Microdol-x replacement

[Christiaan Phleger]

So, I guess there may be hope still that an adequate equivalent might be in the works? Some of us still really love the creamy smooth look of 1:0 and don't mind the speed loss, I for one actually welcome it shooting in bright sun.

 

[Keith Tapscott.]

Bill Troop and I are in constant communication trying to resolve this from patents and information I have.

Please bear with us.

PE

Patiently waiting impatiently. BTW, happy new year to everyone.

 

[Ian Grant]

Throwing mud in the water. It now appears Kodak had a number of approaches to Ultra(Super) Fine Grain developers prior to Microdol and subsequently Microdol-X.

Way back early in this thread I mentioned Ilford's P10 Technical Sheet which suggests adding Ammonium Chloride to ID-11(D76), this was one of Kodak's ideas along with a D25 type developer with Sodium Chloride, or put another way D23 + Metabisulphite & Chloride. They are claimed to be fog free.

The missing link is a pre-WWII Kodak developer "Kodak Ultar-Fine Grain" which appears to have been commercially available in Europe before and then alongside DK-20, disappearing from production during WWII.

Apart from "Kodak Ultra-Fine Grain Developer" Kodak in Europe also marketed two other developers never released in the US market, Kodinol (Rodinal type) and HDD (High Definition Developer), and it's quite probable all these developers all came from the Harrow Research facility rather than Rochester.

Unfortunately like Ilford's ID-48 the formulae for Kodak Utra-Fine Grain Developer and the Kodak Equivalents Microdol then Microdol-X remain commercial secrets, and no matter what Pantents we read the possible formulae will alway's remain pure conjecture/speculation.

However it is probably much easier now to formulate a replacement developer that would match if not out-perform Microdol-X.

Ian

 

[nworth]

D-25 may be worth looking into again. It fell out of favor due to dichroic fog problems with the films of the 60s, but I understand that is far less likely to happen with modern films. It was supposed to give grain similar to DK-20 or Micordol in the 40s and 50s. Addition of sodium chloride (or maybe ammonium chloride) might be interesting experiments, comparing them against straight D-25 and D-76.

 

[tjaded]

I've been reading about another of the super fine grain developers, Edwal Super 20. Here is a quote from The Compact Photo Lab Index:

Edwal Super 20
For Extreme Fine Grain
Edwal Super 20 is a true "super fine" grain developer, meaning that it will consistently produce negatives capable of 15 to 25 diameter enlargements from coarse grain films, 20 to 30 diameters or more from medium grain films, and practically unlimited enlargements when used with fine grain films.
For comparison, its companion developer, Edwal FG7, is a "fin grain" (not super fine grain) developer, capable of 10 to 15 diameter enlargements from coarse grain, high speed films.

After a little digging and some confusion over the mysterious "Gradol" in the formula I came across this:

Distilled water 750 ml

Gradol (derivative of para aminophenol) 5 gr

Fine Grain Sulphite (Sodium sulfite anhydrous) 90 gr

Diamine-P (paraphenylenediamine) 10 gr

Monazol (Glycin) 5 gr

Water to make 1.0 L


The liquid commercial version of this formula was known as Edwal Super 20


This Edwal formula is from 1939/44. It is a staining developer with many Pyro-like qualities, but with much finer grain, better acutance and much better compensating characteristics. For many years the major stumbling block to the formula was trying to find out what "Gradol" was in the formula by Dr. Edmund Lowe (founder of Edwal). Gradol is the hemisulfate of p-aminophenol C6H7NO.1/2H2SO4 and has a molecular weight of 158.14. You can substitute p-aminophenol hydrochloride for the Gradol, use 0.9X of the amount called for. No need to make any other adjustments. Do not add sulfuric acid or any other sulfate to the developer.


http://www.photocrack.com/photovergne_wiki/index.php/EDWAL_20

 

[Ian Grant]

Back in April I tested D25 with Sodium Chloride added as in my early post, there was no trace of Dichrioic fog with Delta 100, Tmax 100 and Fomapan 200.

The films of the 50's and 60's that were prone to Dichroic fog have long gone, but some fast films may still be problematic, but in general you shouldn't need to use a Super Fine Grain developer with a fast film as you'd get better results with a slower film developed normally.

