Making a Dye Transfer Matrix film
Hello Everyone, Ron urged me to post my Dye Transfer Matrix film formulation here, just in case you haven't seen it on the web at www.dyetransfer.org. The web page has much more information than here, listing details on the coating methods, etc. There are many pictures there as well.
A matrix film is an unhardened emulsion used in the production of a Dye Transfer print. The film is exposed through the base, and developed in a tanning developer, and then washed off to form a relief image. The gelatin opn the matrix film is dyed in a dye bath, and then transferred to a photo paper. Usually three matrices are made, one each for Cyan, Magenta, and Yellow. I have made dozens of prints with this film, and several others are using the commercial version of this film.
While I haven't tried this, I believe this emulsion would work well as a paper emulsion of enlarger speed. It could be used as a slow taking film as well, or could be sped up using a gold sensitizer. I would add a hardener and sensitizing dyes for these applications.
The curve shape of the dye print is very linear with a short toe and shoulder. I'm not sure what the curve shape would be when coated on paper or as a taking film, but it would probably be similar. There is a plot of the curve shape in the files section of the yahoo dye transfer group.
The film was produced by Fotokemika (Efke) in Croatia, and 3 miles 50" wide was coated. We are currently working on producing more film.
If you have further interest in the dye transfer process, pease visit the site:
www.dyetransfer.org . There is a discussion group that you can join from that site.
Making the emulsion requires a system for heating a five-liter container (Stainless), and maintaining the temperature accurately. A burette suspended over the container is used to slowly drip solution B into solution A over long periods of time. A paddle stirrer is also mounted over the reaction vessel, and run at slow speed.
The following formulation (Trial # 20) is for four Liters of emulsion:
Potassium Bromide 168 g
Potassium Iodide (5% solution) 62.4 ml
Inert Gelatin 160 g
Distilled Water 3500 ml
Silver Nitrate 160 g
Distilled Water 500ml
Solution C: (for 500 ml of emulsion)
Sodium Thiosulfate (0.1% solution) 1 ml
Gelatin 30 g
(Gelatin added directly to the heated emulsion)
Solution D: (for 500 ml of emulsion)
Potassium Bromide (1% solution) 10 ml
Manganous Sulfate (1% solution) 10 ml
(1 % solution pH 7.2) 7.5 ml
Acid Yellow Dye # 23 (Tartrazene) 1.5 g
Triton X-200 (1% by volume) 3 ml
Sorbitol 3.75 g
Note: Adj. pH of triazaindolizine solution to 7.20 by adding Sodium Hydroxide.
Solution E: (for 500 ml of emulsion)
1-Phenyl-5-Mercapto Tetrazol 0.1% in Ethanol 4 ml
Sodium Azide 6.5% Water Solution 20 ml
(You will probably want to substitute Thymol for the Sodium Azide as a preservative, as it isn't explosive! Solution E is what Fotokemika added as a stabilizer and preservitive)
Emulsification / Physical Ripening
Add B (at 55° C) to A (at 55° C). Use a burette over a heated beaker holding solution A at 55° C. Stir the solution using a paddle mixer. (Approx. 200 rpm). Temperature must be controlled to 1° C using a temperature controller and hot plate.
Addition as follows:
Add 10 ml of B to A in 5 seconds.
Wait 1 minute
Add 245 ml of B to A over 4 minutes.
Wait 10 minutes
Add 245 ml of B to A over 5 minutes.
Ripen additional 15 minutes
Immediately chill the emulsion using an ice bath. Chill until the emulsion is very solid, whack the side of the container, there should be a distinct 'jiggle' feeling.
Cut the emulsion into 'noodles' 1/4" crossection. Wash using distilled water for 8 hours. Change water frequently. Use at least 2 gallons of distilled water. You may use the 'silver nitrate' test, or measure the conductivity of the wash water to monitor washing.
The following steps prepare 500 ml of emulsion for coating one sheet.
Note: To prepare a batch of film having matched speed, do the following steps on the full quantity needed. Multiply the quantities by as many sheets as you are going to coat. Sensitize the emulsion with solution C, and add the final prep (solutions D and E). Filter the entire batch in two stages, first with 40 um filter paper, followed by 5 um filter paper. Use a vacuum filtration system. Pour the emulsion into 1L stainless containers with lids, 500 ml per container. Refrigerate until fully gelled. Remelt the emulsion in one of these containers, and immediately coat. Use the same procedure for each coating. I coat 8 30x40" sheets of Melenex film with one batch of emulsion.
Remelt the emulsion, heat to 60° C. Add the 30-g gelatin to the mix, and stir until fully dissolved. Add Solution C, mix thoroughly. Stir rapidly for 1 hour while maintaining temp at 60° C. Control temp to 1° C. This step should be stirred vigorously. Cover the emulsion with aluminum foil while stirring to prevent fogging from the safelight. The emulsion's speed increases greatly during the sensitization process.
