Improved version of DS-10 by Ryuji Suzuki?

albada · Dec 20, 2011

Jerry:
Thanks for the book recommendation. I just received Mees, and I'll try to find this one as well.

Photo Engineer said:
You are looking in the wrong places. You want developer stabilizers, not silver halide solvents! At least in this context. As for silver halide solvents, you just have to experiment as the level is very much a function of the developer formulation itself. This is grinding plodding work that involves the use of what is called a factorial experiment.

DS-10 and XTOL get some of their fine grain from the solvent-effect of Sodium Sulfite, and we need a substitute for Sodium Sulfite that'll dissolve in Propylene Glycol. That's why I was looking at solvents. I thought that stabilizers didn't remove any silver halide, but merely rendered it unexposable, -or- improved the keeping qualities of an emulsion. Or do I have that wrong? (wouldn't be the first time).

Mark

Alan Johnson · Dec 21, 2011

Regarding solvents,you need to check the availability and safety aspects but I believe diethanolamine bisulfite may suit.
http://www.freestylephoto.biz/pdf/msds/ilford/ILFOTEC_LC29.PDF
Thiocyanate used to be used in Kodak DK20, see the Film Developing Cookbook p65, but appears to have found a new lease of life in Spur formulation, perhaps they solved some problems by advanced methods not generally known.I doubt it will dissolve in propylene glycol or TEA.
This is very advanced stuff if you just started to experiment.

Photo Engineer · Dec 21, 2011

Mark, there are emulsion stabilizers and developer stabilizers. There are even fix stabilizers! Sulfite does this job in all 3 cases but works by different methods in some cases. There are examples of all 3 types in my published work. The problem is that you are trying to fly before you can walk and that will take a bit of time. As Alan says, this is advanced stuff!

PE

Gerald C Koch · Dec 21, 2011

Haist mentions the amino acid cysteine as a silver halide solvent. I know that the amino acid arginine is also a silver halide solvent as it interferes with the classical analysis for chloride with Ag+. Both are available in health food stores as a powder at reasonable prices. They should be soluble in glycols. Cysteine contains a thiol (-SH) group along with many other chemicals which accounts for the halide solvency. Arginine has several amine groups which accounts for its solvency affect. Of the two mentioned cysteine is probsbly better as a first choice.

Ian Grant · Dec 21, 2011

There's mention of Haist's Monobath book but some of the Russian work is rather interesting and perhaps more advanced. I think it was Neville Maude who wrote an article which went a few steps further. I did scan it a few years ago and posted here (on APUG) but it may have been lost like many articles/formulae in updates to the site.

Alan Johnson is right in saying that devs like DK20 went out of use, as newer emulsions in the 1960's suffered dichoic fogging (my comment), but emulsions have changed again and these avenues are used again but with newer formulations.

Another well known person (think backwards) claims that Phenidone versions of MQ paper developerformulae are colder toned. when the exact opposite is true.

So the question is who/what do you believe or trust as films/emulsions change and comments made in the poast may no longer be apt.

Ian

Photo Engineer · Dec 21, 2011

I would have to look this up and perhaps it is in Haist, but some amino acids will severely reticulate film. Be very careful when you try to use them in tests as you may damage your film. I remember doing so many years ago! Sorry I cannot remember which one(s) do so.

PE

albada · Dec 21, 2011

Photo Engineer said:
I would have to look this up and perhaps it is in Haist, but some amino acids will severely reticulate film. Be very careful when you try to use them in tests as you may damage your film. I remember doing so many years ago! Sorry I cannot remember which one(s) do so.

That's no problem. I'll just name the developer "Reticulon".
Seriously, you are right about learning to walk first. I've realized that my knowledge of chemistry is badly rusty after decades of disuse, and that I need to buy a good college freshman level book and read-up.

Alan: Regarding diethanolamine bisulfite, that's a compound of DEA? DEA itself is a solvent, although in another posting, PE indirectly says it's probably a bit weaker than sulfite. Would the bisulfite-version be a stronger solvent?

Gerry: Thanks for the suggestions, and I'll look at the health food store for those amino acids, especially cysteine. Would any cysteine-compound suffice, or must it be cysteine-HCl?

