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analog what is that?
12-23-2011, 10:11 PM
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
12-23-2011, 10:19 PM
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?
12-23-2011, 10:20 PM
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?
12-23-2011, 10:26 PM
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
12-23-2011, 10:44 PM
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
12-23-2011, 11:05 PM
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 (http://www.apug.org/forums/viewpost.php?p=1275474) 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
12-23-2011, 11:08 PM
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
12-23-2011, 11:21 PM
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
12-23-2011, 11:23 PM
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! :D

Best wishes on a nice step forward.

PE

Ryuji
12-24-2011, 03:53 AM
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 donít you just use dry ascorbic acid? That just solves the ultimate problem so that you can focus on shooting.

2. Yes. You canít 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
12-24-2011, 03:59 AM
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
12-24-2011, 04:03 AM
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
12-24-2011, 04:30 AM
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
12-24-2011, 04:54 AM
Guys,

Hereís 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 wouldnít 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 donít you tackle a new challenge that no existing formula adequately dealt with? Still, the golden era of developer chemistry will not come again. Itís 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 donít 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
12-24-2011, 09:58 AM
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
12-24-2011, 10:07 AM
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
12-24-2011, 10:56 AM
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
12-24-2011, 11:47 AM
So, why donít 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

Ryuji
12-24-2011, 03:01 PM
A concentrate that gives XTOL-quality would be perfect for hobbyist-shooters like me, but no major manufacturer makes one.


You might want to know that formulating a good developer is one thing, but formulating a good developer that can be prepared as a concentrated solution is a different thing.

When Silvergrain products were offered commercially, I was strongly advocating among those who were involved to offer powder solutions. They are more green (why do you want to burn extra fuel to carry water and heavier packaging for products that have shorter shelf life?), TSA-friendly, and better formulations can be made. All my proposals were roundly rejected because the consumers are obsessed with the notion of liquid concentrates are superior performers. At this point and time when majority of users are small volume users like you, I really think all powder formula make more sense.



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).

You are assuming business people are rational. At this point and time, majority of smart business people already left, forced to leave and/or abandoned silver halide imaging industry. So the only players are the people with limited business expertise who are fighting for the few remaining pennies. They often donít make rational judgments.



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

Right. Or, as I said above, reconsider all powder formulation.



Did you try cysteine and discover it damages gelatin?

How else would I know? Keep in mind photographic industry is very notorious for not disclosing anything useful unless it is absolutely required to get patents. Many patents have serious flaws but they do not disclose such things until they solve them, at which point they reveal the problem only as a basis for a new patent application. Iíve read MANY patents and repeated many examples given in the patents just to find out the limitation of their inventions. Haistís books are largely compiled from benign published materials including patents, and the manuscript was betted by several Eastman employees just like the CIA and the state department redact documents they release.

Cysteine, thiourea, thiocyanate, etc. all have adverse effects on gelatin. This is largely pH and concentration dependent. But really, another problem with these agents is loss of speed with modern films. If you accept the loss of speed, you could achieve matching granularity by cutting development time or some other means. Some of these legendary "fine grain agents" actually make grains bigger with modern films, depending on the developer formula. Another problem with this type of agents is loss of accutance. If your objective is to achieve maximum enlargeability, it is not just granulrity that impose limitation. Besides, these agents also tend to produce strange sensitometric curves with some modern films, and also increase the tendency to cause silver stains such as dichroic fog. All these problems are not worth fighting for.

Ryuji
12-24-2011, 03:17 PM
Tests on this line of ideas are not described here on APUG as far as I know.

APUG didn't exist back then. Also, it is not a common practice to report negative results unless they resolve a controversy or something.



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.

See my previous response.