Glycin... fresh glycin... what developers to make with it?

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sanking

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RidingWaves said:
What would be the conversion for Agfa 8 if you were to replace the Potassium Carbonate with Sodium Carbonate?

The difference woud be too small to be of any practical consequence in my opinion, at least in most cases. In the great majority of formulas, both paper and film, sodium and potassium carbonat are interchangeable at about the same weight. Be aware, however, that sodium carbonate is much less soluble than potassium carbonate, so in formulas that require a very high percentage solution of potassium carbonate it would not be possile to substitute sodium at the same amount because it would not go into solution.

Sandy King
 

dancqu

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sanking said:
Just for the record, I have found that Ansco 130 has
very good keeping qualities, and gives great results with
AZO. Unless you need water bath control of course.
Sandy King

Tom mentioned water bath control with Amidol but you
say not with Glycin. Do you suppose that has to do with
the low and the high ph at which the two work. I know
Glycin requires at least a carbonate but at just what
ph are users using Amidol? Dan
 

Tom Hoskinson

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RidingWaves said:
So would sodium carbonate work in Agfa 8? 25g does not seem that much.

Agfa 8 works fine with sodium carbonate.
 

Tom Hoskinson

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dancqu said:
Tom mentioned water bath control with Amidol but you
say not with Glycin. Do you suppose that has to do with
the low and the high ph at which the two work. I know
Glycin requires at least a carbonate but at just what
ph are users using Amidol? Dan

A rather low pH, Dan. Here is Michael A Smith's Amidol for Azo recipe:

Water---------------------------------------- 900 ml
Sodium Sulfite----------------------------- 30 grams
Citric Acid----------------------------------- 3 grams
Potassium Bromide (10% solution)------------ 2ml
Amidol--------------------------------------- 8 grams
Water to make--------------------------------1 liter

See: http://www.michaelandpaula.com/mp/startframe.html
 

sanking

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dancqu said:
Tom mentioned water bath control with Amidol but you
say not with Glycin. Do you suppose that has to do with
the low and the high ph at which the two work. I know
Glycin requires at least a carbonate but at just what
ph are users using Amidol? Dan

As Tom noted, the MAS formula is a fairly low pH working formula, and this may indeed have something to do with why water bath contrast control works with amidol and not glycin.

Another thing to note is that the reduction potential of amidol is much higher than that of glycin. Reduction potential is an old term not seen very often in today's literature. It refers to the relative reducing energy of the developer showing by comparing them to hydroquinone, which would be 1. In that comparison glyin is 1.6, amidol is 30-40, metol is 20.

I don't understand the specifc mechanism of water bath control with amidol. However, it seems reasonable to speculate that it is governed by both the low working pH, which allows continuing action in water at low pH, in combination with the high reduction potential of amidol, which means very little of it need to be in the emulsion in the water bath for some continuing action in the highlights.


Sandy King
 

pentaxpete

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also Geoffrey Crawley had a 'Crystalline Potassium Carbonate ' in his FX-2 formula -- I have the 'Ordinary' version -- would it still work do you think at the same weight?
 

Michel Hardy-Vallée

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Here's one I found in my 1969 Focal Encyclopedia of Photography, it looks a lot like Agfa 8:

Stock solution:
Glycin: 37g
Sodium Sulfite, anhyd: 30g
Potassium Carbonate: 175g
Water to make 1L

Dilute 1+6 for normal tank development, and starting time is 45 mins at 65F

For stand development, dilute 1+50 and develop for 4-5 hours.
 

grainyvision

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EXG1 is practically the D-23 of glycin film developers, super simple though a pain to mix. It's made in two parts:

Part A -- 10% glycin in TEA
* 70ml triethanolamine 99% grade, heated (I've only been able to source low freeze grade with water contaminate. This is fine though. I use photographer's formulary TEA)
* Add 10g glycin slowly (too much will cause it to cake up and dissolve slower)
* With continued stirring and heating, it'll eventually just suddenly begin dissolving very quickly
* Top to 100ml with TEA

Part B -- 20% potassium carbonate in water

* 400ml of water, room temperature or colder
* Add 120g potassium carbonate, anhydrous. Solution will heat up
* Top to 600ml with water

Appearance: Part B will of course be clear and should last indefinitely. Part A will be a very mild pale brown.

