Dye-Imbibition (dye-transfer) & Carbon printing

holmburgers · Mar 8, 2011

Eureka!

Well tonight turned out to be an exciting night for me. I created a dye image! I honestly did not expect to, but it just kind of happened. Allow me to explain...

I was exposing some of the DCG matrices, at 10 minutes, 20 minutes and 30 minutes; using 2 CFL blacklights. In each one (after a hot water etch) I could spot a relief image, but it was incredibly hard to see, so I thought 'ahh what the heck' and soaked one of the matrices in some water with half a dozen drops of blue food dye. Then it occurred to me to throw in some vinegar, since it's acid that gives the dye an affinity for gelatin. Lo & behold, after several minutes of soaking, you could spot a faint image in the matrix. The next logical thing was to slap it down on a piece of paper and see what happens. I rubbed a bit of vinegar on a fixed out sheet of RC paper and squeegeed the matrix onto it. 10 minutes or so later I peeled it off to reveal this image.

It's very humble of course, but I could not believe how good it looks considering. For one, it was a food dye, off the shelf from a grocery store! 2nd, absolutely no measuring of either the dye or the acid or timing of the soak or transfer and not to mention the use of vinegar in lieu of acetic acid. 3rd, no special receiving paper or mordant treatment.

The print shows all sorts of flaws that can and will be eliminated. My sensitized matrices were incredibly splotchy and dried puddles of PD created regions of opacity. I've got to get a better sensitizing procedure than soaking I'm afraid, though better squeegee practices might do the trick. Also, the transfer was pretty basic; just slap it down and wipe it flat with a wet sponge. I need to find a good rolling pin that is suitable.

The sharpness is surprisingly good, considering that I kept the negative in a polyethylene sleeve for the exposure and exposed through the base of the matrix film. My UV-light is by no means a point source and was not that high above the printing frame (1 foot tops).

My goal is to make dye-transfer viable for anyone who wants to do it.

Hexavalent · Mar 8, 2011

Congratulations Chris!!!!

It is always such a good feeling when something actually works. Looking forward to seeing some 36 x 48" colour posters

holmburgers · Mar 8, 2011

Thanks Ian!

Color coming right up...

Luckily I have a large sampling of dyes that are suitable for imbibition, but the "success" of food dyes suggests that other types of consumer dyes should work just as well, if not a lot better. Namely, textile dyes. I'm lucky to have had a number of imbibition dyes given to me by a researcher in the field, but to find a truly accessible source (for the masses) would be liberating.

Separation negatives and registration are the next steps to color.

holmburgers · Mar 17, 2011

Cool archive from David Doubley on Dye-Transfer... http://www.daviddoubley.com/DyeTransfer.htm

holmburgers · Mar 18, 2011

Here's a great article about UltraStable carbon printing developed by Charles Berger.

http://www.nytimes.com/1992/12/06/style/camera-color-almost-too-good-to-be-true.html?src=pm

Ray Rogers · Mar 18, 2011

I had been wondering what became of US...

holmburgers · Mar 23, 2011

So I was at my local grocery store and noticed an advertisement for Heinz Vinegar. It said something to the effect that one should add vinegar (an acid) to your Easter-Egg dye's, making the colors stronger.

Ahah! It seems that acid enhancing a dye's affinity for a substance is not unique to dye-transfer! There's hope yet for the world....

Photo Engineer · Mar 23, 2011

That is an old trick. Here is one for you!

Did you know that hard boiling eggs in a pan full of onion leaves give beautiful colored eggs with swirling patterns on them similar to an onion? That is how we used to dye eggs when dyes were scarce during the wars.

PE

Mustafa Umut Sarac · Mar 23, 2011

Iraq war ?

Photo Engineer · Mar 23, 2011

When I was a child??

No, first WWII and then the Korean War.

PE

holmburgers · Mar 24, 2011

Thanks, PE, I had no idea about that. Reminds me of the emulsion maker at Kodak who ate onions and then....

holmburgers · Apr 12, 2011

F.E. Ives Patent #1,121,187 'Photographic Printing Process' from 12.15.1914

This is a patent by one of my favorite innovators in the history of photography, and particularly color photography.

He describes making dye-transfer (imbibition) prints in a manner almost identical to the one I'm proposing.

There are some strange idiosyncracies, like dying the matrices & letting them dry before placing them in contact with the receiver sheet, and then using a wet blotter underneath to bring out the dyes, under heavy pressure.

Also, he talks about using alizarin dyes, using 'pea-cock blue' to describe cyan, which I find quite charming. Furthermore, he discusses the importance of non-soluble mordants in the receiving paper so that previously laid-down dyes don't migrate into subsequent matrices. I'm still reading it, but that's the gist.

