Improved version of DS-10 by Ryuji Suzuki?

analog what is that? · Dec 23, 2011

Funny how negative this is perceived, as a chemist one should rather encourage experiments.....

And as far as I'm concerned Ron, your developers currently on sale simply does not exist! Never heard of them, never seen them on sale anywhere, and they sure as hell never WILL BE on sale here, because supply and demand dictates that such an esoteric piece of trade as pre-packaged film developers will not sell to anyone but two crankpots in this entire country - and its getting worse.

Me getting into home-brew developers, this late in history, when I can no longer walk up to the counter of the closest city Merk's representative and order all kinds of fancy chemicals and have many of them handed me straight over the counter, is a precaution, I just wanna be able to develop films as long as I CHOOSE, not being dictated by businesspeople, by the looks of it I will still be able to find outdated film until I'm approaching 80, so thats what I concentrate on, nothing else is available here any longer, we have been digitalized.

analog what is that? · Dec 23, 2011

The simple solution to PC-glycol and the concentration of silver solvents is suimply to add them with the water!
After all glycol is just a CONTAINER!!

albada · Dec 23, 2011

I followed Jerry's suggestion, and tested the components in water first, in order to verify and tweak the formula, before attempting the PG. Here's the one-liter formula I ended up with:

Ascorbic acid ..................... 10.7 g
Sodium metaborate ............. 9.5 g
Boric acid ........................... 4 g
Sodium sulfite ..................... 90 g
Phenidone .......................... 0.15 g (I used a 1% solution in PG)

Target pH is 8.2 (same as XTOL). Same development-times as XTOL.
The ascorbic acid combines with 4g of the metaborate to form 12 grams of sodium ascorbate.

I tested this scaled down to 200 ml, 6.5 minutes at 20C for TMY.
The results compared to an identical negative from the same roll developed in XTOL under the same conditions:

Same density (gauged visually). Same sharpness. Possibly a hint more grain. A hint more shadow-detail. Possibly a hint more fog.

I think most people could not tell the difference between this and XTOL.

My concern now is that 24 grams of powder may be too much to dissolve into 50 ml of PG (1+19 dilution), and might not even be possible for 100 ml (1+9 dilution).

Tidbit: I read in either the FDC or TDC that boric acid is very slow to dissolve. I discovered that it dissolves almost instantly in near-boiling water. Heating a separate beaker containing a little water for only the boric acid means you don't need to heat the entire working solution.

Mark Overton

Photo Engineer · Dec 23, 2011

Very nice. Congratulations.

Look up Boric Acid in Wikipedia. That may give some help.

PE

Photo Engineer · Dec 23, 2011

AWIT;

The reason I mentioned my developers is twofold. One is to show that a new formula can be compounded in a home lab and can be sold commercially! the second is that this particular developer embodies many of the solutions to problems posed in this thread. It uses electron transport chemistry to give long life to the developer with no change in activity. It is primarily a paper developer, but a film developer is on the books and that uses a new type of Silver Halide solvent.

So, I am working here at home on a number of new solutions to problems that you all are considering. I have the advantage of knowing what was being worked on when these projects were cancelled at EK.

PE

MattKing · Dec 23, 2011

analog what is that? said:
Naaa that is an argument without any practical merit in THIS context.
We are not developing color films you know, (most of us) are not printing in the darkroom any more, fewer will in the future.
We employ a modern gizmo called a scanner. This thing cuts through bot fog and color dyes like a knife in butter.
It is also fully color sentisive, so we can scan any color we, like and change the colors afterward or even turn the thing into B/W with just one click on a virtual button...

So this was an answer looking for a good question....

For your information we come from a running debate on Caffenol, where the guys demand to exchange KBr with iodized table salt, large amounts of it, and accept the acompanying yellow stain as if nothing happened....

Why is this on APUG?

Photo Engineer · Dec 23, 2011

MattKing said:
Why is this on APUG?

Matt;

I asked myself the same question but gave it a pass in the spirit of the holidays.

Maybe I should have resisted the holiday urge!