One problem with these developers is the speed loss and all companies Kodak included were trying to get minimum speed loss with the finest grain, and Kodak were up against some tough competition from other manufacturers who made superb Ultra Fine Grain developers.

Ian

 

[Ian Grant]

I've been reading about another of the super fine grain developers, Edwal Super 20. Here is a quote from The Compact Photo Lab Index:

Edwal Super 20
For Extreme Fine Grain
Edwal Super 20 is a true "super fine" grain developer, meaning that it will consistently produce negatives capable of 15 to 25 diameter enlargements from coarse grain films, 20 to 30 diameters or more from medium grain films, and practically unlimited enlargements when used with fine grain films.
For comparison, its companion developer, Edwal FG7, is a "fin grain" (not super fine grain) developer, capable of 10 to 15 diameter enlargements from coarse grain, high speed films.

After a little digging and some confusion over the mysterious "Gradol" in the formula I came across this:

Distilled water 750 ml

Gradol (derivative of para aminophenol) 5 gr

Fine Grain Sulphite (Sodium sulfite anhydrous) 90 gr

Diamine-P (paraphenylenediamine) 10 gr

Monazol (Glycin) 5 gr

Water to make 1.0 L


The liquid commercial version of this formula was known as Edwal Super 20


This Edwal formula is from 1939/44. It is a staining developer with many Pyro-like qualities, but with much finer grain, better acutance and much better compensating characteristics. For many years the major stumbling block to the formula was trying to find out what "Gradol" was in the formula by Dr. Edmund Lowe (founder of Edwal). Gradol is the hemisulfate of p-aminophenol C6H7NO.1/2H2SO4 and has a molecular weight of 158.14. You can substitute p-aminophenol hydrochloride for the Gradol, use 0.9X of the amount called for. No need to make any other adjustments. Do not add sulfuric acid or any other sulfate to the developer.

http://www.photocrack.com/photovergne_wiki/index.php/EDWAL_20

A few of us are working on updating/modernising and evolving some PPD type UFG formulae, Edwal 12 in particular which many thought was superior to Edwal 20, while we aren't working on exactly the same tack our experiences & knowledge gets pooled.

The current research I'm doing into Kodak's developers has thrown up some quite unexpected avenues that seem to have been over looked by Kodak with fine grain developers, yet are in Kodak Patents for Graphic Arts developers. Strange, but possibly work was halted (or not published) later because of a couple of competitor Patents.

Ian

 

[Photo Engineer]

Other posts would tend to dispute the fact that modern films are free of dichroic fog formation in solvent developers. In fact there was a recent post on this. I can verify that this is true, and that modern films can "fog" easily if one is not careful.

OTOH, it is now possible to formulate fine grain developers that do not do this to film and it is possible to formulate fine grain, high acutance developers that surpass some of the best on the market and without any loss in speed. This work was terminated at EK in the 80s and 90s, but I know of some of the chemicals used. Unfortunately, it is a pain to reformulate something with my current facilities and workload. It is also difficult to get some of these chemicals as they are not just off-the-shelf items. I cannot have most chemistry shipped to me due to current legal restraints in the US.

So, as I said, please bear with me. Bill and I have searched hundreds of patents and have yet to decide on a final formula that will not take too long to "develop". It may take 6 months to a year to test the possible formulas to pick the best one.

PE

 

[Keith Tapscott.]

However it is probably much easier now to formulate a replacement developer that would match if not out-perform Microdol-X.

Ian

Yes, I have to agree, even Microdol-X is an early to mid 1960`s formula and B&W film emulsions have improved radically since then.
Microdol-X and Perceptol work nicely when they are well diluted for compensating development for brightly lit scenes. Modern films are fine-grained enough not to require solvent development.
It is better to have a speed maintaining developer that minimises graininess, without making the grain fuzzy like true fine-grain developers do. Enlargements look much better when the film grain has been sharpened up a bit.

 

[Photo Engineer]

There are two recent threads on Microdol-X that essentially repeat the same things over and over. In particular, it is said that modern films do not suffer from dichroic fog, OTOH it is said that modern films do suffer from dichroic fog. It is said that Microdol X has a secret ingredient, while at the same time it is said that Microdol-X does not have a secret ingredient.

Posters have observed dichroic fog with modern films in solvent developers. This is reported here and in the other thread, along with opposing comments. Who is right? I know that dichroic fog occurs! So, I lend my weight to that side of the argument.

