Kodachrome yellow stain removal

Discussion in 'Color: Film, Paper, and Chemistry' started by DarkroomExperimente, Dec 5, 2007.

  1. DarkroomExperimente

    DarkroomExperimente Member

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    I developed some Kodachrome 64 last night in DD-X and tried to remove the yellow stain using citric acid & rapid fixer according to the instructions in the kodak document AE-31 ( if I remembered that # right..)

    I ignored the inital photoflo/rinse steps since the film was still wet from processing...

    Well, it says 7-14 minutes...but I didn't notice any change in the color

    at 15 minutes I cut off a small piece and left the roll in for a total of 30 minutes

    at 30 minutes I washed the film and it was certainly lighter than the small piece I cut off @ 15 minutes....but the yellow stain was far from gone

    The instructions do say to only process one "negative" at a time..and I was doing a whole roll. So I'll assume I was trying to do too much film at a time........BUT....since I will be processing entire rolls, not single negatives, I need to figure out the right way to do this

    I called Kodak Tech Support, but the guy wasn't familiar with this process.


    Help me Obi-Ron Kenobi , you're my only hope
     
  2. Mike Wilde

    Mike Wilde Member

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    Yoda says..

    My bet is that Obi Ron will not advse those twisting the powers of the force.

    As Star Wars admonsihes - you have been given a great power Luke. Use it wisely and do not torture the full colur world with monochrome processing antics.
     
  3. Photo Engineer

    Photo Engineer Subscriber

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    Check again. That document is for removing yellow stains from B&W materials not from color materials. The yellow color is Cary Lea Silver which is a yellow filter layer sandwiched between two of the color forming layers (Y/CLS/M) and is present in all color materials.

    It is intensely yellow and is intended to remove all blue light from the light that gets to underlying layers. It is removed in the normal color process, but cannot be removed (safely) from a B&W process of any color material.

    Your best hope is to use the force Luke! But, I have a bad feeling about this.

    PE
     
  4. DarkroomExperimente

    DarkroomExperimente Member

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    I feel the spectral power Mike, this is but a step along the road to understanding the wonders of the polychromatic world.

    A few years ago I developed Kodachrome as color reversal & got encouraging non-gorgeous results (ENGR).

    I'm warming up for another set of attempts
     
  5. Photo Engineer

    Photo Engineer Subscriber

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    Developing Kodachrome as an E6 type product should give you clear film!

    PE
     
  6. DarkroomExperimente

    DarkroomExperimente Member

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    No need to check again: AE-31 is titled: "Printing Color Films Developed as Black and White"

    the process I used was under the heading: "To remove the stain from Kodachrome and Kodak Ektachrome films"
     
  7. Photo Engineer

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    Well, it won't work! Sorry.

    IDK who thought that one up, but as you see it does not. It was probably intended for an earlier version of the films which used a yellow dye.

    I said I had a bad feeling about this.

    PE
     
  8. Photo Engineer

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    Kodak's knowledge base does not have a document AE-31 listed. So, I can't help by reading it through.

    PE
     
  9. DarkroomExperimente

    DarkroomExperimente Member

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    I didn't use E-6....IIRC it was BW 1st dev ( don't recall which ) each red/blue/white light re-exposure was followed with a water/alcohol solution with a color coupler, then with C-41 developers with added color couplers...then C-41 Blix

    the images were muddy from the CLS and at the time I didn't know about REMJET which also messed it up a bit...but I did get colors in the right places, but it was rather unsaturated and faint...I had to increase saturation in Photoshop to see the colors well...but they were there
     
  10. Photo Engineer

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    The CLS would be removed by the blix and fix. What couplers did you use? They are generally hard to get.

    PE
     
  11. DarkroomExperimente

    DarkroomExperimente Member

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    I just sent you an email with the PDF file

    My first attempt at B&W reversal was with kodachrome...and it looked beautiful.

    Would the acid/dichromate bleach from BW reversal work in a color process - or is that bleach harmful to color dyes?
     
  12. DarkroomExperimente

    DarkroomExperimente Member

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    Ah...I had tried extra Blix...but it didn't do much..and I don't think it was expired.

    I got the couplers from Rockland Colloid...from their "selectachrome" product..which is now called "Polytoner"
     
  13. Photo Engineer

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    Ok, here are a few thoughts.

    1. Thanks, I read the document and it is 'modern' having been revised in April of 1999. Unfortunately, that will not work. IDK why they published it. Acidic hypo is known to bleach and fix (blix) finely divided sillver, but I don't think it will work on this time scale. It is much too slow. The photo flo might help speed things up, but I doubt it. A dichromate bleach will remove all silver image. You will end up with blank film. At best, a tiny amount of silver sulfide might remain.

    2. Many couplers are what are called 4 equivalent, and they need a ferricyanide bleach to oxidize them and form the final dyes. Modern films contain 2 equivalent couplers which form dyes in the developer. I cannot tell what Rockland sent you, but I would suggest using a sulfite stop after each developer, with a good wash. Then after the final developer and sulfite stop with wash, use a ferricyanide bleach (with bromide) and then use a fix and wash. This should clear coupler and developer after each color development, and should oxidize all leuco dye to the final colored form.

    The Kodachrome formulas are published for all to see in the US patent. It is under the names of R. Bent and R. Mowrey. Sorry, I don't have my copy here to give the number, but I have posted it several times on APUG.

    PE
     
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  15. DarkroomExperimente

    DarkroomExperimente Member

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    thanks!