Here's a formula that I'm thinking of mixing up and using as a basis of experimentation:

Propylene glycol .............. 48 ml (adjust so result is 50 ml. or 100 ml if too viscous)
Ascorbic acid ................. 10.7 g (alternate: Sodium ascorbate 12g)
Sodium metaborate ......... >=8 g (4g to convert ascorbic, + 4g for XTOL)
Boric acid ...................... ?? g
Phenidone ..................... 0.15 g

Makes 1 litre of working solution. The intention is that the metaborate would react with the ascorbic acid in situ, creating the 12g of ascorbate specified in the XTOL-patent. Other byproducts concern me, especially H2O. The remaining metaborate would be the alkali and form a buffer with the boric acid. The boric and/or metaborate would be adjusted to give a pH of 8.2, making this similar to XTOL but with no halide-solvent. And then would come the fun part of trying halide-solvents and probably tweaking other things. As always, comments about all this are welcome.

Mark Overton

cmacd123 · Dec 21, 2011

Photo Engineer said:
Mark...... The problem is that you are trying to fly before you can walk and that will take a bit of time. As Alan says, this is advanced stuff!

PE

If Mark is the same Mark Overton who used to post on Usenet, he actually does know how to fly, and spin.

Photo Engineer · Dec 22, 2011

Mark;

The ingredients you list are incompatible. Again you have mixed organics with inorganics and you cannot make a concentrate out of that mix. It will precipitate. If you dilute it with water it will mix though.

PE

Gerald C Koch · Dec 22, 2011

albada said:
That's no problem. I'll just name the developer "Reticulon".
Seriously, you are right about learning to walk first. I've realized that my knowledge of chemistry is badly rusty after decades of disuse, and that I need to buy a good college freshman level book and read-up.

Alan: Regarding diethanolamine bisulfite, that's a compound of DEA? DEA itself is a solvent, although in another posting, PE indirectly says it's probably a bit weaker than sulfite. Would the bisulfite-version be a stronger solvent?

Gerry: Thanks for the suggestions, and I'll look at the health food store for those amino acids, especially cysteine. Would any cysteine-compound suffice, or must it be cysteine-HCl?

Here's a formula that I'm thinking of mixing up and using as a basis of experimentation:

Propylene glycol .............. 48 ml (adjust so result is 50 ml. or 100 ml if too viscous)
Ascorbic acid ................. 10.7 g (alternate: Sodium ascorbate 12g)
Sodium metaborate ......... >=8 g (4g to convert ascorbic, + 4g for XTOL)
Boric acid ...................... ?? g
Phenidone ..................... 0.15 g

Makes 1 litre of working solution. The intention is that the metaborate would react with the ascorbic acid in situ, creating the 12g of ascorbate specified in the XTOL-patent. Other byproducts concern me, especially H2O. The remaining metaborate would be the alkali and form a buffer with the boric acid. The boric and/or metaborate would be adjusted to give a pH of 8.2, making this similar to XTOL but with no halide-solvent. And then would come the fun part of trying halide-solvents and probably tweaking other things. As always, comments about all this are welcome.

Mark Overton

Mark

Remember the rule that like dissolves like, sodium metaborate is an inorganic salt and would not dissolve in a glycol to any extent. The boric acid would probably form a borate ester with the glycol just as glycerine does. As I mentioned you need one or more compounds such as DEA and TEA to adjust the pH.

The addition compound of DEA and sulfur dioxide in a developer like HC-110 is used to supply sulfite ions when it is dissolved in water. It is used because an inorganic sulfite like sodium sulfite will not dissolve in organc solvents.

You will need to use the amino acid cysteine and not its HCl salt. I saw it quoted on one health site for $10.15 for 100 g but have seen it even cheaper. This is all somewhat speculative but cysteine having a thiol group is in the class of compounds mentioned as silver halide solvents. How much would be needed in a developer to reduce grain would have to be arrived at by trial and error. I would suggest first mixing working strength trial developers directly in water solution to arrive at a useful combination. Only then would I work on a glycol concentrate.

Jerry

Tronds · Dec 22, 2011

Gerald C Koch said:
Mark

Remember the rule that like dissolves like, sodium metaborate is an inorganic salt and would not dissolve in a glycol to any extent. The boric acid would probably form a borate ester with the glycol just as glycerine does. As I mentioned you need one or more compounds such as DEA and TEA to adjust the pH.