Usage: Add 20ml of part A to 900ml of water. If using a graduate make sure to rinse the graduate several times. Then add 60ml of part B and top to 1L with water. Use working solution within a few hours, it is not stable. Develop FP4+ for 11m. See my website or massive dev chart for more developing times: https://grainy.vision/blog/exg1-a-bare-bones-glycin-film-developer

Shelf life: Part A will discolor and change in activity over time. I'd estimate that the safe shelf life is 1-2 months, though it will continue to work for much longer with different activity levels. The most notable thing in aging is that the amount of grain will increase. The contrast curves are otherwise fairly linear in the ways they decrease and so an age affected developer will not cause abrupt failure, but will give a change in results. Developer "goodness" can be tested when making the working solution by observing the following:

* The part A stock solution should be a somewhat pinkish orange before introducing water, maybe more yellow when very freshly mixed. If it is a deep brown or orange, it will likely have a difference in results
* When adding the part A to water, if you can catch it, there is sometimes a color change to orange that only lasts very briefly
* After mixed into the water after at most a minute, the solution should then change to a pale straw yellow with a hint of pink. This is the final color. If the solution is brown or a deeper yellow, expect a difference in results
* When adding the carbonate, the solution will turn a deep orange, sometimes even slightly brown. This is expected
* After 30s or so, the solution should return to a the pale final pale pinkish yellow color. If the solution does not undergo the final color change to pale pinkish yellow, then you should expect a significant difference in the results
* The solution should remain close to this color even after development (assuming no antihalation dyes of course)

Characteristics:
* Full speed results with no staining or fogging, even when pushing and with long development times. (note: stand development is untested)
* Fairly normal to slightly increased contrast with slightly increased scale. Tends to give brilliant results when printed with lower contrast highlights that are a bit further away from shadows than normal
* Coarse and sharp but "honest" grain. Grain does not seem to increase very much with additional development. Delta/T-grain films will be VERY grainy, even the slow speed ones.
* Ideal for pushing, additional time seems to maintain a reasonable amount of contrast
* Tends to become slightly more grainy as developer ages, but with minimal differences in contrast until after the "goodness" test becomes questionable.
 

DREW WILEY

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Mix enough 130 for a daily session. Unused powder in a well sealed bottle will remain stable if frozen. Opened bottles of fresh off-white powder are good for a number of months in powder form. As the powder oxidizes to a more chocolate color, the glycin stains more. I have no idea why people want to mix up a big batch all at once. That's like re-using dirty dishwater. As far as amidol comparisons go, it tends to be quite different in effect. My personal amidol formula is acidic and similar to one already posted, with no carbonate. I use glycin and amidol strictly in paper developers, though I once experimented with film usage.
 
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Michel Hardy-Vallée

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I tried out Agfa/Ansco 72 today:

800 mL water (52C)
125g Sodium Sulfite, anhydrous
250g Potassium Carbonate
50g Glycin
Water to make 1L

Agfa gives times/dilutions that are way too intense for modern films. They suggest 1+5 for 20-25 min, or 1+4 for 5 min.

I tried it on HP5+ and I had to cut down dilution to 1+19, for 5 min, and got spot on negatives. 5-7 min would be a useful starting bracket.
 

Louis Nargi

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Keep your Glyin in the freezer in the bag it comes in it will last longer
 

bnxvs

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Para-hydroxyphenyl glycine (glycine-photo) can be reduced and purified using hydrosulfite in the presence of ammonia. It is enough just to boil the glycine solution with the addition of ammonia (10/4) and a small amount of bisulfite (metabisulfite). After cooling and filtration, add 30-40% bisulfite solution - crystals of pure para-hydroxyphenyl glycine will precipitate.
 

grainyvision

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Para-hydroxyphenyl glycine (glycine-photo) can be reduced and purified using hydrosulfite in the presence of ammonia. It is enough just to boil the glycine solution with the addition of ammonia (10/4) and a small amount of bisulfite (metabisulfite). After cooling and filtration, add 30-40% bisulfite solution - crystals of pure para-hydroxyphenyl glycine will precipitate.

Wouldn't this require vacuum distillation or something else a bit more involved? Specifically the glycin that precipitates would be soluble in the solution... or do you mean to add enough bisulfite solution to make the solution neutral and thus the glycin insoluble?

