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  1. #1
    holmburgers's Avatar
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    Color Dye-Transfer Prints for the Modern Hobbyist - *Imbibition for For the People!*

    HISTORY of the PROCESS

    In 1994 Kodak discontinued the "Kodak Dye-Transfer Process". Since that time, only those who have hoarded those materials or have been enterprising enough to manufacture their own silver-halide matrix films (Jim Browning) have been able to make dye-transfer prints.

    However, this is a curious & unfortunate state of affairs! The earliest dye-transfer (or dye imbibition) prints were made by exploiting the same mechanism that modern day carbon & gum printers use; the ability of potassium or ammonium dichromate to harden gelatin upon exposure to UV light.

    The 2 most common ways to a make a dye-imbibition print both rely upon a gelatin matrix.

    In recent times (Kodak) the preferred method was with a silver-halide emulsion on a clear base. A negative is exposed through the base and developed in a tanning developer which hardens the gelatin in situ with the developed silver. This is then "etched" in hot water, which removes the gelatin that remains untanned (soluble) to reveal a relief image that clings to the base. This gelatin relief consists of varying depths that correspond directly the shadow density in the photograph.

    The other method is very similar, but instead of using a silver-halide emulsion, a gelatin layer is sensitized with dichromates and exposed (again, through the base) under a negative and etched in hot water. It is this variable gelatin relief that absorbs dye to varying degrees, thus continuous tone is possible.

    An obvious difference between these 2 methods is that the silver-halide emulsion can be exposed under an enlarger whereas the DCG (dichromated gelatin) requires an enlarged negative for contact printing. This is one important reason for the success of the silver-halide method.

    However, the use of DCG matrices has many precedents, most notably the Pinatype process; outlined here in this British Journal of Photography article from 1907. However, the first application of this property that gelatin will imbibe & transfer a dye was disclosed by Charles Cros, a Frenchman, who called it the Hydrotype process in the late 1800's. Another process was Jos Pe. It should be noted that the Pinatype uses a slightly different type of matrix (one that is not etched = planographic, as opposed to relief) and correspondingly uses a different class of dyes and is exposed under positives, interestingly enough. No need to go into this in depth at the moment however....

    So, to make a dye-transfer print, a relief matrix is soaked in a bath of an acid-dye, the dye imbibes (or migrates) into the gelatin relief image and this is then rolled into contact with a sheet of receiving paper. The dye transfers from the matrix to the receiving paper.

    If 3 matrices are prepared from color separation negatives, and dyed in the appropriate secondary dye colors (CMY), and finally transferred in register to the receiving paper, a full color image is formed. This is the process in a nutshell.

    METHOD

    Although my work on this technique is far from complete, I want to at least disclose and compile all the information so far gathered, so that other people who are interested may join the effort.

    - PREPARING THE MATRICES

    First, the modern worker needs a suitable clear support. This is found in Photo Formulary's Estar Melinex (mispelled on their website as 'melenex'). This is a thin, clear support that is subbed to accept emulsions. This subbing cannot imbibe any dye itself, which is ideal becaue otherwise you will get stained highlights. Although I have not tested any other materials, I'm curious what else might be suitable. Overhead transparency paper perhaps? Whatever the substrate is, it must be treated so that it "grabs" the gelatin, otherwise it will easily peel off. Search "corona discharge" for more on this, or APUG member hrst's work with substrates. Fortunately, there is an existing product at the moment.

    The melinex scratches easily, and care should be taken to keep it as unblemished as possible. Vaseline or some kind silicon oil (PE) might be able to hide the scratches when it comes time for exposure (remember, we're exposing through the base).

    As a side note, another option would be to do a "carbon transfer" of the clear relief image (or pigmented relief image for that matter) and this could become the matrix. This would eliminate the need for exposing through the base and a special substrate for the matrix.

    2nd, you must coat the melinex with a gelatin layer. This is effectively no different than pouring carbon tissues (sans pigment). I have chosen 6% gelatin with 1% sorbitol, though there is nothing yet to suggest that this is superior to any other concentration, and not enough testing has been done to see what effect the gelatin composition will have upon the matrix characteristics. This gelatin solution pours nicely and makes a thin coating; this has been my only criteria so far. Each worker will probaly find their preferred way to achieve this, just like in carbon pouring.