The addition compound of DEA and sulfur dioxide in a developer like HC-110 is used to supply sulfite ions when it is dissolved in water. It is used because an inorganic sulfite like sodium sulfite will not dissolve in organc solvents.

You will need to use the amino acid cysteine and not its HCl salt. I saw it quoted on one health site for $10.15 for 100 g but have seen it even cheaper. This is all somewhat speculative but cysteine having a thiol group is in the class of compounds mentioned as silver halide solvents. How much would be needed in a developer to reduce grain would have to be arrived at by trial and error. I would suggest first mixing working strength trial developers directly in water solution to arrive at a useful combination. Only then would I work on a glycol concentrate.

Jerry

I don't know how different propylene glycol is from etylene glycol, but consentrated engine coolant, etylene glycol can dissolve 12g sodium ascorbate, some phenidone, 20g borax and 4 g lye in 100ml. PC-glycol-metaborate.

Borax and lye in proper amounts is equal to sodiium metaborate.
Boric acid may not be a good idea in glycol. Haven't tried so I don't know for sure.
Sodium metabisulphite will not dissolve to any extent in glycol. I have tried, but only a very small part is dissolved. Less than 1g /100ml. I suspect that sodium sulphite wll behave the same way.

Gerald C Koch · Dec 22, 2011

Tronds,

When heated sodium metaborate decahydrate (borax) will dissolve in its own water of crystalization. I suspect that something similar is happening with ethylene gycol in that the borax is dissolving in what is essentially a mixture of glycol and water. This points out a problem since the purpose of using glycols is to provide a waterless solution to prevent oxidation of the developing agents. Inorganic compounds with water of crystalization will defeat the concept of a water-free developer concentrate since they add water to the solution.

Thanks for mentioning this.

Jerry

albada · Dec 22, 2011

Gerald C Koch said:
Tronds,
When heated sodium metaborate decahydrate (borax) will dissolve in its own water of crystalization. I suspect that something similar is happening with ethylene gycol in that the borax is dissolving in what is essentially a mixture of glycol and water. This points out a problem since the purpose of using glycols is to provide a waterless solution to prevent oxidation of the developing agents. Inorganic compounds with water of crystalization will defeat the concept of a water-free developer concentrate since they add water to the solution.
Thanks for mentioning this.
Jerry

I dissolved .1 g of the following borates into 5 ml of propylene glycol at room temperature: Borax, sodium metaborate, and boric acid. These were purchased from Photographers' Formulary. The borax solution was not used for the sodium metaborate and boric acid solution. I know that borax has many water molecules on it, but aren't boric acid and sodium metaborate anhydrous? If so, why did they dissolve in PG? Or should I have tried much more than .1g/5ml? Or perhaps my PG has some water in it (impurity).

Maybe a good experiment would be to heat the test tube containing an above mixture to 100C to drive out the water, and verify that the borates precipitate out as PE posted. Now that I think about it, PG is hygroscopic, and my 5 ml probably absorbed some water. Grrr.

Mark

analog what is that? · Dec 22, 2011

Does it really matter, if its hygroscopic, and if it stores chemicals protected from the atmosphere and oxygen for a long time while being hygroscopic, does it really matter?
Clearly this protection works any ways. I think this is questions that needs to be adressed....

Also two types of glycol was mentioned, I think the similarities and differences between them needs to be discussed too....

albada · Dec 22, 2011

Tronds said:
I don't know how different propylene glycol is from etylene glycol, but consentrated engine coolant, etylene glycol can dissolve 12g sodium ascorbate, some phenidone, 20g borax and 4 g lye in 100ml. PC-glycol-metaborate.

PE said inorganics should precipitate out. Could you try heating a sample of this mixture to 100C to drive out any water? Also, you can measure the volume or weight of the sample before and after heating to test whether some water was lost. I'm curious about this.

Best,

Mark Overton

analog what is that? · Dec 22, 2011

PE might be wrong there you know, or mentioned that in another context, not thinking on this....

I read that as a specific observation, not up for debate................

albada · Dec 22, 2011

analog what is that? said:
Does it really matter, if its hygroscopic, and if it stores chemicals protected from the atmosphere and oxygen for a long time while being hygroscopic, does it really matter?

I'll ask this differently: What fraction of water can be tolerated in a glycol-solution before storage-life is compromised due to oxidation?