I've noticed glycin stored in acid is some freaky stuff. It will dissolve but is pretty reluctant in it, but if you try to bring it up to an alkali, like with carbonate, it'll all fall out of solution and be even more reluctant to go back into solution afterwards. Could this be done as a method of purifying (but not recovering) oxidized glycin? Like if you have some glycin that has gone off and is black, could you dissolve it into acid, filter off the tar, then bring it to exactly neutral so the glycin falls out of solution and filter/dry the precipitate? I guess it depends on what exactly glycin oxidizes to and what the properties of that are. I've tried to research how glycin oxidizes and what makes it work how it does but I have turned up absolutely nothing on the internet.
 
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I tried out Agfa/Ansco 72 today:

800 mL water (52C)
125g Sodium Sulfite, anhydrous
250g Potassium Carbonate
50g Glycin
Water to make 1L

Agfa gives times/dilutions that are way too intense for modern films. They suggest 1+5 for 20-25 min, or 1+4 for 5 min.

I tried it on HP5+ and I had to cut down dilution to 1+19, for 5 min, and got spot on negatives. 5-7 min would be a useful starting bracket.

Even at 1+19, your working solution (1l) has 2.5g glycin, 12.5g carbonate and 6.25g of sulfite. Compare this with the working solution (1l) of GSD-10 which has 1g glycin, 7.5g carbonate and 5g of sulfite. So 1+49 might work right albeit with increased developing time. It would save a lot of chemistry for sure.
 

Michel Hardy-Vallée

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Even at 1+19, your working solution (1l) has 2.5g glycin, 12.5g carbonate and 6.25g of sulfite. Compare this with the working solution (1l) of GSD-10 which has 1g glycin, 7.5g carbonate and 5g of sulfite. So 1+49 might work right albeit with increased developing time. It would save a lot of chemistry for sure.

Yep, but it was working pretty decently at 1+19, so at 1+49 I would probably have to up the developing time to 10 mins. At 1+19 I'm good around 5 mins.
 

Bikerider

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Call me a stick in the mud, but if you're setting off to mix up something new, try some tried and true formulae, and see what they do before venturing off into the unknown.
.

Absolutely we have a saying in UK, learn to walk before you run. Oh by the way welcome back from the dark side.
 

Michel Hardy-Vallée

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Well, after doing some prints, it looks like Agfa 72 is an interesting developer.

It's not the sharpest one (compared to a typical MQ like Agfa 48M or DK-50), but it has very nice gradations.

So when used on Ilford FP4+, which has good inherent sharpness, the results are pretty nice.
 

grainyvision

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One glycin developer I formulated and really enjoy is called GVK1. It is relatively unusual being a metol+glycin developer and with a significant amount of TEA. It tends to give moderate grain, hold down contrast particularly well when pushing, and is speed increasing.

Full post about it with examples: https://grainy.vision/blog/gvk1

Part A:
  • 700ml of hot water
  • 5g metol (typical “pinch of sulfite” beforehand)
  • 50g sodium sulfite
  • 200ml propylene glycol (this works to reduce the amount of oxygen water contributes and makes the glycin more easily soluble. Can likely be substituted with water though)
  • 5g glycin
  • Top to 1L with water
Part B:
  • 700ml of hot water
  • 20g potassium carbonate, anhydrous
  • 200ml triethanolamine (TEA) 99% grade
  • Top to 1L with water
Use 100+100+800 to make 1L of developer. Use at temperatures no colder than 72F/22C and if under developed or developed too cold will give an extremely high amount of grain. Seems to become finer grain with longer development time or higher temperatures. FP4 12m, Foma 200 10.5m, HP5+ 18m. It doesn't follow a development curve of any other developer I can tell, so testing will be required for each new film its used for.

Shelf life should practically be nearly forever. I've noticed no difference in results nor color of solution over 3 months of storage in a half full bottle.
 

bnxvs

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Wouldn't this require vacuum distillation or something else a bit more involved? Specifically the glycin that precipitates would be soluble in the solution... or do you mean to add enough bisulfite solution to make the solution neutral and thus the glycin insoluble?
[/ QUOTE]
In principle, correct. Bisulfite gives acidic pH. Ammonia, on the other hand, is alkaline. Plus, SO2 is a reducing agent.
This cleaning method was patented back in the 80s of the last century))) I can give you a link to the patent, but it is in Russian.
 
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