A concentrate. PM me for the recipe.

I also designed a TEA version of ID-78 but didn't mix it or test it.

Craig, a URL for the PN thread would help.

Basically though, I find that many common print developers are not very stable and will not give me consistant results either through one printing session or over several days.

I need a good stable developer for my emulsion work. I find that my darkroom stays dark for several days while making emulsions and coating, and it is a pain to mix up fresh working solution (or what is worse, the stock solution) in near total darkness. I need to be able to start printing in the AM and end late at night and get identical results without tinkering with development time or exposure. Or, I have to print one morning what I coated the previous night, then recoat, dry overnight and retest in the morning, all with the darkroom nearly totally dark. Mixing developer in the dark is too error prone.

I have tested a number of products that have been quite dissapointing to say the least, and have begun developing my own print formulation in conjunction with Bill Troop.

For testing, I use a method I developed at Kodak (well, it really was an offshoot of work I learned earlier on and what was already in use at Kodak). As I go along, I hope to at least post this testing method. It is quite vigorous and quite revealing.

In any event, to answer you, more is involved than alkali. A developer must last a long time in the presence of oxygen in the air, carbon dioxide in the air, and useage (number of prints). So, a good developer must contain a mix of ingredients that satisfy all of these conditions. The pH and the alkali used are important as well as the antioxidant and the developing agent(s). All must be tested.

PE

I make concentrated stock solutions for long term storage convenience (like Kodak's HC-110) and for easy mixing of working solutions (liquids vs dry chems). Once working developers are prepared from these concentrated stock solutions, their useful life is pretty short.

For me, a stock solution should not be viscous and should last at least one year in a partially used bottle. It should be a 1 part developer, and should use even number dilutions for easy use.

The working developer should last one day to full capacity (number of prints) or should last up to 2 days or more in a tray with no change or a mix of the above. It should last longer if you wish to compensate in development time.

Dektol will just about do all of this. For example, the stock solution will only keep about 2 months or so as one example. But, it has other defects.

The items I mention above are doable, and infact can be exceeded by quite a bit.

PE

Have you tried ethol lpd? The concentrated solution easily lasts a year, and I have let it sit out in a tray for a couple days at a time.
If you rebottle the working solution it would last much longer.

Thanks;

If I can get some I will surely try it.

PE

I had a liter of PC-TEA stock that I wasn't using for film and one night when I didn't feel like mixing a more standard print developer for some quick tests, I mixed it 1+20 and it worked quite well. The stock was about a year old. The developer was still working the next day. For mw, such a developer has the advantage that I can use my very hard faucet water and not get cloudiness.
I have taken to throwing in a tablespoon of sulfite to the half gallon. I don't know if it does anything but maybe keep the solution from turning too brown for a little longer.

PE Wrote: For me, a stock solution should not be viscous and should last at least one year in a partially used bottle. It should be a 1 part developer, and should use even number dilutions for easy use.

All of those goals can be met with a Metol/Ascorbic Acid/TEA developer stock concentrate (or Phenidone/Ascorbic Acid/TEA developer stock concentrate) whose viscosity has been lowered by the addition of Propylene Glycol.

Tom;

This could go on interminably (the discussion and the tests). It is possible that your developer may indeed be all of those items in the quote, but then it might not meet the rest of my criteria which you didn't quote, and I cannot test every developer formula everyone suggests, nor every commercial product.

As stated before, we are working on one of our own formulation, and I am testing commercial products. That is sufficient for the time being. I am no where ready to post results or make recommendations.

I can say that until I find better, I'm using Dektol.

PE

Just some rambling thoughts:

Is TEA alkaline enough to make a one-solution print developer? Aren't print developers rather more alkaline than you could get just from TEA?

And does not the high alkalinity (or should i say higher pH) of most print developers cause faster deterioration? Maybe the answer to a print developer with a long life is to aim for a lower pH than normal, which might make it a warm-tone developer. Someone around here reported that ID-78 lasted very well, better than Neutol-WA (warm tone) which I found lasted very well (though it was in a Nova vertical slot processor).

john_s; said:

Just some rambling thoughts:

Is TEA alkaline enough to make a one-solution print developer?

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Yes, depending on the reducing agent(s) used, John.

john_s; said:

Aren't print developers rather more alkaline than you could get just from TEA?

Depends on the developer/reducing agents. Amidol paper developers will work at low pH.

Michael Smith's Azo Paper Amidol developer contains 8 grams/liter Amidol, 30 grams/liter sodium sulfite and 3 grams/liter Citric Acid.

And does not the high alkalinity (or should i say higher pH) of most print developers cause faster deterioration? Maybe the answer to a print developer with a long life is to aim for a lower pH than normal, which might make it a warm-tone developer.

Amidol comes to mind again - some folks report that it is active over a period of a few days. I use paper developers (including Amidol) as one-shots, so I have no first hand knowledge.

Someone around here reported that ID-78 lasted very well, better than Neutol-WA (warm tone) which I found lasted very well (though it was in a Nova vertical slot processor).

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Ian Grant, I believe.

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My darkroom seldom gets below 65 F. TEA alone can freeze there, but it has a strong tendency to supercool, so it is usually pourable. Also, the dissolved solids probably lower the freezing point. I have a brisker oven that stays at 104 F in which I keep some TEA solutions.

