Amidol/Propylene Glycol and Azo: Initial results

[Tom Hoskinson]

On June 21, 04, I mixed a stock solution of Amidol in Propylene Glycol. Yesterday (July 25, 04) I used the Amidol stock solution to prepare 1 liter of Michael Smith's Amidol formulation for Azo paper.

I developed a total of 20 8x10 Azo prints over a period of 5 hours. Development time was 1 minute plus or minus 5 sec at 70F (digitally timed). The developer activity was unchanged from print 1 through print 20.

Print exposure times ranged from 16 seconds to 35 seconds.

I was printing on the latest manufacturing lot of contrast grade 2 Azo. The Amidol developer produced a contrast grade result that was between grade 1 and grade 1.5, in my opinion.

The end result was a very nice set of work prints with excellent micro-tonality. The only other prints that come close (in my 4 print developer comparison with these negatives) are the prints I developed in Ansco 130.

To be completely fair, I am going to give PPPD another chance - I may have added the wrong quantity of restrainer to it. I got low contrast prints that lacked "snap." The PPPD prints looked pretty good until I compared them to the Ansco 130 prints and the Amidol prints.

I tried PPPD without the restrainer just to see what would happen and I got very warm toned prints with red tones in the dmax but good "snap."

 

[sanking]

On June 21, 04, I mixed a stock solution of Amidol in Propylene Glycol. Yesterday (July 25, 04) I used the Amidol stock solution to prepare 1 liter of Michael Smith's Amidol formulation for Azo paper.

Tom,

This is very interesting and sounds much more convenient than having to mix the developer from scratch for every printing session.

Did you give directions in another message on how prepare this mix? If not I think many of us would be very interested in exactly how you did this. I have personally found some a case where having the popylene glycol too hot breaks down the chemical and don't want to risk that.



Sandy

 

[Tom Hoskinson]

Tom,

This is very interesting and sounds much more convenient than having to mix the developer from scratch for every printing session.

Did you give directions in another message on how prepare this mix? If not I think many of us would be very interested in exactly how you did this. I have personally found some a case where having the popylene glycol too hot breaks down the chemical and don't want to risk that.



Sandy

Sandy, I believe that 8 grams of Amidol will dissolve in about 200ml of propylene glycol at 170F (or lower). As you will see below, I actually raised the temperature of the Amidol/PG solution to 270F in the process of trying to get the whole 8 grams of Amidol into solution in 150ml of PG. The elevated temperature does not appear to have affected the activity of the reagent over my 1 month "life test."

I will be mixing another (larger) batch of Amidol/PG stock solution this week and will post the results. Again, I will do this under a vented hood and will start with room temperature polyethylene glycol (~70F) for safety reasons.


Before trying propylene glycol as an Amidol solvent, I tried mixing 8 grams of Amidol in about 130ml of Methanol at room temperature. I estimate that about 5 grams of the 8 went into solution. The resulting solution was blue/violet in color. I did not life test this mixture.

Here is a quote from my June posting on Amidol/PG on the Chemistry thread in the Azo Forum:

"I also tried dissolving 8 grams of Amidol in 150ml of Propylene Glycol (PG). I put 150ml of PG in a 300ml Pyrex beaker, dropped in a teflon coated stirring magnet and poured in 8 grams of Amidol. Some of the Amidol slowly went into solution at room temperature (dark blue solution color). I increased the temperature with continuous magnetic stirring (under a vented chemical hood). Most of the Amidol dissolved by the time the solution reached 170 deg. F. I continued heating and stirring until the solution reached 270 deg. F. I could see that there was still some undissolved residue at that temperature. I slowly cooled the solution and decanted it into a bottle. There was about a gram (estimated) of undissolved material left in the beaker. I added 30ml of methanol to this residue, stirred and it dissolved (violet color). I added this to the PG mix (now a indigo color)and saw no color change. I will watch this solution for changes (color, activity, etc)."

 

[Tom Hoskinson]

Anyone try dissolving the Amidol in TEA for a simple one-solution/single agent paper developer?

I kicked the idea around, but Amidol likes a slightly acidic environment so from that perspective, TEA didn't seem like the best choice.

Also, I have some safety/toxicity concerns with mixing Amidol and TEA. Evolution of toxic fumes is one potential problem. Also, TEA is easily absorbed through the skin and mucous membranes.

 

[Tom Hoskinson]

Now that Amidol prints have dried, they are definitely warmer in tone and lower in contrast than the corresponding prints developed in Ansco 130, Gainer PC-TEA and PPPD:

MS Amidol - Contrast Grade 1.5, warm brown/black tones

Ansco 130 - Contrast Grade 2.5, cold Blue/Black tones

Gainer PC-TEA plus Benzotriazole - Contrast Grade 2, cold Black tones

PPPD plus KBr and Benzotriazole - Contrast Grade 1.75, cold Brown/Black tones

Depending on the subject matter, I found that I preferred the Amidol and Ansco 130 prints over the PC-TEA and PPPD prints. However, I owe PPPD another chance since I'm sure I fouled up when I added the restrainer.

