Making a Dye Transfer Matrix film

mgarelick said:

...It should be noted here that Ron had two 25 sheet boxes of 16x20 Kodak Pan Matrix film and about 300 sheets of 16x20 Kodak Dye Transfer paper that he gave to Mr. "Ctein" a few years ago. I truly believe those materials should have been given to someone here so they can have the opportunity to learn DT. Mr Ctein is not entitled to old DT materials, where others should be....

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Hello mgarelick,

Does this mean that nobody can go out for recess until we find out who took Betty's nickel?

Cheers,
Clarence

I have to add 2 cents here....

mgarelick said:

Since this forum concerns coating matrix film my goal is to educate, inform and encourage people that may be interested in coating this type of film. However I question what Ron's goals are. It should be noted here that Ron had two 25 sheet boxes of 16x20 Kodak Pan Matrix film and about 300 sheets of 16x20 Kodak Dye Transfer paper that he gave to Mr. "Ctein" a few years ago. I truly believe those materials should have been given to someone here so they can have the opportunity to learn DT. Mr Ctein is not entitled to old DT materials, where others should be.

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Michael,

I sit here at my computer, awestruck at the unbridled hubris and unmitigated loathing that you feel necessary to unleash upon the people who use and work with dye transfer and photo emulsions.

You claim your goal "is to educate, inform and encourage people that may be interested in coating this type of film". Your actions completely invalidate this statement.

I defy you to even approach Ctein's level of work, his artistry, and last but not least, his published works in magazines and in book form.

I defy you to approach and surpass Ron Mowrey's 32 years as an emulsion chemist, his patents, his research disclosures, and his direct and continued association and work with the very same professionals who are directly responsible for inventing a good many of the photo products we are talking about.

I defy you to better Jim Browning's work, his contributions, his inventions, and the fact that he literally brought back a method destined by Kodak for the scrap heap all by his lonesome.

You have a real tough act to follow, for someone in his early 20's.

Prove it. Prove your assertions and accusations to be true, plain and simple. Or, take your toys and go home.

Bob M.

Well, first may I say that I can give anything I own to anyone I want.

Ctein and I have developed a good working relationship and I certainly respect his work. I object to anyone telling me what to do with my property. If I had known Jim Browning at that time, it might have gone to him or might have been split with him and Ctein. I don't believe that I would ever have given it to MG given the cirmcumstances and invective.

As for DT being painted:

You can make a DT matrix from a B&W original, and then dye it with a black modeling dye. Then, on a light table you paint it with DT dyes mixed to give various hues. Then when satisfied you transfer it to DT paper. It gives an original color print with your own colorization. Very striking sometimes.

The modeling dye is a black dye such as was used in Pan Matrix Film. It therefore represents a C/M/Y/K set.

PE

Oh, BTW.

I have no Pan Matrix Film in my posession. This is utter fabrication.

I have 2 boxes of 8x10 Matrix film and that is it. I have a 1 gallon Dye Kit and several DT chemicals. As I said above, I was not an afficionado of DT due to the complexity, expense and pressure at work.

In fact, I was kind of drafted into teaching color printing at the Kodak Camera Club when the new papers came out seeing that I was one of the "experts". Kodak never had a course in-house at the camera club in DT AFAIK.

Also, I would like to stress that one of the reasons for exiting the DT field was the use of Thorium Nitrate as the mordant in DT paper. This is radioactive and Kodak had problems in the plant with it. Government regulations were gradually squeezing them on this chemical. I think that this is getting way out of hand! This subject is one that is very important to the history of photography and as an excellent method of making good prints, but should not be overstressed in the absence of real data.

PE

mgarelick said:

Jim Browning's film is a 19 century film and in no way does it work "nearly perfectly".

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Have you produced a better matrix film? If so, show us. I think that is all anyone is asking.

Curt said:

Let's see a show of hands of those who actually have made a dye transfer print.

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I have, in 1981, using Kodak materials that -- as we all know -- are no longer available.

I've never made a dye transfer print, but if Jim Browning or someone else is able to describe a method using essentially 19th century techniques that could be replicated in a home darkroom, then maybe one day I'll be able to do it.

Jim Browning's methods are more like those used in the 40s, but in a lab equal to the current century, and with a mentality of a 21 century engineer to go with it.

Jim has the patents and the research background to go with it, and the degrees as well. He is too modest to mention all of this. He is creative and quite adept in the lab with a knowledge of engineering, chemistry and physics equal to the task of desiging and making emulsions, and the coating machines to coat them.