Add solutions D and E, mix. The Tartrazene dye is used to absorb blue light to cause the depth penetration exposure effect and to minimize scattering. If you want to store the film for a long period of time, make sure you add Solution E, the PMT stabilizer is very effective, with the film being usable after one year at room temperature storage. A wetting agent Triton X-200 is added to promote even coating. Triton X-200 is an an-ionic surfactant. It is available from Union Carbide Corp. 1-800-568-4000. The Sorbitol is a plasticizer used to minimize reticulation, drying marks, and minimize curl. Mix a full batch of emulsion, and pour into separate containers. Store chilled.
Coat 500 ml over a 32" X 50" area. At > 100° F.
Note - coat about 1/2 this much for a taking film or paper coating.
Regards - Jim Browning
This is probably the most complete and best description of an entire emulsion that I have seen published on the internet. It works!
I would add, that I have suggested that the 4' and 5' times be reversed, as this is a growth equation (see my earlier post) and has to do with growing a surface on a crystal with acceleration. Otherwise it is near perfect. The only other precaution is in the use of Sodium Azide. I suggest using some other preservative due to the problems associated with this compound.
This is a very good starting point. Jim should be commended for creation of such a fine formula for us all.
Thanks for bringing your emulsion recipe over from dyetransfer.org; I know you have a huge investment in blood, sweat and tears in this undertaking (as well as money) and I, for one, really appreciate your unselfish sharing of your work.
Sorry I haven't been very active on the list. Hope I can eventually do some dye transfer images.
Hardening the coating and adjusting the coating levels of silver and gelatin will give a pretty respectable camera film.
So this is the actual formula that Fotokemika used for the Efke dye transfer matrix film?
Wow. This must be the first time any industry is so "open source" ! That's very commendable. Has Ctein used the product?
Using film since before it was hip.
"One of the most singular characters of the hyposulphites, is the property their solutions possess of dissolving muriate of silver and retaining it in considerable quantity in permanent solution" — Sir John Frederick William Herschel, "On the Hyposulphurous Acid and its Compounds." The Edinburgh Philosophical Journal
, Vol. 1 (8 Jan. 1819): 8-29. p. 11
My APUG Portfolio
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Thanks for posting this.
Any emulsion work is very interesting.
Edit: OK, thanks for having the decency to remove your post.
Last edited by ben-s; 07-06-2007 at 07:22 AM. Click to view previous post history.
Reason: Certain comments no longer valid
Lens caps and cable releases can become invisible at will. :D
your real contributions along with those of pe and a few others are making reading all this an education and a joy
NO GOOD DEED GOES UNPUNISHED
let the games begin
vaya con dios
Efke coating project
The only reason that is it 'open source' is that I developed the formulation, and decided to put it in the public domain. In fact, if I hadn't done that, it would never have been produced commercially. My theory was that you only get back something if you contribute freely - sort of like the open source movement, or perhaps Karma.
Originally Posted by mhv
This is the formulation we had Fotokemika use to produce the Efke Matrix Film. I worked on the emulsion over three years during the period that we were developing the Chromira printer. Once I was making prints from matrix film that I coated myself, I was satisfied that the formulation was a good one.
Egbert Haneke, approached Fotokemika with my public domain formulation, and they agreed to produce it. We spent a week at their plant in Samobor while they made test runs. They duplicated my techniques as closely as possible, including the rates of additions, rate of cooling, etc. It was suprising that their techniques weren't that much different than my experimental setup. Instead of mixing 4 L at a time, they would mix 500 L. Once we had tested the samples, we were good to go coating 3 one mile long rolls of Melenex film that Egbert had located in Europe. All of this film has been sold, and exists in several people's freezers. We are planning another run soon.
Ctein tried the emulsion, but isn't using it. He uses a panchromatic matrix film.
Regards - Jim Browning
Modification of Matrix film formulation
Hi Ron - Could you describe what you have done with this emulsion formulation? I remember you talking about having made a taking film from this emulsion. Did you add any sensitizing dyes? Gold Sensitizing? What approx. speed did you acheive? Also, you did an analysis of the iodine deposition (interior -vs- exterior of the AgBr crystals), and perhaps have some suggestions for improving the efficiency?
Originally Posted by Photo Engineer
My grain size was optimized for its hardening effect on the gelatin (too small doesn't work), but I think that the grain size is appropriate for a taking film. I saw the cubic crystals under a microscope at FK, it was fun to actually see this - makes it seem more real than theoretical.
Regards - Jim
I didn't make your emulsion. There must have been a misunderstanding there. The formula is entirely familiar to me from Kodak work except for the addition rates being reversed and the use of Sodium Azide. Therefore, I can comment that it is an entirely normal emulsion formula.
In fact, with a bit of calculation I could tell you what grain type you are getting and etc...
This is a near camera speed emulsion when coated in the right manner (ie. Hardener and sensitizing dye if desired) and appears totally normal to me in my context of a Kodak engineer.
Thats about all I can add. I understand about the grain size relationship to hardening, but if hardener is added, this is irrelevant.
Up in temperature and down in gelatin would increase speed. Longer hold time after PPTN would increase contrast. All of this would enhance the speed in-camera.