PE

analog what is that? · Dec 23, 2011

Good Ron, what I'm after is not stealing you thunder, nor infringing on any commercial interests (no market - absolutely zero! around these parts), but some solid info, so when you mention you have developers out there selling, why put your light under a shade, give us the name, it is nothing to be ashamed of, on the contrary.

Also when discussing actual recipes, I feel it is in the spirit of the internet to offer real advice, not hints.

Its akin to "try metol instead of pyrocatechine, it will give you better results in IMHO" - this is not like if you are giving out any life inheritance......

Also those new solutions : are they compatible with chemicals available on the open market? If that is the case it might be of some interest to amateurs like us, but what we really need is stuff we can buy at the mall, paintshop or auto and hardware store, unless that it can safely be forgotten.....

Or are you actually planning to bring out a NEW developer in todays business climate? With all the capital costs involved in such a venture, your banker will probably land in jail....

Photo Engineer · Dec 23, 2011

AWIT;

There is a whole thread on this developer with examples. I don't intend to belabor the issue on that as I fully discussed the chemistry involved. It is known well enough. And, I have already given substantial information here such as saying that there are better Phenidone developing agents than Phenidone itself due to hydroxide instability.

One of the posters listed ALL of the methods I used but one and IDK how he missed one important possible compound. Oh well, I am not gong to give details. I used to have a professor that was like me. He would give hints and say that the answers were in the textbook and these references! I learned a lot from his class! I want you guys to learn, not have it handed to you on a platter.

Which do you want? You will get results quicker one way, but you will learn more the other way.

PE

analog what is that? · Dec 23, 2011

Oh well I'll bow out of this Matt, and go back to having fun with & fine-tuning Twinningole(s) & Liptonole(s) and publish full recipes on blogs and elsewhere, have to take you seriously when you start rattling sabers............. happy holydays!

analog what is that? · Dec 23, 2011

One last thing: It is common courtesy, when there is a thread adressing the subject at hand to give the actual link right here, or ask if anyone remembers / has it, in case it slipped the mind, so that people get to know where to start looking, anythingg else can be seen as footdragging, disinformation and stall tactics - to actually discourage unsuspecting newbies from ever trying out anything for themselves.

Thank you.

Photo Engineer · Dec 23, 2011

AWIT;

I have been asked to disassociate myself from my developer and any thread regarding Ryuji's products as they are in direct competition. As this fact seems to have escaped you, as has the existence of my process chemistry and my credentials, I'll just let this sleeping dog lie as is.

As for keeping references, I keep none anyhow. As you can easily see from my post count, I simply cannot keep track of them, especially with my schedule regarding the book and the DVDs. If you don't follow those comments, then sorry again. So, there you are stuck with a number of non-sequiturs from your POV I guess. Basically, you have walked into the middle of a long standing discussion on a very complex discussion and have been at a loss all along as to what is going on. It is one that stretches out over 3 or more years on this same topic with Pat Gainer, Kirk Keyes, myself, Ryuji and many many others. And no one has done any homework.

PE

albada · Dec 24, 2011

Photo Engineer said:
Very nice. Congratulations.
Look up Boric Acid in Wikipedia. That may give some help.
PE

And it says that it dissolves in boiling water. As you said in a recent posting, folks learn better when they dig up facts for themselves.

More news:

I went ahead and mixed my formula ((there was a url link here which no longer exists)) into PG, keeping the sulfite separate. The following numbers are for 200 ml working solution. When heated, it all dissolved easily in 16 ml (total volume) of concentrate. I ended up with 19 ml after adding the 1% phenidone solution. There was no precipitation upon cooling, even when cooled down to refrigerator-temperature. Obviously, viscosity went up, but viscosity was reasonable at room-temp. 15.4 ml would probably be fine, and that represents a dilution of 1+12. To make one-liter, you'd have 77ml of concentrate for 1+12. I think that's reasonable.

The pH of the resultant working solution was correct, yet the test-strip was a little thin. I can speculate on a few possible causes:

I damaged the developer when heating.
Having those large PG molecules in the way hinders development (think "obstacles").
The PG is forming esters with the borates, changing their behavior (Jerry suggested this).