PE

Dear Bob M.,

My motives are to promote the dye transfer process just like Jim Browning does. In some ways we share the same goals. I have no secret agendas here. I find it necessary to point certain things out that often do insult and offend some people. However this is not my intention.

In the case of Ron Mowery everything I find from his information on emulsion technology is that, his actual knowledge of emulsion technology is for the most part 19-century technology. Part of this analysis is from a few experts I have spoken to that designed special emulsions for certain applications during the 1950’s. I do not know exactly what areas in emulsion technology or silver halide processing technology he has expertise in. I was able to find his patents and some were actually Canadian patents. The journal Research Disclosure allows submitters to remain anonymous if they chose. I did a search there and nothing came up but that may have been due to an error, I don’t remember.

Edited

I think its great that Jim Browning made a matrix film although he was not the first to do this after 1994. In 1990’s Dr. Patterson had an orthochromatic matrix film formulated. From people I spoken to he wasn’t satisfied with it. But from what I hear about the film it was very similar to Jim’s film. In some ways it was better and in some ways the Browning film was better, although I don’t have much information on Patteson's emulsion to really say. The basic technology of the emulsion is probably 19 century although films like this were used early in the 20 century. The 1930’s Eastman Wash off Relief matrix film is superior technologically to Jim’s film, because by that time knowledge of sensitization and gelatins were much greater than in the 1880’s. Jim believes his film produces good results and that is fine for him or others that want to coat their own matrix film and are not concerned with making a copy of the Kodak film.

I may be interested in releasing a product myself, but I would rather work with someone that could fund such a project. So there are no plans at this time. I am doing work on dyes and working on a procedure that an amateur can follow for successful synthesis. I have successfully made a cyan dye that should be far superior to the old Acid Blue 45 Kodak cyan and I am still running tests on it now. I am also working on a synthetic route for a yellow dye superior to the old Kodak yellow.

I have written a paper of a project I did involving structure determination and identification of the Kodak magenta dye and a special cyan imbibition dye. The chemical family of the magenta dye was known, so this made it relatively easy to find the group in question. It is not published but I can supply anyone a copy of it if they want. This is how I know Kodak gave the wrong structure for the magenta dye in their supposed disclosure in Kodak Technical Publication CIS-154. This project involved the use of NMR (only analyzed H), ft-IR and mass spectroscopy to determine structure of both dyes.


M.

Additional information on the dye - gelatin interaction

Bone gelatins are made by a process called Liming. This is treatment with Calcium Hydroxide. It leaves behind a residue of Calcium in the gelatin.

Early gelatins were Calcium rich and contained allyl thiourea, an emulsion sensitizer. Washing of emulsions was carried out by using water high in Calcium and Magnesium salts to minimize swelling.

Dyes used in Dye Transfer were sulfonic acid dyes supplied as the sodium or ammonium salt. The early DT process had preliminary steps intended to remove or reduce the existing calcium salts before imbibing the dye or they would react and precipitate in the coating, never to come out until treatment with a strong alkali solution. Therefore, often, depending on Calcium level, matrices would not completely transfer dyes and would build up dye in them to a certain level unless the Calcium and dye were removed somehow.

In addition to this, the early methods of making gelatins allowed a variation of isoelectric point over a fair range which influenced swell. In fact, companies such as Technicolor kept track of coatings as being hard, normal and soft based on the gelatin swell, not on silver imaging itself. The Isoelectric point is the point at which gelatin has its minimum swell.

Modern gelatins, since about 1950 on, are oxidized and deionized. They contain no allyl thiourea and no calcium. Emulsions contain no calcium. All bone gelatin today is carefully kept at an isoelectric point of about 4.5 - 4.8. These gelatins are supplied by Kind and Knox (Gelita brand), Rousselot, and Eastman Gelatin. I have used all 3 brands in my work and they are all very good. Eastman gelatin is the brand I am most familiar with followed by Rousselot. I have been told that Eastman gelatin may be bought from the Photographers Formulary AAMOF.

So, current modern gelatins are a very narrow and clean subset of the gelatins of yesteryear that were studied in the 40s and even 50s. They certainly give excellent results in the dye transfers that I have seen.

Pig gelatin has an isoelectric point of about 9, and is not currently in use at Eastman Kodak. They recently disposed of all old stocks of this type of gelatin. AFAIK, it was never used in DT materials.

Several black dyes were used in pan matrix films. One mentioned in the literature is Nigrosine.

I hope this clarifies some matters.