Enjoy!

History side-note, Ives was the first person to demonstrate the remarkable ability of tri-color synthesis to simulate reality. Of course there were others that demonstrated this theory, such as du Hauron, Maxwell, etc., but until Ives did it justice, many people (including leading photographic researchers of the time) did not believe that it was actually capable of excellent results. He made a lot of people "eat crow" when he demonstrated his Kromskop device, and his color-superposition projections.

Apparently he was a fantastic lecturer, and could describe things in a manner that anybody could understand. He approached his problems systematically and also used scientific practice over "rule of thumb". Basically, he was a really awesome dude. Oh, and his son was largely responsible for color TV.

He was also a very strong proponent of using the proper terms to describe the subtractive primaries, magenta, cyan (or peacock blue I guess...) and yellow. At the time, many people erroneously used 'red, blue and yellow' to describe the proper printing colors.

holmburgers · Apr 18, 2011

So I reread Friedman's chapter on "Transfer Processes" and some fascinating things came to light. For one he says that Ive's work in the area of dichromated-gelatin (DCG) matrices could act as a "text on the subject" and indeed he leaves it at that, going on to discuss silver-halide matrices.

IIRC, the original technicolor printing was done with DCG matrices and switched to silver-halide later on.

Another very interesting prospect is using basic dyes. All dye-transfer schemes generally use acid dyes (except Pinatype, which used 'pina' dyes which I beileve were not necessarily acid dyes... need to clear up the details there...). Acid dyes have a natural affinity for gelatin and are also much more stable to light. HOWEVER, basic dyes are incredibly brilliant and pure and superior in terms of hue and saturation, but not light-fastness. Furthermore, the methods to transfer them using gelatin matrices is necessarily different.

Now, I'm not going to pursue basic dyes at the moment, but the allure of making prints with them is very strong. It would be an interesting prospect, to make a picture that is incredibly brilliant and colorful, but without any long-term keep stability. For some kind of "special occasion" it would be incredibly cool to see a print made with basic dyes; but alas it would be fugitive. But just imagine the color quality....

holmburgers · Apr 20, 2011

Pinatype

This is exciting!

So I put out a call on several Yahoo! groups for information regarding Pinatype, an early dye-transfer process that was used to make 3-color prints from dichromated gelatin matrices. It is very similar to the method I'm pursuing except for 1 very important caveat, it uses a planographic matrix and thus is printed from positives, not negatives.

A planographic matrix is not hot water etched as in a relief matrix, and thus the tanned portions absorb none or less dye than the soft gelatin. "Pina" dyes are perhaps in a class by themselves, unlike acid dyes in that they don't have a natural affinity for gelatin. I'm not 100% clear on this fact however..

Anyways, a friendly fellow photohistory lover sent me these images of a complete Pinatype outfit that he snagged on eBay. He said it would be fine if I shared them on APUG (he's a lurker himself).

Here is his description, a good synopsis of the history:

"Pinatype was patented in 1903 by Leon Didier. From 1905 kits were manufactured and sold by the chemical firm Meister Lucius & Bruning (known later as Hoechst AG) of Höchst, Germany.

The Pinatype kit contains the specialized supplies that are needed to make color prints from color separation negatives. Pinatype is an imbibition or dye transfer process, first described by E. Edwards in 1874 and later, independently, by Charles Cros in 1880. Leon Didier was the first person to commercialize the process."

holmburgers · Apr 20, 2011

Here are two pinatype prints found on wikimedia commons.

http://commons.wikimedia.org/wiki/File:Nicola_Perscheid_-_Frl._Jungmann_1900.jpg
http://commons.wikimedia.org/wiki/File:Rosen_(Pinatypie).jpg

Ray Rogers · Apr 20, 2011

Thanks Chris,
That was fun!

Where are the instructions that come with the Pinatype set?

holmburgers · Apr 20, 2011

Now that I don't know, but perhaps said 'photo friend' can share(??). It would be very interesting to know.

RedGreenBlue · Apr 20, 2011

Unfortunately the instructions were missing from the kit. The only other item that is missing is a "piece of oiled silk". I located instructions for making Pinatype prints on the Web but they were generic in nature and not specifically written for this kit.

...Scott

CMB · Apr 20, 2011

Dichromate vs Tanning Developers

Originally Posted by holmburgers , 10-29-10

So my question is, is gelatin hardened in a tanning developer fundamentally different than gelatin hardened by K-dichromate?

and answered by holmburgers, 11-01-10

Seek, and you shall find....