Comments from the chemists are eagerly awaited!
Also, the boric acid is there to form a buffer-system with the metaborate. Would this buffer be effective if those molecules have formed esters with the PG? If not, omitting the boric acid and reducing the metaborate would permit a greater concentration.

BTW, I want to thank those who've posted helpful suggestions in this thread, especially Ron (PE) and Jerry. You guys are a lifesaver! There's no way I could have gotten to this point so quickly (or at all?) without your help.

Mark Overton

Hexavalent · Dec 24, 2011

analog what is that? said:
One last thing: It is common courtesy, when there is a thread adressing the subject at hand to give the actual link right here, or ask if anyone remembers / has it, in case it slipped the mind, so that people get to know where to start looking, anythingg else can be seen as footdragging, disinformation and stall tactics - to actually discourage unsuspecting newbies from ever trying out anything for themselves.

Thank you.

There is also a button with the label "advanced search", it does wonders.

albada · Dec 24, 2011

Photo Engineer said:
One of the posters listed ALL of the methods I used but one and IDK how he missed one important possible compound

Oops, looks like I better re-read those patents...

Mark Overton

Photo Engineer · Dec 24, 2011

Mark;

You are closing in. Boric Acid reacts with many Polyols to form rubbery compounds that may or may not help this situation. I do NOT recommend the use of Phenidone. I've said this 3 times (IIRC) in this thread. Try Dimezone or Dimezone @! Phenidone decomposes upon heating in base!

I could go on, but congratulations. AWIT does not agree with you about learning.

Please re-read Edens and Mowrey. Lots of antioxidants in there!

Best wishes on a nice step forward.

PE

Ryuji · Dec 24, 2011

albada said:
Two questions for Ryuji about DS-10 (I hope he's still watching this long thread):

1. Could the Dimezone and Ascorbic acid be kept in a separate concentrate in propylene glycol? I would hope that both concentrate and working solution (containing no developers) would last at least a year. Before using, some concentrate would be added to working solution for one-shot use.

2. If the answer to question 1 is "yes", then are TEA and Salicylic acid still needed? Your older posts indicate they are used to chelate iron to protect the developers to improve storage-life. Does the TEA affect image-quality?

1. Yes. But if you do that, why dont you just use dry ascorbic acid? That just solves the ultimate problem so that you can focus on shooting.

2. Yes. You cant just change on ingredient without affecting some other roles in the developer. If you try to remove or replace one thing, it would generally have to be balanced out by changing something else.

Ryuji · Dec 24, 2011

albada said:
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 suggest to scrap that line of effort. The logic is right, but that line of ideas have been tried and retried a great many times, some by myself. Many chemists still prefer sodium sulfite.

Ryuji · Dec 24, 2011

Gerald C Koch said:
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.

What you don't realize is that cysteine deteriorates gelatin. I wouldn't use it in practical processing solution. When reading literature, you always have to keep practical factors in mind.

Ryuji · Dec 24, 2011

albada said:
Would this buffer be effective if those molecules have formed esters with the PG? If not, omitting the boric acid and reducing the metaborate would permit a greater concentration.

BTW, I want to thank those who've posted helpful suggestions in this thread, especially Ron (PE) and Jerry. You guys are a lifesaver! There's no way I could have gotten to this point so quickly (or at all?) without your help.

Another piece of dangerous half knowledge. Ester of borates with polyols is a very slow reaction that needs to be accelerated to be practical, but then the reaction is condensation reaction. Dilute your mixture in water and it will be undone in a moment. Nothing to worry about.

Incidentally, ascorbates can form ester with borates if properly reacted. Again, it is not a concern with aquaous developer solutions.

Ryuji · Dec 24, 2011

Guys,

Heres what I think after reading this long thread.

If your purpose is to tinker about basic chemistry, I think you can find more fun and easier projects to learn basics. Developer chemistry is complex, yet not very rewarding because there are so many rigid and exacting requirements for practical developers, and then any difference in developers is not going to make a night-and-day difference in photography. A new developers just provide another way to arrive at the same result. Most of you already spent more effort being on this topic than the entire amount of effort that could be saved by being able to avoid weighing powder sulfite and ascorbate each time you develop film.