The pH of a TEA solution in water depends on thec oncentration. I used to have a chart from Dow that showed many interesting curves, but my hard drive crashed and I haven't replaced those charts. Diethanolamine has higher pH for a given concentration, but TEA is capable of 10 or so in moderately strong solutions.

PC-TEA as formulated several years ago has about 10 grams of ascorbic acid and 0.25 grams of phenidone in 100 ml of TEA. When this is added to 2 liters or 2 quarts of water (it's not that critical for paper) will develop RC papers fully in about 90 seconds when fresh. 2 minutes won't hurt.

You don't absolutely have to make a stock solution. It is easy enough to add 1 tbs + 1 tsp ascorbic acid to the 2 liters of water. about 1/8 tsp of phenidone or 1 tsp of metol and 100 ml of TEA will complete the mess. The phenidone will dissolve easier if you add it to the TEA first. It's almost as quick as opening the stock solution bottle and measuring out 100 ml. If you don't believe you can do without the balance or scale, try it both ways.

I did a Google while you weren't looking and found that 100 ml of TEA in 2 litrs of solution should give a pH slightly greater than 10. The commercial grade is a little higher. The impurity in it is IIRC mostly diethanolamine. It has pH > 11 at the same concentration.

If you are interested in such data, get the PDF file Overview of Ethanolamines from Dow Chemical. Its about the first site that comes up when you search Google for TEA, or ethanolamine or triethanolamine.

I'll throw in Ansco 130. It's not a concentrate, but I've mixed up the standard 1-liter formula, then diluted it 1:1 and decanted it into two one-liter bottles. I use one bottle as my working solution developer, then, at the end of a session, pour it back in the bottle. Then I top off the bottle with developer from the second bottle. I continue in this manner until the second bottle is used up - frequently about a year. I believe using glass, rather than plastic bottles is important.

Pat, the idea of using PC-TEA is interesting, too.

Juan, Glycin is soluble in TEA. About 2 years ago, I dissolved 11 grams of Glycin, 2.2 grams of Metol and 11 grams of Hydroquinone in 100ml of TEA. It's been sitting in my lab since I mixed it.

Think I'll add sufficient water to make a liter and then check the solution pH - if it's high enough I'll be pretty close to Ansco 130. I'll need to add some sodium sulfite to kill the stain and some KBr for fog and image tone.

john_s said:

Maybe the answer to a print developer with a long
life is to aim for a lower pH than normal,

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You will see Ansco 120 results from D-23; sulfite
activated. Both are metol only developers. Hydroquinone
will require a higher ph and or temperture before it takes
an active roll. An interesting post recently mentioned
temperature as a variable contrast control when
using a hydroquinone incorporated developer.

Some developers use hydroquinone only for it's
regenerative character; ie D-76. Beer's contrast
control developer phases in hydroquione in a
carbonted developer to increase contrast.
Hydroquinone disproportionately develops
more so the highly exposed areas of
the emulsion.

Phenidone reputeadly works at a lower ph and may
offer some possibilities for low ph processing.

Some one mentioned Ansco 130; a developer
with glycine included. Glycine does have a reputation
for imparting very long life. Glycine only developers are
at least carbonated. I think though that a lower ph
could be used with a number of developers given
and allowance for increase in exposure and time
in the developer. Dan

The composition of print developers is not as important as that of film developers. Why not just mix up fresh developer before a printing session using one of the teaspoon measure formulas available on the web.

Gerald;

I'm sorry, but I have to disagree with you there. I can see differences in toe and shoulder density among so-called identical print developers. I can also see differences in prints processed at the start and at the end of a printing session, or after a meal break.

If you look in my posts here in this thread, you will see that scratch mixing in the dark (or dim safelight) is a pain just as much as diluting a viscous or thick pre-mix stock solution is.

I want an easy to mix, rock stable developer that gives results like Dektol.

I plan on trying some of the suggestions here, but so far my tests have been dissapointing.

PE

Thanks Tom.

Yes ID78 does keep far better than liquid Neutol WA, someone else posted that it lasted days in a tray which is not true, and something I wouldn't contemplate doing.

Ian

Tom Hoskinson said:

Quote:
Someone around here reported that ID-78 lasted very well, better than Neutol-WA (warm tone) which I found lasted very well (though it was in a Nova vertical slot processor).

Ian Grant, I believe.

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craigclu said:

I find that I'm in the darkroom more erratically of late. A recent post on Photo.net got me thinking about long shelf life paper developers. Has anyone been experimenting with this? Would it be too difficult to load the concentrate to levels that would leave a sufficiently alkaline developer after dilution or would it likely require some 2 part procedure? I'm stuck in the house with the flu today and the mind tends to wander.....

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See the Chemistry recipe section for my article on my experiments with a variant of E-72 as well as various threads in the forum reporting updates.

I mix a 3X concentrate of the ingredients of my variant of E-72 (Includes some HQ) which I dilute 1:9 for working solution. I leave the alkaline out of the concentrate, however, and this makes the concentrate last virtually forever. When I'm ready to print, I simply mix the concentrate with water, then throw into the open tray, two tablespoons of sodium carbonate per liter of solution. It dissolves in a minute or so, and I'm ready to go. The solution in the tray has long life--I once tested it by leaving a partially used solution in the tray for nearly four days, and it was still fine, except for some discoloration due to oxidation.

Larry