 

[Sean]

Hi Tom, have you ever tried Rodinal with AZO? I've heard very conflicting stories, some saying it's a no go, and some saying it made their best prints yet..

 

[Tom Hoskinson]

Hi Tom, have you ever tried Rodinal with AZO? I've heard very conflicting stories, some saying it's a no go, and some saying it made their best prints yet..

No, but there's no reason not to try it. I always have a jug of Rodinal on hand. The last story I read about Rodinal/Azo described the result as "chalk and soot."

PC-TEA was designed as a film developer and it produced good results with Azo - but not very close to the Amidol results - or the Ansco 130.

 

[juan]

It's interesting that you got warmer tones from Amidol than 130. I got cold tones from Michael's amidol formula (using distilled water) - and warmer tones with 130 (the kit from Photographers Formulary.) I wonder if the glycol is the variable, or something else.

I tried Rodinal with Azo a couple of times. The first time, I used a dilution of 1:20, I believe, and thought the results were soot and chalk. Later, I tried 1:10 and liked the results better. Someone on this forum was using Rodinal with good results. Maybe he'll jump in.
juan

 

[juan]

Not yet, Jay. Unfortunately my boss thinks I need to be doing some extra work at the job that pays for film, paper and chemicals.
j

 

[photomc]

I Someone on this forum was using Rodinal with good results. Maybe he'll jump in.
juan

Juan,
I have done a little (key word, Little) work using Rodinal on Ilford MGIV and MGWT diluted 1:10. The print is posted in the Experimental gallery, it preformed the way I wanted - was trying from a warm print that would tone well in Viradon and that is what it did. Not sure the negative I picked was the best one, but it had more of an old processed feel to the print. Have not had time to try printing with more contrast or other dilutions, but the print has a very different look to it.

 

[Tom Hoskinson]

It's interesting that you got warmer tones from Amidol than 130. I got cold tones from Michael's amidol formula (using distilled water) - and warmer tones with 130 (the kit from Photographers Formulary.) I wonder if the glycol is the variable, or something else.

I tried Rodinal with Azo a couple of times. The first time, I used a dilution of 1:20, I believe, and thought the results were soot and chalk. Later, I tried 1:10 and liked the results better. Someone on this forum was using Rodinal with good results. Maybe he'll jump in.
juan

Hi Juan, I am virtually certain that the restrainer (KBr) quantity is the variable.

I mix all my chemistry with 18 megaohm deionized water (continuous quality monitoring) so that shouldn't be a factor.

I made a mass spectrometer run on a sample of the Glycin powder and it is the real stuff - high purity, too.

I mixed my Ansco 130 (and my PPPD) without KBr. I developed several work prints and observed high developer activity and warm tones (warmer than the MS Amidol).

Then I added 6 ml of 10% KBr to the Ansco 130. The developer activity slowed down and the tones went to blue/black (deep blacks - very nice). The prints have a lot of visual "snap."

I expect that if I use 2ml of 10% KBr per liter of working solution Ansco 130 I will get a warmer toned image than the MS Amidol. According to the literature, I can lower also the contrast with Ansco 130 by increasing the dilution.

Time for a second round of tests!

 

[juan]

The KBr cold be it. The Formulary 130 has 5.5g KBr in the 1-liter kit.
juan

 

[Tom Hoskinson]

The KBr cold be it. The Formulary 130 has 5.5g KBr in the 1-liter kit.
juan

Excellent pun, Juan.

Yes, I put twice that amount of KBr into my working developer. I won't call it a mistake - just serendipity.

 

[gainer]

It might be cheaper to use an essence of Rodinal. The magic of Rodinal is in its concentration and use of p-aminophenol HCl. This formula came from a Air Force photography manual of 1941.

p-aminophenol HCl 7 grams
sodium sulfite (desicated) 50 grams
sodium carbonate (anhydrous) 50 grams
water to 1 liter

It was specified for tropical use on film. No change up to 80 F. Add sodium sulphate above 80 F. Should work for paper as well.

 

[juan]

Any idea where to buy reasonable quantities of p-aminophenol HCl? A quick look at the usual suspects, and a quick Googling, turn up nothing except site dealing in hundreds of kilograms.
juan

 

[Tom Hoskinson]

Any idea where to buy reasonable quantities of p-aminophenol HCl? A quick look at the usual suspects, and a quick Googling, turn up nothing except site dealing in hundreds of kilograms.
juan

I have a sealed, 1 pound brown glass jar of it that I bought some time ago as a hedge against Agfa stopping production of Rodinal. I think it came from Baker, but I'll take a look.