If you are trying to make money by coming up with a great product, it wouldnt be a darkroom product, either. There is no money in darkroom products. At this point and time, there is not. One answer is skin care products, cosmetics and pharmaceuticals.

If you are genuinely trying to make some difference in photographic chemistry, why dont you tackle a new challenge that no existing formula adequately dealt with? Still, the golden era of developer chemistry will not come again. Its not lack of your million dollar budget. It is the result of what we already know from the past research and what we will probably never find out due to known difficulties. The current film based imaging is rather perfected in many ways, and there is little room to improve upon.

So, why dont you pick up a camera and shoot more film? Kodak and Fujifilm need you. Kodak will raise the price in a few months. Time to burn some old stocks and buy more bricks.

albada · Dec 24, 2011

Ryuji said:
If your purpose is to tinker about basic chemistry, I think you can find more fun and easier projects to learn basics.

I shoot maybe one roll a month in 35mm, and I can't use my 5 liters of XTOL before it goes bad. A concentrate that gives XTOL-quality would be perfect for hobbyist-shooters like me, but no major manufacturer makes one. Even if a small company made one, I wouldn't feel comfortable because: What happens if the little company closes? My developer vanishes. So I want the concentrate to either (1) be made by a large company, or (2) have a published formula so I can mix it myself (in case the company vanishes).

Also, I enjoy learning about new things. And sometimes I invent something useful. Here's an example:
http://drdobbs.com/tools/229625477

For hobbyist shooting, there is no problem mixing the sulfite separately, as you suggested, which makes designing a concentrate easier.

Anyway, thanks for responding. Did you try cysteine and discover it damages gelatin? I don't have Haist's monobath book, so I don't know what he reported about it.

Mark Overton

Alan Johnson · Dec 24, 2011

Ryuji said:
I suggest to scrap that line of effort. The logic is right, but that line of ideas have been tried and retried a great many times, some by myself. Many chemists still prefer sodium sulfite.

Tests on this line of ideas are not described here on APUG as far as I know.
It would be interesting to know if you tried the grain solvent ammonium thiocyanate as it is available and not expensive.Particularly,will it dissolve in glycol,are there associated hazards and why it was not used.

Photo Engineer · Dec 24, 2011

Actually, thiocyanates are a good idea as are Mono Ethanol Amine and Di Ethanol Amine. Potassium Sulfite comes to mind as it is very much more soluble in water and some other solvents than is the Sodium salt.

And in Edens and Mowrey, what is NOT said is important. HAS (Hydroxyl Amine Sulfate) and its successor Di Ethyl Hydroxyl Amine Oxalate are very soluble and do inhibit oxidation of AA/PD developers. I have not come to a full conclusion on this, as my tests had to stop too early due to emulsion work, but HAS does stabilize.

So, there are hints for you Mark.

There were 2 paths being undertaken in the late 80s by Bill Lee and others who wished to make a better version of XTOL or HC110. This work was terminated in about 1988, but the experimental formulas are still rattling around in my head. They all used things mentioned here as well as things not mentioned. Most was the combination of the above ingredients in new ways.

One key I can tell you of is that the best of all possible worlds is slow development with long times. This maximizes speed and sharpness while minimizing grain. But then, that should not be news to those of you using 1 hour development times. So consider a known formula but reduced in potency to achieve a slow rate of development.

PE

Gerald C Koch · Dec 24, 2011

Ryuji said:
So, why dont you pick up a camera and shoot more film? Kodak and Fujifilm need you. Kodak will raise the price in a few months. Time to burn some old stocks and buy more bricks.

Yes, Kodak, Fuji, and Ilford need us to buy their film. Shoot enough film and you don't have to worry about developers going bad. Two birds, one stone.

Happy holidays to all and a prosperous New Year!!!

Jerry

Improved version of DS-10 by Ryuji Suzuki?

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