PE

Gelatin swell profile

I had trouble finding this. Here is the swell profile as found at another site on the internet. More information is found in my lengthy post on hardening on Photo Net.

PE

What a Pathetic Sack of Horse-Puckey

Ron, I appreciate your goal of permitting the knowledge of hand-made emulsion technology to be made available to the 'photo-hobbyist', or 'amateur' (as in 'lover of photography'), such as I. I am deeply appreciative of all you have done to simplify the process such that it can be reproduced by non-scientists, such as myself.

Edited

Ron, my personal advice is to not respond at all to this 'mgrelick' person's attacks, as hard as that is to do. They are not based on an honest intellectual disagreement, and only hurt yours, and APUG's, reputation. They speak volumes for themselves if merely left alone.

Edited
~Joe

Good response, Ron. What it contributes here is that it only addresses the data and doesn't address other persons.

I would recommend that anyone who contributes to this thread do the same, given the surprising volatility of the topic. We'd rather not have to edit individual posts.

My information on emulsion making spans the entire gamut of making from the 1900s (Wall and Baker for example) up through the more modern makes of Wey and Whiteley and beyond. I have stated this before.

I CHOOSE to make and teach earlier emulsions at this time so that the average person can make them without elaborate equipment and knowledge of chemistry and engineering.

Anyone who cares to take the time will see engineering drawings of the control systems and other items needed to make modern emulsions properly using double run of silver and salt (sometimes triple or quadruple run) with carefully metered flow rates. These are posted in this forum. Look them up.

There are two other reasons why I don't post exact formulas. First, I would have to reconstruct them from memory and old notes and second, I have an obligation to Kodak not to disclose confidential information or trade secrets. As Kodak exits the analog field, this latter becomes less important to me and to Kodak, I'm sure. That time will probably come, when I feel free to disclose more information.

I would turn most people away if I told them they had to invest in a computer controlled process control system with peristaltic pumps, constant temperature baths and the whole works with conductivity meters and all of the software to go with it.

As it is, these emulsions of mine and Jims require no more than a good hotplate and stirrer and a burette or syringe. And, the chemistry is just cookbook.

I'm noting here that this is a statement of my philosophy at the present time to bring emulsion making to the masses with simple technology.

PE

RE: Additional information on the dye - gelatin interaction

The dyes used in dye imbibition transfer processes are normally anionic that contain sulfonate groups and sometimes carboxyl groups. Usually yellow imbibition dyes can contain carboxyl groups in addition to the sulfonate groups. They are usually prepared in sodium salt, potassium salt, ammonium salt or free acid form. They all have different ionization characteristics. The Kodak magenta dye concentrate solution is mainly in the sodium salt form with a small amount of the free acid form, which is buffered with Triethanolamine.

The gelatin in the 1942 paper I mentioned used de-ionized gelatin. It also has swelling curves for two different types of gelatins. I know I have a few peer reviewed papers that have gelatin swell profiles for types of chemically modified gelatins. Not all of them exhibit a single swell minimum at its isoelectric point. Ron will insist the swell minimum is always found at the pH of its isoelectric point. The swell curve Ron has posted is of a lime extracted gelatin that comes from bone collagen.

Pig skin extracted gelatin has an isoelectric point between pH 7 and 9. These are usually not preferable for matrix films. I know for a fact the 1940’s matrix film gelatins were chemically modified. If Ron disagrees I will ask him to provide some evidence [edited]. I do in fact have evidence if Ron wants to keep fighting with me on this.

The dye Nigrosine may be known as CI Solvent Black 7. This depth penetration pigment used in Kodak pan matrix film is water soluble and not very soluble in organic solvents. Ron is free to test this is he wants.

I have a copy of the 1935 Eastman Wash-off relief process publication and there is no procedure listed for removal of alkali from the matrices. The number of prints possible from a set of matrices were much lower in the 1930’s than that of the more recent Kodak matrix film technology.

Chemically modified gelatins such as phthalated gelatins were not used (AFAIK) in Dye Transfer materials. The modified gelatins may have been, but to this point, they have never been mentioned in this thread. I have certainly not commented here on modified gelatins before. They certainly have different isoelectric points depending on the degree of modification. They were used in the 50s - 70s approximately, for ISO washing of emulsions until ultrafiltration replaced it as the preferred method. I have mentioned this elsewhere many times. I have, as I said, never mentioned them in connection with DT materials.