As for the secret ingredient? Yes, there is one. What it is and how much? IDK. I have a note from a meeting with Dick Henn in which he says that this is true. It comes from about 1970, and was recorded in my pocket notebook.

So, there it is. Two facts about Microdol X.

Now, it took a long R&D effort at a modern research facility to come up with this formula. Doing it in a home lab will be a long task as I indicated above. Dabbling will not do. It must be proven! It is also going to take money to buy the oddball chemicals needed to devise the correct formula.

So, say what you will or imagine what you will. I've BTDT for over 15 years in product and process development. I know what is involved. This is not an overnight job. Of course, most APUG members are not long on wanting proofs. If someone says their developer is better and they say it long enough and loud enough, then the membership at large will accept those claims.

PE

 

[Venchka]

I said this before. I'll say it again.

Would it break the bank and ruin Kodak if they published the formulae for discontinued products? Could they license the formulae to an outside company for a modest, but realistic price, so that production might continue? Maybe Microdol-X would do better than than some of their digital triumphs?

 

[Mick Fagan]

Wayne, there are some things business will not do, releasing trade secrets is usually foremost amongst these things.

The worlds fourth computer is on display in my local science museum, "CSIRAC". When you are shown the computer, they tell you that there are quite a few things they are not allowed to physically show, they can describe them, but not show them, otherwise it may break a patent (I believe). By the way, SCIRAC is the only first generation computer, still in one piece in the world, none of the others have survived!

In the past, I signed a confidentiality agreement with Kodak, even though I have never worked for them, just with them. Twenty five years after signing that agreement, I received a notification from Kodak reminding me about what I had signed.

As I was well and truly out of the graphic arts and photography arena by then, I was astounded, to put it mildly.

After receiving the notification I spoke with a personal friend who is a top end lawyer specialising in industrial law, she informed me that after a certain level, this is a reasonably common business practice with companies that have intellectual rights that are often cross referenced with different and many varied, but somehow associated products.

Kodak I'm sure, would have much more to lose than one imagines. From their point of view, if that formula has a secret ingredient, then other manufacturers would love to have the insight to that research and development, which probably cost squillions to find, or figure out.

They are not in the business of giving their competitors a free ride. They would have long memories of their loss with colour, other companies, literally, received a free ride from Kodak.

Mick.

 

[Venchka]

US Patents have a lifespan of approximately 20 years. Microdol-X is older than that. How does Kodak keep the secrets going? My company's primary patent expired a few years ago. Nobody jumped out of the woodwork to make cheap copies.

If a company decides to lock away a product and never produce it again, the paptent should expire. I also suggested that Kodak could license another company to produce the products that Kodak doesn't see fit to make.

Never mind. I think I'll switch to Pyrocat. Sandy King is a nice person who shares his experience with others.

 

[Trask]

nworth mentions the use of ammonium chloride as an additive to a developer. I've done that, after coming across a reference to this technique in a mid-50's Nikon rangefinder handbook, in developing tables in the back of the book. That book is in storage at the moment, but I recollect that one was told to add 40 grams of ammonium chloride to one liter of D-76 (I'm pretty sure about the 40 grams, less so that it was to one liter -- but it seems reasonable). Halve the ISO you shoot at and double the development time.

I'm attaching two photos I took using this developer. It seems to produce creamy images, though not unsharp. When looking at the emulsion side of the film when dry, it did seem to have a sheen to it that may in fact have been the re-deposited silver that the use of ammonium chloride is supposed to produce.

The bicycle shot is on TMAX 400, taken with an 85mm f/1.7 Rokkor wide open. and I believe the clown head is on Arista 400 (reported to be re-badged Tri-X) taken with a Leica M2 and perhaps a Canon 35mm f/2 or Canon 50mm f/1.5 lens.

 

[Ian Grant]

That's the exact directions given by Ilford in their 60's Technical Sheet P10, and mirror's Kodak's use of Ammonium Chloride in the mid 1930's, the work was done by Crabtree who formulated D76.

In the early 1950's Kodak suggested a modification to Microdol to give even finer grain, by adding Benzoriazole.

Ian

 

[Keith Tapscott.]