    3rd, the matrix blank must be sensitized. Having very little experience with this personally, I can only say that it will be necessary to have the back surface clean of any splotches before exposure, and also the deepest layers of the gelatin must be sensitized. It has been suggested (Vaughn) that this is not really a concern.

    Fortunately, the rigid densitometric requirements of traditional dye-transfer printing can likely be thrown out the window when using DCG matrices. Traditional AgX matrix films had but one contrast grade, necessitating strict control of contrast in the sep negs. Thanks to the contrast control available from dichromate sensitization, considerable leaway should be had.

    Chalk one up for DCG-imbibition!

    4th, UV exposure under negatives. The ins & outs of making color separations are best left alone in this discussion, but tri-color gum printers will probably find their negatives excellent for preliminary testing. I am exploring the route of making enlarged negatives on mammography x-ray film (with an intermediate panchromatic step), which so far has proved promising.

    5th, etching in hot (120°F) water, just like carbon. Due to the nature of the hardening by dichromates, control should be exercised to ensure consistency. This difficulty is eloquently (if not somewhat discouragingly) described in this post.

    6th, at this point, one should probably clear (sodium sulfite?) the matrices and perhaps harden them. However, I can't recommend anything at the moment. Some hardeners, like chrome alum, might act unfavorably as mordants in the matrix, where we don't want them. Will advise.

    - DYES

    As it stands now, obtaining appropriate dyes is the single biggest roadblock. Recently, a couple boxes of Kodak dyes came through eBay and sold for over $100 a pop. Not a sustainable solution.

    Jim Browning has listed the following dyes in his PDF for Dye Transfer Materials: Acid Blue 45 (or 25; bluer and transfers slower), Acid Red 80 (or 289*), Acid Yellow 11 (or 23*) [*brighter colors at the expense of light-fastness].

    J.S. Friedman, author of the monumental "History of Color Photography", lists a number of textile dyes that may be suitable for the process and I would encourage people to explore that route. Although the color demands might not be perfectly met, textile dyes are easily obtainable and might be perfectly satisfactory for the imaginative printer. These textile dyes, known as "Acid Fast", will likely work and are available very cheaply. I suspect that their light-fastness is good if they are well regarded by textile folks.

    Many sellers on eBay have large quantities of dyes, usually being liquidated from old labs, etc. All dyes have multiple names, so consult a book like Sigma-Aldrich's Handbook of Stains, Dyes & Indicators (easily available from most University libraries) to find out alternate names, chemical information, lightfastness and color quality.

    The best option might be to find a manufacturer that offers samples of their dyes. A sample is likely to be sufficient for many, many prints, or alternatively, you might wish to see what their minimum quantity is.

    When all is said and done, availability of dyes will be the key to truly making modern-day dye-transfer a reality. I am fortunate to have a wide variety of old dyes given to me by a chemist who researches dye-transfer, in addition to synthesizing his own dyes. So, perhaps there is hope that in the future we can provide better options in this regard. In the meantime, I will use these dyes to test my materials and will be simultaneously exploring alternative dye options, such as textile dyes.

    A word about dyes: acid dyes happen to have an affinity for gelatin, that is, they will stain it. This affinity is increased with lower pH (more acid), and thus the receiving paper is soaked in an acid solution to encourage the dyes to leave the matrix and transfer more completely. Logically enough, to clear the matrix after transferring, a dilute ammonia solution will liberate the dye from the gelatin. A matrix can be reused many times, another reason why this process was so successful (ultimately superceding carbro in the industry).

    There have been other methods to make prints with different classes of dyes like Pinatype above, which used "Pina" dyes... a.k.a. a proprietary dye (though Friedman lists the probable candidates). Also, there have been methods to use basic dyes, which are exceptionally brilliant & pure, but are very quick to fade. Since these dyes react differently with gelatin, different materials & methods are required. See Friedman if interesetd.

