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mgarelick
08-09-2007, 06:08 AM
Jim Browning states on his newsgroup "I've heard that there is an electrostatic effect which pulls the dye molecules from the low pH matrix into the high pH gelatin receiver, but I don't know if this is true or not." Jim may have the correct theory somewhere.

Actually in looking through my notes I may have a peer reviewed paper that lists path lengths and the theory of dyeing for proteins below or above the isoelectric points. The isoelectric point or basically the charge induced by the acid (or basic) solution is the main determining factor for determining dye density for anionic (or cationic) dyestuffs. The path length of the proteins does not from the abstract I have produce a significant change in dye absorption. I have more than enough sources to disprove Ron Mowery. I would need to read through many of these papers to track down the exact source if anyone is really interested. I am not just going to get this for the purposes of fighting with Ron, since he will never read it and no one will win this argument. Ron will always insist he is correct.

I think if Ron really has anything constructive to add he should state a source for his alternate dyeing theory of proteins. If Ron doesn’t have any real information I feel that that what Ron is doing is making insinuating remarks against me.

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. Edited

I should also note that I am receiving word that people are in fact disagreeing with Ron's position on this forum. I would strongly urge others to post if you do disagree with Ron and why. I'm not suggesting an attack; just let us know what you find wrong with Ron's approach to this topic.

Curt
08-09-2007, 07:08 AM
Let's see a show of hands of those who actually have made a dye transfer print.

rmazzullo
08-09-2007, 08:35 AM
I should also note that I am receiving word that people are in fact disagreeing with Ron's position on this forum. I would strongly urge others to post if you do disagree with Ron and why. I'm not suggesting an attack; just let us know what you find wrong with Ron's approach to this topic.

Michael,

So far, the only thing you have succeeded in doing, is slamming everyone else's work in dye transfer and emulsion making. Ron Mowrey, Jim Browning, now Ctein. You even mentioned Bob Pace. I think you even mentioned Dr. Patterson, too. People who have worked with and produced dye transfer, and in Jim Browning's case ---resurrected -- dye transfer nearly single handedly.

Did you leave anyone out?

Yet all of them are rank amateurs compared to you, and your results and research are beyond theirs. How fascinating. You state that you have done some work with dyes, but REFUSE to provide anything more than bile-laden rhetoric when ANYONE disagrees with you. Unless you are suffering from a stratospheric case of colic, what on earth are your motives? If your plan is to alienate every single person in the dye transfer / emulsion making world, then bravo! you are well on your way, grasshopper.

Ron has posted examples of his emulsion making formula on APUG which have worked very well and were explicitly designed to be reproducible by the amateur. I don't recall him ever saying he made a pan matrix emulsion. He just forwarded a suggestion for a POSSIBLE VARIANT that interested parties may try.

If your work and results are far and away better than everyone else's, then please make every effort to show what exactly you are referring to with micrographs, or examples of some sort. You no doubt have access to the appropriate equipment to produce micrographs to show us.

Are you planning a product release to totally astonish the dye transfer world?

Or perhaps your efforts to discredit everyone is actually someone else's idea, and you are just the "straw man" in this nefarious and sinister plot.

Perhaps you are being funded by foreign powers unknown in their overarching goal to control all emulsion making on the planet. I could go on, but I digress.

If this work you "have done" is so important, you must have published a thesis that we can look up. You don't even have to supply the paper. The professionals who lurk and / or post on these forums will be able to find it easily. What school did you attend? Since you must have had papers published concerning this work, simply supply the references, and we will find them, I assure you (I honestly have a hard time imagining you losing sleep over inappropriate gelatin swelling or doing this level of work as a hobby).

If you have better methods of making emulsions, or dye transfer film, by all means please let us know how to improve our results.

The windup here is that the methods and formulas presented on these forums, and shared with everyone else at great personal expense to the people involved -- WORK, and WORK WELL. There is no need to go into the realm of the subatomic to achieve results on this level. The esoteric principles you have graciously sprayed us with are beyond the scope and intent of the forum.

Besides, there are far better ways to disagree with people, and remain on cordial, friendly terms. In this regard, your efforts have been less than stellar.

Bob M.

Photo Engineer
08-09-2007, 09:32 AM
In one case, the guaizulene dye, vs a similar azo dye, the molecular formulas may be adjusted to be identical or nearly so but the huge difference in shape of the molecule causes a big change in behavior in gelatin.

The fused ring guaiazulene vs the rather linear slim azo molecule would have different ways of traversing the path. This, BTW, came from studies in the course of work on fixation where diffusion outward of the silver complex is important depending on the structure and size of the components.

There is a reason why dye diffuses out of a matrix in any case whether it is placed in water or onto a sheet of mordant containing paper. It is the concentration gradiant created by the water or mordant. This too was found to be the same in dye transfer as in fixation (and the wash after fixing). I have a rather lengthy post on this somewhere on APUG.

The gelatin used in 1942 is NOT the same gelatin used today. That definitive statement should help explain why the more modern papers are more relevant.

I have made dye transfers. I don't enjoy it due to the time and cost. Also, to tell the truth I'm not very good at it as I didn't work hard enough to hone my skills. My boss wanted me to become an expert with type "C" and type "R" papers instead, as we were doing no research on DT. I did make some nice Flexichromes though. And, they were more fun to me, involving the painting step. I used to transfer them to DT paper and reuse the Flexichrome original. I finally ended up using Matrix film, painting it and using modeling dye and then transferring that to DT paper. More fun to me.

PE

CRhymer
08-09-2007, 09:57 AM
....I finally ended up using Matrix film, painting it and using modeling dye and then transferring that to DT paper. More fun to me.

PE


Hello PE,

I wonder whether you could expand on this a bit. I have to not raise my hand as one who has made a DT, but I did buy some Matrix film from J&C when it was on sale last fall with the hope of trying it someday. I had no idea how much work it is. I would still like to use it, so anything that makes it easier would be appreciated.

Cheer,
Clarence

CRhymer
08-09-2007, 10:06 AM
...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....

Hello mgarelick,

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

Cheers,
Clarence

rmazzullo
08-09-2007, 10:47 AM
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.

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.

Photo Engineer
08-09-2007, 12:21 PM
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

Photo Engineer
08-09-2007, 12:28 PM
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

Neanderman
08-09-2007, 03:11 PM
Jim Browning's film is a 19 century film and in no way does it work "nearly perfectly".

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

Neanderman
08-09-2007, 03:12 PM
Let's see a show of hands of those who actually have made a dye transfer print.

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

David A. Goldfarb
08-09-2007, 03:35 PM
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.

Photo Engineer
08-09-2007, 04:16 PM
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

mgarelick
08-10-2007, 09:14 AM
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.

Photo Engineer
08-10-2007, 09:40 AM
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

Photo Engineer
08-10-2007, 10:03 AM
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

Joe VanCleave
08-10-2007, 10:41 AM
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

David A. Goldfarb
08-10-2007, 10:53 AM
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.

Photo Engineer
08-10-2007, 10:54 AM
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

mgarelick
08-11-2007, 06:08 AM
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.