On a different topic: cmacd123 said I can fly and spin. I guess that's referring to aerobatics, so I'm thinking that's a different Mark Overton. I've never had a pilot's license, but I can claim to have been at the controls of a friend's Helio Courier.

Mark Overton

Gerald C Koch · Dec 22, 2011

The chemical maxim that like dissolves like is true. Borax, an inorganic salt, is insoluble in methyl alcohol, an organic solvent. Diols, where the two -OH groups are on adjacent carbons, such as the glycols presents a special case with borates in that they form borate esters. This increases the solubility. The large water of crystalization, 10H2O, also helps.

Gerald C Koch · Dec 22, 2011

My earlier post was incorrect in that I said that sodium metaborate is borax. I really shouldn't post things late at night when I cannot sleep. What I should have written was sodium tetraborate. My bad.

Alan Johnson · Dec 22, 2011

Concerning how much water is allowable in TEA before oxidation occurs, Pat Gainer originally suggested 100ml water per liter of TEA (this was a method he devised so that PC-TEA could be made at low temperature).I tried this and found it failed after 9 months.Pat Gainer then revised his recommendation to 10.2 ml water per 1000 ml TEA but I have not seen any reports on the keeping of this.Anyhow, 10% water definitely fails quite rapidly.
It's in this long thread:
(there was a url link here which no longer exists)

Photo Engineer · Dec 22, 2011

Anhydrous Boric Acid is soluble in low molecular weight alcohols and poly-alcohols such as PG and EG. Not very, but soluble nonetheless. Sodium salts of Boric acid are not very soluble and any solubility is probably due to the waters of hydration. Boric acid + TEA forms a salt which may or may not redissolve. I have not tested this. In any case PG is better than EG from a toxicological standpoint and either is better than antifreeze due to the anti-rust chemicals in antifreeze.

The problem is that one must exclude oxygen and water from the concentrate. Kodak spent millions doing this and designing foolproof equipment to make hC110. Heating something on the stove can cause severe problems. When heated, and EG or PG mix with water in it can "bump" or create bubbles explosively when the temperature reaches or exceeds 100C. This can then cause the liquid to boil over and can create a fire if one is not careful. In addition, at this temperature EG and Phenidone create fumes that are not human friendly. Although the fumes from Phenidone are rather pleasant in odor, I don't believe you should subject yourself to the problem.

You need alkali, an oxygen scavenger (antioxidant) and a silver halide solvent that are soluble in one common solvent without water. There are chemicals that fit these criteria and still allow admixtures with developing agents. I repeat again - this can be done.

The adducts mentioned above may be available commercially and should be used if possible. This is the Sulfur Dioxide adduct of TEA and the HBr adduct of TEA. They can be home made at great expense and with great risk!

PE

Tronds · Dec 22, 2011

Gerald C Koch said:
Tronds,

When heated sodium metaborate decahydrate (borax) will dissolve in its own water of crystalization. I suspect that something similar is happening with ethylene gycol in that the borax is dissolving in what is essentially a mixture of glycol and water. This points out a problem since the purpose of using glycols is to provide a waterless solution to prevent oxidation of the developing agents. Inorganic compounds with water of crystalization will defeat the concept of a water-free developer concentrate since they add water to the solution.

Thanks for mentioning this.

Jerry

Let me see....... Where did I write heating or hot?
Scanning my text.... .... .... .... .... ... .... Nope. Didn't write anything about heating.
So, when I dissolved 20g borax in 75ml. etylene glycol WITHOUT heating, did it dissolve in it's own water?
If so, just placing it in a bottle on the bench should give the same result. It should dissolve in it's own water.
Surprise! It doesn't!

Try to dissolve 20g borax in 75ml methylated spirits. (Denaturated ethyl alcohol 95%.)
You can use as much heat as you want, but you can't make the borax dissolve "in it's own water" in ethyl alcohol.
In other words: It won't work!

From http://incidetech.net/tdsborax5mol.pdf

When heated in a closed tube, SODIUM BORATE begins to melt in its own water of crystallization at 128oC (262oF) and
is completely fluid at 140oC. Heated in the open, SODIUM BORATE loses its water of crystallization to complete
hydration and fusion at 742.5oC (1367oF)

Dissolving the borax was absolutely no problem. In fact, engine coolant DOES contain borax in it's concentrated form.
Solubility in propylene glycol at 25C is about 30% according to what I can find.
Solubility in ethylene glycol at 25C is 41.6%

That is way more than 20g in 75ml, is there is no need for heating the glycol to dissolve it.
Besides that, you need to heat the glycol/borax to 128C to make it dissolve in it's own water.
When I can handle the bottle with my bare hands, it is in no way close to that temperature.