    But acid dyes are the preferred class because they are quite good in color, and are the most permament of dyes. Other dyes that will act in the same manner as acid dyes are "direct" and "reactive" dyes, though I am far from an expert on these matters.

    For an excellent paper on the requirements & testing of dyes, please follow these links -> Part 1, Part 2, Part 3, to Dyes For Imbibition Printing by Colton & Thronson.

    - TRANSFER

    Any information on dye-transfer printing, such as that given by Jim Browning, or Ctein, or Kodak's publication E-80 will give you a solid idea of what is necessary for transferring the print, as this function is independant of the kind of matrix used. At the moment, this is my least studied area of the process so I'd hate to give misinformation. It is however, pretty straight forward.

    Basically you soak the matrices in their respective dye baths until they reach equilibrium (that is, the time it takes to absorb all the dye that they can hold). Then, you transfer them to a dilute acetic acid bath of about 2%. This rinses the excess dye off. At this point, in the acid bath, the dye will not exit the relief, and if the 3 matrices are not registered yet, they can be visually aligned in this bath and punched. The color image will be visible at this point.

    Each matrix is then rolled onto the receiving paper, one after the other. The time that it takes for the dye to exit the matrix and migrate to the receiver paper will be a function of the dye, and will likely vary (as it did in the Kodak process). Standard practice is to transfer each color twice.

    Another important aspect is the receiving paper itself and the pre-treatment bath. Kodak supplied a pre-bath for the receiving paper, but at the moment I couldn't tell you exactly what is in it. It stands to reason that it would be an acidic bath, and indeed, a sloshing of vinegar (not very scientific, nor ideally probably) helped a down & dirty test succeed while testing with a food dye. See here.

    So as you can see, considerable room for experimentation is present. For initial testing, fixed out photo paper will be more than sufficient and actually the hardeners present in the emulsion, or from some fixers, will act as mordants in their own right.

    An idealized receiving paper will have a dedicated mordant. F.E. Ives first suggested this method in U.S. patent #1,121,187, 'Photographic Printing Process', from December 15th, 1914. Basically, the mordant increases the paper's affinity to hold onto the dye (from the French word mordere, "to bite").

    F.E. Ives has many earlier patents describing the use of DCG matrices for imbibition printing. Friedman doesn't spend much ink in discussing dye-transfer matrices of this type, instead simply saying that F.E. Ive's patents on the subject can be considered the authoritative text. Indeed, I would recommend anyone interested to seek them out, and I'll be more than happy to include the patent #'s. (p.s. They are listed in Friedman, and that book is available on Google books).

    CONCLUSION

    So as you can see, the work is just beginning. But all the information is out there and nothing is beyond the scope of the hobbyist. It just isn't formalized as of yet, so there is a lot of original & novel work that must be done before we can start "spreading the gospel" and telling people exactly how to do it.

    I hope this will encourage a few people to give it a go, and remember that if tri-color seems daunting, there's certainly nothing wrong with monochrome prints. That would greatly expand the list of possible dyes for the process.

    More to come in the future...

    - Chris Holmquist, holmburgers, 2011 -
    Last edited by holmburgers; 05-25-2011 at 04:20 PM. Click to view previous post history.

  2. #2
    michaelbsc's Avatar
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    Well done Chris. My hat is off to you!

    All Hail Chris!
    Michael Batchelor
    Industrial Informatics, Inc.
    www.industrialinformatics.com

    The camera catches light. The photographer catches life.

  3. #3
    holmburgers's Avatar
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    Thanks michael!... now please.. put your hat back on.... hahaha.

    You know, when I first heard about dye-transfer I had just set up my darkroom (about 2 years ago) and I honestly thought that I would never live to make a dye-transfer print after learning what is "necessary". It seems that most people doing the process are from a time when it was a commercial product for color photographs, and not an "alternative process" for art or experimentation. In all my perusing of modern information on dye-transfer, I never found any mention of this DCG method, which is very frustrating indeed. On the internet, I think there might only be 1 person who has ever proposed it, buried deep in the Yahoo! dye-transfer archives by Greg W. He recommends diazo sensitizers (screen printers use this stuff) and indeed, it's reasonable to assume that we might have difficulty obtaining dichromates in the future.