That's the exact directions given by Ilford in their 60's Technical Sheet P10, and mirror's Kodak's use of Ammonium Chloride in the mid 1930's, the work was done by Crabtree who formulated D76.

In the early 1950's Kodak suggested a modification to Microdol to give even finer grain, by adding Benzoriazole.

Ian

I thought it was J.G. Capstaff who formulated D-76.

 

[BradS]

US Patents have a lifespan of approximately 20 years. Microdol-X is older than that. How does Kodak keep the secrets going? My company's primary patent expired a few years ago. Nobody jumped out of the woodwork to make cheap copies.

If a company decides to lock away a product and never produce it again, the patent should expire. I also suggested that Kodak could license another company to produce the products that Kodak doesn't see fit to make.

Patents are, by their very nature not secret. A patent is a public disclosure. A patent rewards a company for this public disclosure of technology with a short term monopoly on that technology.

I suspect that Kodak has decided to keep the formula of Microdol-X a trade secret....that is, it explicitly did not disclose the formula in a patent.

 

[Photo Engineer]

Brad;

You are exactly correct! It is what is called a "Trade Secret".

PE

 

[Keith Tapscott.]

Brad;

You are exactly correct! It is what is called a "Trade Secret".

PE

I believe that manufacturers also reserve the right to modify their formulae if it improves the performance, so some developers might have had certain components replaced over a long time span since they were first introduced.

 

[Photo Engineer]

Yes, this is true of unpublished formulas, but not of the published formulas.

As a side note, use of Ammonium salts in developers can release a lot of Ammonia gas. Since Ammonia is a very powerful silver halide solvent all on its own, it is a tossup as to which ingredient in the addition of Ammonium Chloride to a developer is doing the job. It is usually a mix of both, but at the same time the pH will change due to this addition (It should not when Sodium Chloride is added).

Since the Ammonia evaporates, this developer will not keep well in open trays. The effect will vary with time.

PE

 

[Ian Grant]

I thought it was J.G. Capstaff who formulated D-76.

The team working on these developers included Crabtree, Capstaff and later Henn, each published Patents, but decisions of importance would have been made by someone more senior.

So yes Capstalff's name is gived for D76, but Crabtree worked on the variants too and with Henn on the Super Fine Grain Developers.

Ian

 

[Keith Tapscott.]

nworth mentions the use of ammonium chloride as an additive to a developer. I've done that, after coming across a reference to this technique in a mid-50's Nikon rangefinder handbook, in developing tables in the back of the book. That book is in storage at the moment, but I recollect that one was told to add 40 grams of ammonium chloride to one liter of D-76 (I'm pretty sure about the 40 grams, less so that it was to one liter -- but it seems reasonable). Halve the ISO you shoot at and double the development time.

I'm attaching two photos I took using this developer. It seems to produce creamy images, though not unsharp. When looking at the emulsion side of the film when dry, it did seem to have a sheen to it that may in fact have been the re-deposited silver that the use of ammonium chloride is supposed to produce.

The bicycle shot is on TMAX 400, taken with an 85mm f/1.7 Rokkor wide open. and I believe the clown head is on Arista 400 (reported to be re-badged Tri-X) taken with a Leica M2 and perhaps a Canon 35mm f/2 or Canon 50mm f/1.5 lens.

Those images seem to have good sharpness and tone graduation. Could you check your book to confirm the 40 grams of ammonium-chloride to each litre of D-76 stock-solution?

 

[Keith Tapscott.]

This patent describes the use of chloride in fine-grain developers.

 

[Ian Grant]

That's about 10 years after the earlier work and the formula published by Crabtree with 40g Ammonium Chloride added to a Litre of D76. It's also in the first Patent referenced in that one.

The interesting one (not in a Patent) is the use of Benzotriazole in Microdol which improves fine grain even further but at the xpense of even greater speed loss.

Ian

 

[Venchka]

Come on Kodak!

The patent for Microdol-X expired ages ago. Kodak claims they will never make Microdol-X again. Publish the formula please. Kodak will score massive PR points.

Patent lifespan
In Canada, a patent lasts 20 years from the date of application, for applications filed since 1 October 1989. In the United States, the term is also 20 years from the date of the first filed U.S. application; however, for applications filed since 29 May 2000, the term may be extended based on any delays in issuance of the patent caused by the U.S. Patent and Trademark Office.