So, how much water does 20g borax decahydrate contribute with?
About 6.42g.
In 100ml soluton this is about 6.42%
Does this render the solultion useless for storing developing agents? I don't think so.

What if you heat the ethylene glycol above 100c? Does the 6.42g of water evaporate?
Yes, it will.

So if you think this minute amount of water is a problem, just heat the glycol-borax solutuon above 100c fo some minutes.

BTW, engine coolant glycol is designed to protect the engine components from oxidation. I suppose it will do the same for developing agents.
In engines it protects from oxidation down to a concentration of about 30%. 6.42% water and 93.58% of etylene glycol mix is far more than 30%.

Maybe, but just maybe it will reduce the shelf life from 10 years down to 9.5 years, but I don't care. If I can't use 100ml of PC-glycol in 9 years, I just have to mix caffenol the few times I need to develop a film.

albada · Dec 22, 2011

Gerald C Koch said:
The chemical maxim that like dissolves like is true. Borax, an inorganic salt, is insoluble in methyl alcohol, an organic solvent. Diols, where the two -OH groups are on adjacent carbons, such as the glycols presents a special case with borates in that they form borate esters. This increases the solubility. The large water of crystalization, 10H2O, also helps.

Fascinating exception to the rule.
Here are a couple of tidbits that I forgot to mention which support what you said:

borax.com states that 21.53% of borax pentahydrate can be dissolved into PG (weight/weight). I don't know about decahydrate. Also, I'm leary of putting any borax into PG because of the H2O, and that's partly why I avoided it in my proposed developer from yesterday.
Boric acid is commonly mixed with PG in insecticides used to treat wood such as Bora-care, Penetreat and Timbor.

My question: Will the borate esters affect the functions of boric acid and sodium metaborate in a developer?
I think prior postings have already said "maybe" regarding boric acid, but how about metaborate?

Anyway, if borates dissolved in PG will function okay, then that's a good tool to have in our toolkit.

PE: Thanks for the warning about heating PG to 100C. What temperature do you think would be enough to drive out the H2O? When dissolving components into PG, I'd like to use a temp that's hot enough to keep H2O out, but no hotter.

Mark Overton

Tronds · Dec 22, 2011

albada said:
PE said inorganics should precipitate out. Could you try heating a sample of this mixture to 100C to drive out any water? Also, you can measure the volume or weight of the sample before and after heating to test whether some water was lost. I'm curious about this.

Best,

Mark Overton

I didn't heat it to dissolve the borax, but I had to heat a bit to dissolve the lye pearls and the sodium ascorbate. Not more than 50c though.
When heated and cooled again, it stayed in soluton, nothing precipitated out.

Heating to more than 100c will drive out any dissolved water, but since the engine coolant is designed to protect the engine components from oxidation, even in a 30% mix with water, I think this will be quite fine with the 6.42g of water introduced by the borax decahydrate.

Besides that, you need to heat the glycol-borax soluton to above 128c to split the water from the borax molecules. Storing at 20c or even 30c is quite safe if you think of it. This according to the datasheets for borax.

In an eralier attempt, where I tried to introduce 2g sodium metabisuphite in the solution. That won't dissolve. Adding 5ml of water made it possible to dissolve some of it, but not all of it.

Borax has the ability to bleach out colour of liquids. In the version with 5ml of water, it lost it's blue-green colour in 24 hours.
Without adding the 5ml of water, nothing happened.

Both versions is stored in bottles, so I will test both after 6 months, and after a year if both are still active after the 6 month period of storage.
The version with water and sulphite may loose its power, but then again, the sulphite and other components in the angine coolant may in fact preserve it.
Only testing will show what is happening over time.

What puzzles me is why is propylene glycol choosen as a container? Concentrated blue engine coolant is easier to get and may in fact be better suited to the task.

Trond Solem.

Tronds · Dec 22, 2011

About borax, glycol and formation of esters, and why the pH is lower than 9.2

This post explains a lot about what happens when dissoving borax in glycol.

(there was a url link here which no longer exists)

Improved version of DS-10 by Ryuji Suzuki?

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