    So, basically I see an opportunity for a completely new alternative process; one that is capable of producing high-quality color prints. In alt processes, this isn't really possible at the moment. Tri-color gum can't be considered "straight color printing", and the difficulty of color-carbon is very discouraging to the hobbyist.

    When all the color papers have been discontinued, this might be the best way to make analog color prints into the 21st century & beyond. At least.. here's to hoping!
    If you are the big tree, we are the small axe

  4. #4
    holmburgers's Avatar
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    A Few Corrections & Ammendments

    HISTORY

    E. Sanger-Shepherd and O.M. Barlett were perhaps the 1st to propose the use of a relief matrix to produce dye-imbibition prints in 1902. US Patent #728,310

    METHOD

    One of Ives' most important contributions to the art, one that was used in all subsequent schemes, was the effect of the pH of the dye-bath on contrast. Since acid raises gelatin's affinity for the dye, lower pH will cause more dye to enter the matrix, thus, higher contrast will be obtained. To have 3 or 4 dye-solutions of each color, each with differing acid contents, would be an excellent method to have contrast control in the transferring stage. This is described in the British Journal of Photography, Vol 46 (1899), p. 409, 470 & 537.

    Some of Ives' Patents are: USP1,106,816 & USP1,160,288, Ger.P.308030, Eng.P. 15823/13 & 15823/14, Fr.P. 463,737.

    My explanation of why the dye transfers into the receiving paper might've been somewhat misleading The main reason for the transfer, according to Friedman, is that the matrix is necessarily very hard (tanned) comapared to the receiving sheet, which will have softer gelatin, and thus the migration.

    The acid rinse after soaking the matrices in their dye baths should be a 10% solution of acetic acid, not 2%. This highly acidic bath will remove the excess dye on the matrix, but will cause the gelatin in the matrix to adhere tightly. The matrices can be left in this, registered if necessary, until ready for transfer. This prevents the possibility of them drying out between transfers.

    A recommendation for testing textile dyes is a 2% dye solution in 5% acetic acid. However, this was for the purpose of making transparencies, so for prints the 2% concentration of dye could be reduced significantly.

    Mat or Semi-Mat fixed out photo papers will work best as receiving papers.

    A UV-restraining dye (yellow) has been added to matrices historically as standard practice to limit the depth of the relief. This might be something to explore in the future. Unfortunately, the K-dichromate stain is not sufficient to have a great affect, according to Friedman.

    Lastly, if anyone is confused or needs clarification on something, it would be my pleasure to talk about it.
    If you are the big tree, we are the small axe

  5. #5
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    Two points to add here:

    1. The matrix is exposed from the back! This causes the tanned image to begin forming at the surface of the film support for the purposes of adhesion. The yellow dye (tartrazine) is added to limit light penetration all the way to the surface thus confining the tanned gelatin image to be sharp and close to the support.

    2. The best receiving material contains a mordant which attaches to the dye. It can often shift the dye hue by a considerable amount. The mordant used in Kodak's process was a Thorium salt and was slightly radioactive. It caused hue shifts that were slight but could be easily seen. I have seen a mordant shift a magenta dye to a good cyan dye upon attachment, but this is rare.

    PE

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    holmburgers's Avatar
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    Thanks PE,

    I think I clearly stated that you expose through the base. Tartrazine would be an option for a light-restraining dye, but does it wash out or stay in the matrix? Tartrazine is actually suggested by Friedman as one of the textile dyes to use in the image transfer stage; so it would need to clear out of the matrix completely or would cause some problems I think. A yellow pigment might be an other option, and this could stay in the matrix indefinitely, as long as it didn't affect the dyes in some way.

    For starters though, it's not necessary to complicate things with a light-restraining dye. First it will be necessary to see what can be done with a plain matrix, and only fix problems as they arise.