Photographer's Formulary lists it for $41.00 a pound and they also list it in various smaller quantities.

 

[juan]

Ah, it's under the "A" not under the "P"
juan

 

[gainer]

I had some p-aminophenol from P. F. and tried 1/2 tablespoon of that with a tablespoon each of sulfite and carbonate in a liter for a quickie. It needed to be diluted 1:1 to resemble the potency of working strength Dektol. A print from 35 mm on Arista VC FB showed good tones, but I have no AZO to test it on.

This was the plain p-aminophanol, no HCl. The p-aminophenol HCl I had in stock (no wonder Kodak calle it Kodelon) had turned so black that I couldn't see a print thorugh a half inch of it

 

[Tom Hoskinson]

I had some p-aminophenol from P. F. and tried 1/2 tablespoon of that with a tablespoon each of sulfite and carbonate in a liter for a quickie. It needed to be diluted 1:1 to resemble the potency of working strength Dektol. A print from 35 mm on Arista VC FB showed good tones, but I have no AZO to test it on.

This was the plain p-aminophanol, no HCl. The p-aminophenol HCl I had in stock (no wonder Kodak calle it Kodelon) had turned so black that I couldn't see a print thorugh a half inch of it

Hi Pat, I'll give it a try with Azo.

Have you tried dissolving p-aminophenol in glycol or TEA?

 

[gainer]

Yes, but I don't remember the results. I can try again. IIRC, the HCl was more soluble. Actually, if you can humble yourself as I have to using teaspoon measurements, It will be just about as quick to mix up the stuff in water solution as needed. I would probably play with the amount of sulfite, and probably use ascorbic acid with little or no sulfite to see what effect it has on print quality. I know there is a degree of synergism between p-aminophenol and AA as I found with Rodinal and AA.

It would be nice if a mixture were found that mimiced amidol at less cost and longer shelf life. I have an old 5X7 view camera that I seldom use. Maybe I should get it out and get some Azo while I still can.

 

[gainer]

I should add, my Daddy used to say every once in a while, "Let's don't and say we did" or " let's do and say we didn't" especially when he wanted to play a trick on someone. He was a Doctor of Philosophy and Philology in English Literature, so he had to get some fun somehow. If we could not use amidol and get away with saying we did, wouldn't that be fun?

 

[gainer]

I measured 1/2 tablespoon of the p-aminophenol and found it was only 4 grams. In other words, the developer I found to be about as active as Dektol had 2 grams PAP (for short), 20 grams sodium sulfite, and about 25 grams sodium carbonate in a liter.

I added about 6 grams of isoascorbic acid (obtainable from the KIC Group at a good price as erythorbic acid) to the liter I had just ued and reprinted the same negative. There is no visible difference between the two 8X10 prints. The rate of development was about the same, probably because the reduction in pH due to the added acid countered the expected inrease in activity due to superadditivity. My next trial will be to decrease the sulfite, thus depending on the ascorbate to preserve as well as superadd. Unlike hydroquinone, ascorbic acid or its mirror image do not need sulfit for superadditivity with phenidone or the aminophenols. If we are trying for an easy-mix print developer that works like Rodinal, a minimal amount of sulfite is what many say gives Rodinal part of its mystique. IMHO, adding some ascorbate to Rodinal working solution leaves the Rodinal sharpness but reduces its granularity a smidgeon.

To invert a phrase: "OK, it works that way in real life, but will it work that way on paper?" We'll see.

 

[Tom Hoskinson]

To invert a phrase: "OK, it works that way in real life, but will it work that way on paper?" We'll see.

Ah Pat - I see that you are out on the slippery slope already!

Next, you'll be hauling out that 5x7.

I could send you a dozen sheets of 8x10 Azo to get you hooked...

 

[gainer]

Hey, I live in West Virginia about 1000 feet above sea level with another 200 or so to the top of the mountain. In the winter and sometimes in the summer, there's nothing but slippery slopes around here.

 

[Tom Hoskinson]

Here is an P-Aminophenol/Hydroquinone Universal Formula - Kodak DK-93

Water (125 F) ----------------------------- 500ml
P-Aminophenol Hydrochloride (HCL) ---------- 5 grams
Sodium Sulfite ----------------------------- 30 grams
Hydroquinone ------------------------------ 2.5 grams
Sodium Metaborate ------------------------ 20 grams
Potassium Bromide ------------------------- 0.5 grams
Cold water to ------------------------------ 1 liter

For roll film developed in tanks, as a starting point, use without dilution and develop for 9 minutes at 68 F .

For warm tones on paper use without dilution and develop for 2 minutes at 68 F.

For colder tones on paper, double the quantity of metaborate and develop for 1 to 2 minutes at 68 F.