J.S. Friedman, History of Color Photography, pg. 443
Quote:

"...tanned gelatin has properties identical with light-exposed dichromated gelatin."

This is not completely accurate. While the chemical cross linking may (no one really is sure) be "identical" the results are not. Gelatin hardened by tanning developers (think carbro, dye-transfer) has a fixed end point or "boundary" beyond which no more can be washed away without physically abrading the emulsion. Dichromate hardened gelatin (think carbon,Fresson) has a very soft boundary between the soluble and insoluble that easily washes away and is difficult to control. This difference in repeatable results, most evident in highlight detail and neutral color balance, is why it is so difficult to make two continuous tone color carbons look exactly alike.

If a Cr3 hardened gelatin emulsion is used to make matrices for tricolor dye transfer , the unpredictable results would require that the printing of each color be individually and laboriously determined by trial and error. Silver-reactive tanning developers, by comparison, provide the controlled and repeatable results which are necessary for a viable color print process. Technicolor, a contact printing process with no need for the enlarger-speed silver based matrices of dye-transfer, switched from dichromate to silver for this reason.

holmburgers · Apr 20, 2011

This is news to me and very welcome information to boot.

Looking back at Friedman now, I see that I basically took it out of context. It was describing the inability of tanned gelatin to absorb aqueous solutions in general.

So going forth, is my best defense against this to strive for a tightly controlled etching regime? (temperature, time, agitation)

On the bright side, at least a matrix can be reused and some control can be exercised in dying characteristics.

I can see how carbon might be very frustrating!

holmburgers · May 20, 2011

Reading Luis Nadeau's book on the History of Carbon Printing, I came across the best pigments for 3 color carbon.

His first recommendation is from Ciba-Geigy:

Yellow
65% Chromophtal Yellow 3G (CI pigment yellow 93)
35% Chromophtal Yellow GR 65 (CI pigment yellow 95)
-- These are disazo condensation pigments

Magenta
Chromophtal Magenta 5077 (G) (CI pigment red 222)
-- A non laked high molecular azo pigment

Cyan
Irgalite Blue L GLD (CI pigment blue 15.3)
-- a copper phtalocyanine

Another set offered by DuPont, is:

Yellow
Dalamar (17) - a mono azo yellow

Magenta
Monastral Red - a quinacridone

Cyan
Monastral Blue - a phtalocyanine

I haven't looked extensively into obtaining these pigments, but there do appear to be a number of companies that make them. The question is of course, what is the minimum quantity and will they even give you the time of day if you're not a large manufacturer?

Now, something very interesting and that is also easily available to everyone are these Liquitex Proessional Acrylic Inks

The Phtalo Blue Green Shade is made with phtalocyanine blue (PB 15:3) - a direct hit!
The Quinacridone Magenta is made with quinacridone magenta (PR 122) - suspiciously close to CI pigment 222
The Yellow Medium Azo is made with arylide yellow 5GX (PY 74 LF) - a monoazo pigment

So it would appear that these inks are excellent matches in terms of the pigments for 3-color reproduction, the only concern being how an acrylic based emulsion would act in carbon printing. Any thoughts on that?

holmburgers · May 20, 2011

Definitely a good idea... who knows, a sample set might last a hobbyist a long time.

holmburgers · May 20, 2011

As it turns out, monoazo yellows are not very light fast. A disazo condensation pigment would be much more resistant to fading. In this respect, the CIBA recommended pigments would be better and the liquitex ink would not necessarily be ideal.

See here... http://www.handprint.com/HP/WCL/pigmt1d.html#monoazo

The more I read about acrylics in general, the more it seems that they wouldn't work. Acrylics become completely insoluble after drying; therefore I don't know how well that would work in carbon, though perhaps the concentration wouldn't be enough to pose a problem.... testing is in order.

Photo Engineer · May 20, 2011

Remember that only Azo dyes have a dual purpose of acting as pigments and as azo dyes in dye bleach imaging. Others do not.

PE

holmburgers · May 20, 2011

Does that go for monoazo arylides, the disazo diarylides and disazo condensation pigments? ...that's a mouthful!

So you're telling me I could use these in a home grown Cibachrome??

edit/update: I requested a sample of 3 process-color pigment candidates. . . we'll see how that goes.

These would be the appropriate product lines from BASF (has incorporated Ciba):
http://www.basf.com/group/corporate/en/brand/CROMOPHTAL
http://www.basf.com/group/corporate/en/brand/CINQUASIA
http://www.basf.com/group/corporate/en/brand/HELIOGEN

Dye-Imbibition (dye-transfer) & Carbon printing

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