If they were used, they certainly did not help Technicolor as they described to others the need to segregate coatings into the 3 classes I describe. If Kodak were modifying the swell through manipulation of isoelectric point, I would think they would do a better job, as we had many levels of modification expressed as percent modification. This would have allowed a very fine level of control and a more consistent product.

Modification causes the gelatin to coagulate and then redisperse. I teach this method to my students in the workshops I conduct. Over acidification however, will coagulate the emulsion permanently, and therefore would be a precaution to take in using such a film in dye transfer as it would then produce an unusable (unswellable) matrix. It is therefore advisable to never go below a pH of about 3.5.

The curve I posted above is typical of all of the bone gelatins that are in current photographic use. My work at Kodak included testing of gelatin swell as a function of hardening level using a swellometer. We were trying to find the optimum level of the new hardener. I have mentioned that also here and elsewhere.

I point it out to indicate that there are many confidential reports and experiments that exisit not known to the general public.

In any event, the acid base cycle in the DT process is, in part, present to remove metal salts from the emulsion. The presence of these metals would immobilize the dye and prevent diffusion. It is also used to 'exercise' the gelatin and keep it supple during the imbibition process.

It is an intersting note that the depth penetration pigment is water soluable. Carbon black is not water soluable. It may form a dispersion that can be suspended in water, but is not in any way soluable in water itself. As for removing alkali from matrices, there was no alkali in the matrices that I know of. The matrices were merely soaked in alkaline solution and acid solution to 'temper' the swell, and the alkaline soak was used to remove residual dye trapped in the matrix. A common reason was formation of a calcium salt from retained calcium and that is why there was a pre-treatment.

The number of prints possible from matrices was due to the improved gelatin technology as it developed from the 40s onward. I have mentioned this before here.

PE

Gelatin usage in emulsion making and coating

In all of the emulsion formulas I have described, I have used the same gelatin for precipitation and for coating, unless I describe ISO washing where I use phthalated gelatin.

I should mention here that before phthalated gelatin was used, and now in modern times, two different gelatins were often used during making and coating.

One gelatin was used for precipitation and another was used for 'make up' commonly called 'make up gelatin'. These did not have to be the same gelatin types. The ratio of silver halide to the total gelatin quantity was different in different products and therefore the make up gelatin could be present in different ratios.

In addition, polymers, humectants and other ingredients were used to extend the gelatin for one reason or another. Polymers included poly vinly alcohol and poly vinyl pyrrolidone and humectants included glycerin and sorbitol. The humectants often washed out during coating.

There was also the comment about modification. In the early days before ISO wash, the term modified gelatin was often applied to gelatins that were either purified or had the allyl thiourea removed the so called 'oxidized' gelatins or nowdays 'photograde' gelatins.

Also, there were methods called grafting in which certain chemical groups were grafted onto the gelatin. Phthalation was just one example.

In many cases, with makeup gelatin, these methods were applied to change viscosity and therefore allow coating at higher speeds. It should be noted that sulfonic acid organic compounds increase viscosity and tartrazine used in Matrix film is such a compound. It therefore would increase the viscosity of the gelatin and depress the chill point of the gelatin. This might, in itself, have dictated the actual coating conditions and pre-preparation of the gelatin.

I have coated sulfonic acid dyes with great success, but my first tries resulted in a disaster due to the above modifications of viscosity and chill set point due to miscalculations on my part. I ended up with a putty knife helping the coaters clean out the mess from the chill section. I have also 'mordanted' dyes in gelatin by using calcium and magnesium sulfates.

PE

More on dyes and transfer and ETA developers too

If you look at USP 4409315, you will find listed several sets of modern azo dyes making up cyans, magentas, and yellows.

These sulfonic acid dyes were to be used in the 3000 speed Kodak instant film that never was. They were mordanted to a quaternary salt cationic mordant along with Nickel ion which complexed with them to achieve stunning color purity and image stability.

In this patent there is considerable discussion about ETA development and the theory behind the cross oxidation etc. that I brought up elsewhere. Along with this is a long list of patents that describe other aspects of ETA and dye transfer. This is where I basically learned how to design ETA developers.

My point here is that to build an instant imaging product that is integral, the development rates and diffusion rates of everything in the package must be known to a very fine degree to prevent color shifts, high dmin and a host of other problems that might arise. This involves the construction of timing layers that open or close exactly at the right time regardless of temperature or age of the coating(within reason).

My associates and I, in working with a large group on this had to understand how to move dyes, developers, alkali and other ingredients around within this tiny package and orchestrate things to work together or the image was useless.