    I've heard about this hue shift with Kodak's cyan dye and their mordant. I need to learn more about making receiving paper, but I can assure you I won't be using thorium! It will be interesting to see what affect a mordant might have on the dye-color, but again, we're talking about an incredibly sophisticated and complicated product by Kodak. The hobbyist need not concern himself with these matters, at the present.
    If you are the big tree, we are the small axe

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    Tartrazine washes out of the Matrix during processing. I don't know what the final yellow imaging dye was, but the conditions are different for dye the dye imbibition step and the transfer step so I don't think there would be a problem using tartrazine for two purposes.

    You might want to check Jim Browning's work, as it may indicate problems with other receiving sheets without Thorium salts. A salt is needed for proper image stability. The dye must remain in the proper "matrix" for proper stability.

    PE

  8. #8
    holmburgers's Avatar
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    Ok, well if the tartrazine washes out, it indeed could be a good light restrainer. It also might be suitable for imbibition itself, which would be nice because it is an easy dye to get a hold of. Afterall, you're ingesting it everytime you drink a mountain dew!

    Again though, I don't want anyone to think that they need to worry about light-restraining dyes at the moment. Last night I exposed & etched 2 new plain gelatin matrices and did a quick and dirty transfer. Preliminary results are very promising and I will post an example soon.

    As for mordants, I know that thorium is not the only option, unless you're specifically referring to the use of Kodak cyan, which yes will probably shift without it. Not a big deal though, because the whole point here is to find a new set of dyes that can be worked into a scheme for hobbyists.

    Mordants are another thing for 'down the road', but I know for a fact that fixed-out photo papers will work, and indeed, plain gelatin would even work. The key issue is the "dye absorption index". If the receiver absorbs dye very easily, diffusion of the image will occur and you'll lose sharpness. If the receiver has low dye absorption, then contrast will suffer. Technicolor tested the absorption indices of their gelatin blanks (film strips) and categorized them into different classes so that depending on their separation negatives, whether they were too hard or too flat, they could match it up with a complementary blank to produce consistent, balanced prints
    If you are the big tree, we are the small axe

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    Your last paragraph is critical in understanding what is going on or what might go on. Without the proper mordant, you can even lose dye from the print back into the second or third matrix as you are doing transfers. There are a number of things that can go wrong without mordants, but you have touched on some of them.

    As for the rest of it, I think it important to know what is going on in the real, perfected dye transfer process marketed by Kodak. If you don't a lot of things may get lost over the years. But, much of this is covered in Jim Browning's web site and I cannot stress the importance of his information enough.

    PE

  10. #10
    holmburgers's Avatar
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    I agree with the importance of studying Kodak's scheme, and looking at Jim Browning's website. It would be interesting to see if we could get some of EKC's information regarding the sensitometry of their dyes and perhaps the formulation of their materials. From a history perspective, it would be very useful information.

    Unless of course they have plans to bring back the product........(long pause).... HAH!

    I guess some of my reluctance to acknowledge these issues at the moment stems from the fact that I've yet to see what the limitations of the simplest means are. I'd like to see what can be done with the least amount of effort, and then scale up from there. That's why I'm calling this imbibition for the people; although Jim Browning has done a noble and great thing by effectively "open sourcing" his whole production method, it's still beyond the scope of 99% of the people out there. I'd like to lure people into the idea that they too can create dye-transfer prints.

    I see the major steps to success as this:

    1) a good matrix formula and simple means for preparing it (check); with the possible addition of a light-restraining dye.

    2) a good understanding of how different sensitizing concentrations will affect the contrast of the matrix, and in turn, how the pH of the dye bath can affect the contrast of the transfer. These are 2 very important controls, and I'm imagining there's a yet-understood 'Venn diagram' involving these two variables.

    3) dyes and the appropriate dye solution (buffer). That Colton & Thronson paper gives a good idea of what's needed for a dye-solution.

    4) receiving paper and mordant. Much in the same manner that we prepare carbon papers from Arches watercolor paper, and the like, I'm imagining a basic formula for hobbyists to create suitable papers.
    If you are the big tree, we are the small axe

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