    I did this back in 2000 and I think they sent me the MSDS on their couplers, but I don't think I have that information anymore..I'll have to ask them again
     
  16. DarkroomExperimente

    DarkroomExperimente Member

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    found the MSDS...You'll notice these are the "wrong" colors...Rockland gives you a table for how to mix the couplers to get different colors.

    I'm assuming the last entry is in all 3 coupler bottles

    here it is:

    ===========================================================================
    Ingredients/Identity Information
    ===========================================================================
    Proprietary: NO
    Designation: RED COUPLER
    Ingredient: 4-NITROPHENYLACETRONITRILE
    Ingredient Sequence Number: 01
    Percent: 10
    NIOSH (RTECS) Number: N/A
    CAS Number: 555-21-5
    --------------------------------------------------------------------------
    Proprietary: NO
    Designation: YELLOW COUPLER
    Ingredient: P-CHLOROACETOACETANILIDE
    Ingredient Sequence Number: 02
    Percent: 10
    NIOSH (RTECS) Number: N/A
    CAS Number: 101-92-8
    --------------------------------------------------------------------------
    Proprietary: NO
    Designation: BLUE COUPLER
    Ingredient: 2,4 DICHLORO 1-NAPHTHOL
    Ingredient Sequence Number: 03
    Percent: 10
    NIOSH (RTECS) Number: N/A
    CAS Number: 2050-76-2
    ---------------------------------------------------------------------------
    Proprietary: NO
    Ingredient: 2-BUTANONE (METHYL ETHYL KETONE) (MEK)
    Ingredient Sequence Number: 04
    Percent: 90
    NIOSH (RTECS) Number: EL6475000
    CAS Number: 78-93-3
    OSHA PEL: 200 PPM
    ACGIH TLV: 590 MG/CUM
    Other Recommended Limit: 590 MG/CUM
    ===========================================================================
     
  17. Photo Engineer

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    Ok, those are the 3 couplers used in an old book by Leadly and Stegmeyer. They work slowly with CD-4, but will still work ok. The MEK is just a solvent, as the 3 compounds you have there are rather insoluable in base. Leadly and Stegmeyer used acetone instead of MEK, and you could use alcohol as that would be even better. So, here goes.

    Rem jet removal
    wash
    D-19 first developer
    wash
    red exposure
    C41 + napthol (about 0.2 grams / liter to start)
    stop + sulfite
    wash
    Blue exposure
    C41 + acetanilide (about 0.2 g/l for starters)
    stop + sulfite
    wash
    white light exposure or E6 reversal bath
    wash
    C41 + nitrile (about 0.2 g/l for starters)
    stop + sulfite
    wash
    ferricyanide + bromide bleach
    wash
    hypo
    wash
    photo flo
    dry

    This is based on L&S roughly. They did it with single layers, so you will probably have to use more coupler. Use the developers at once, as these are one-shot developers. You also might find that it works better at pH 11 with a Phosphate buffer, as if IIRC that is where the Kodachrome developers are for better activity.

    PE
     
  18. DarkroomExperimente

    DarkroomExperimente Member

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    thanks!

    so it's normal acetic acid stop bath plus sodium sulfite?

    the developer that comes with the Rockland Colloid kit is supposed to be mixed with alcohol...I assume that's for helping the couplers dissolve like you said


    "You also might find that it works better at pH 11 with a Phosphate buffer, as if IIRC that is where the Kodachrome developers are for better activity."

    is this pH 11 for the D-19 or the color developer?
     
  19. Tim Gray

    Tim Gray Member

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    Could I get a copy of that PDF? Sounds like an interesting read...
     
  20. Photo Engineer

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    It is pH 11 for the color developers.

    The stop is 2% acetic acid + 10 g/l of sodium sulfite (either anh or monohydrate, this isn't exact).

    The pamphlet is interesting but moot as the method does not appear to work with current films.

    PE
     
  21. DarkroomExperimente

    DarkroomExperimente Member

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    <img src="http://i260.photobucket.com/albums/ii36/DarkroomExperimenter/kchrometest-thumb.jpg"></img>

    this is what I got from my experiment back in Feb of 2000

    the actual image looks much muddier and fainter....I increased saturation in Photoshop...probably upped the contrast too
     
  22. Photo Engineer

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    Looks pretty good.

    The swirlies look like undissolved coupler. Was there an oily residue in or on the developer solution? If so, that was your main problem.

    PE
     
  23. DarkroomExperimente

    DarkroomExperimente Member

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    I don't remember any oily residue

    I know I was worried I wouldn't have enough coupler...so before each color developing step I put the film in a coupler/alcohol bath for a few minutes then into the dev/coupler....I wouldn't be surprised if I added too much coupler to be "safe"

    also...at the time I didn't know I had to remove the REMJET...so I wonder if that messed things up a bit..especially the red exposure

    I don't think I have an original scan...before Photoshop it looked pretty brown
     
  24. Photo Engineer

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    Remjet would have prevented any red exposure, but your examples seem to have cyan dye where expected.

    Interlayer contamination through exposure error or wandering chemicals can be a big problem. Too much coupler-alcohol can lead to oiling out of the coupler in the developer.

    PE
     
  25. DarkroomExperimente

    DarkroomExperimente Member

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    I seem to remember black goop coming out after the first developer...but some remaining REMJET could have at least made red exposure uneven
     
  26. Photo Engineer

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    That could be the cause of swirlies too.

    The thing is that these films are made to a specific balance in layers and interlayers to match a set of 4 specific developers and it would be a rare event to get a good result out of a process such as yours. I recommend that you read the patent. All of those ingredients are there for a purpose.

    PE