This work evolved out of modern chemistry and physics and the modern mathematical models of dye diffusion and interaction with gelatin that I have been discussing. Comparing the actual in-house internal information at Kodak to what was published in 1940 or thereabouts is like comparing the math of Einstein to that of Witten. There was a lot learned in the last 60+ years regarding development and diffusion as well as dye-gelatin interactions.

I hope that those of you who wish to see the complexity of a real dye diffusion transfer process will take a look at this patent. It will show you where Dye Transfer went to and how it evolved within Kodak (and Polaroid).

PE

Kudos for Jim Browning

At our lunch of former Kodak engineers and friends at George Eastman House today, I showed our group a DT print of Jim's, one of the 3 he has given to me.

Our group included a former engineer who worked with DT materials.

I also showed some color prints of Jim's coating machine and the methodology used in operation.

The group were impressed with his results as a photographer, a lab operator and an engineer for desiging the coater and I wish to pass on their commendations to Jim for preserving this process for us all.

Thanks Jim from our little group. Good job!

PE

Photo Engineer said:

At our lunch of former Kodak engineers and friends at George Eastman House today, I showed our group a DT print of Jim's, one of the 3 he has given to me.

Our group included a former engineer who worked with DT materials.

I also showed some color prints of Jim's coating machine and the methodology used in operation.

The group were impressed with his results as a photographer, a lab operator and an engineer for desiging the coater and I wish to pass on their commendations to Jim for preserving this process for us all.

Thanks Jim from our little group. Good job!

PE

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That is very positive. Good news. I am not surprised, but it needed to be said for all to see.

Cheers,
Clarence

Photo Engineer said:

The group were impressed with his results as a photographer, a lab operator and an engineer for desiging the coater and I wish to pass on their commendations to Jim for preserving this process for us all.

Thanks Jim from our little group. Good job!

PE

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Thanks for you kind remarks, Ron. Also thanks to your fellow Kodak associates. It is refreshing to hear something positive these days.

Regards - Jim

Hello Photo Engineeer,

You are more appreciated than you will ever know - which unfortunately makes you a prime target for trolls and the like... if you want to see a trail of the behaviour of trolls elsewhere, look about for a troll who seems to have popped up first as: Mike Scarpitti - presumably a real name. After being banned from various bulitin boards for intollerable behaviour, it is said he then showed up as: Hans Beckert - his first fake name.

After being banned as HB, one Ladislav Lowenstein, III appeared - evidentlty a second fake name. It seems all the many faces of Mike are now banned everywhere, a fate I believe might be more broadly applicable to tormentors of the righteous makers of photographic materials, i.e. PE.

Note he deprectates the best liked, the most sacred of the sacred cows, items he knows will cause insult.

A great faux latin saying: "Illigiterum Non Carborundum"; don't let the bastards wear you out.

Best,

C

I have found more on Pan Matrix Film on the DT forum and wanted to bring this thread up to date with information on the processes mentioned there.

Kodak made a series of products or experiments based on direct reversal emulsions. These were referred to as Reversal "F" and Reversal "P" based on the emulsion chemistry involved.

Apparently, Louie Condax had some film made using one of these emulsions to make a trial Pan Matrix Film or a Matrix Film. At the time this was done, the emulsions were being used in an experimental Type "R" paper (sold in Europe for a time but never in the US) that was to be called Directachrome. The emulsions were also used in Kodak PR-10 instant film.

The required emulsions would therefore have been readily available for experimentation within Kodak, but alas the DT product was never sold.

As for a reversal process for Matrix Films, I have never heard of it being done, but I assume it can be. On another topic, a process that reverses the hardening is very difficult, if not impossible to achieve. It has less image discrimination than the hardening process done by tanning developers and therefore has a tendancy to decrease quality.

I have no information on either of these latter two except to know it might be possible, and that there are inherent problems in both approaches.

PE

Melinex 582 now available.

Photographer's Formulary is now selling cut sheets of 0.007" Melinex 582 polyester stock. This is the cut from the roll I used when developing my matrix film. This is the last remaining stock of this particular film, and it is the only substrate suitable for coating matrix film because the subbing layer doesn't pick up dye stain. It is coated with a great subbing layer on one side, and an antistatic layer on the reverse side. Works great with any gelatin emulsion. Get it while it lasts!

Regards - Jim Browning, the Dye Transfer Guy.

"Use a black dye in place of the Tartrazine"
Hi Ron, Would Pylum "Acid Black#1" be appropriate?
Th at is the only black dye I happen to have on hand.