Looking for dyes, additives or a formula to sensitize collodion to >800nm (infrared)

Discussion in 'Alternative Processes' started by Frank Gosebruch, May 9, 2013.

  1. Frank Gosebruch

    Frank Gosebruch Member

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    After reading the giant thread 'A real formula' with PE in the Forum: Silver Gelatin Based Emulsion Making & Coating, I'm a little confused.
    There are lots of hints ond advices for dyes to create an emulsion with superpanchromatic or, at least, expanded red or infrared sensivity. But these formulas are all just for dry plates.

    My collodion plates are just sensitive to blue light.
    After production of Kodak HIE was stopped and there was no other real infrared film material on the market anymore (forget Rollei and SPX, just 700nm / EFKE and Konica stopped production) there is no chance to continue real infrared photography.
    So I just wanted to try some dyes to expand/shift sensitivity up to 800 or more nm with collodion wet plates.

    The wet collodion process is devided in two parts.
    1. The collodion
    2. Sensibilization in silver nitrate sol.

    Where, when, how and how much do I have to add the Neocyanine or the 3,3'-Diethyloxatricarbocyanine iodide.
    Do I have to change the developer (iron(II) sulfate), then?
    How about fixing, then? Any experience?

    ...and sorry about my horrable English!
    Thanks

    Frank

    [h=1][/h]
     
  2. Andrew O'Neill

    Andrew O'Neill Subscriber

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    I suppose you would then have to sensitize the plate in total darkness then. When you sensitize with neocyanine is beyond me. Time for you to start experimenting... and spending heaps of money! Those dyes are not cheap!
     
  3. Mustafa Umut Sarac

    Mustafa Umut Sarac Member

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    Use APUG Search Engine. There are hundreds of posts invested on that subject. Or surf the APUG threads , many of them are at archive dungeon.
     
  4. Frank Gosebruch

    Frank Gosebruch Member

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    Hi Andrew,

    well, I already sensitized my plates in the darkroom tent in a small box with silver nitrate sol. (inside the box in complete darkness).
    So I hope, after a few tests there won't be need for any further check views on the plate.
    But I actually still don't know how much and which dyes to add, how to develop then (still just iron (II) sulfate sol. in darkness - what time then) and how to fix then.
    Maybe here is someone else, who tried it - I hoped it's worth asking here ;-)
    Maybe you're right and in the end I will need to try it alone the whole rocky way...
    CU

    Frank
     
  5. Frank Gosebruch

    Frank Gosebruch Member

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    Uhm... no Mustafa, there are no combined results for 'collodion' and 'infrared' in the search engine (It was my first try) for APUG forum posts... (so why do you claim the opposite?)
    That's why I asked the community.

    Do you want me not to ask anymore?
     
  6. Mustafa Umut Sarac

    Mustafa Umut Sarac Member

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    Frank ,

    I found that there was no reply to your post and wanted to help. Post thousands of posts in time , I read and answer if I could.

    Your post was first to find a answer on collodion sensitizing for infrared. I am following the forum since 2006 and never saw one.

    But there is red , green , panchromatic sensitizing posts , many.

    May be you can learn from these posts. In my experience , patents and old books are only references.

    Try to private message to Ian Grant or Photo Engineer and ask their opinion.
     
  7. Mustafa Umut Sarac

    Mustafa Umut Sarac Member

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    I googled and found a patent. I took some part referencing many important patents.

    The infrared sensitizing dyes to be used in the present invention can be directly dispersed in the emulsion. Alternatively, they may be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixture thereof to add them to the emulsion as a solution. Processes for adding the infrared sensitizing dyes to the photographic emulsion are described, for example, in U.S. Pat. Nos. 3,469,987, 3,676,147, 3,822,135, 4,199,360, and in U.S. Pat. Nos. 2,912,343, 3,342,605, 2,996,287 and 3,429,835. The aforesaid infrared sensitizing dyes may be uniformly dispersed in the silver halide emulsion before coating on a suitable support. Of course, this dispersing procedure may be conducted in any suitable step of preparing the silver halide emulsion.

    Infrared sensitive silver halide color photographic elements for use in the present invention are preferably those described in U.S. Pat. No. 4,619,892, which is incorporated herein by reference. More preferably, the infrared sensitive silver halide color photographic elements for use in the present invention are those having all of the silver halide emulsion layers sensitized to different infrared regions of the electromagnetic spectrum. The order of these layers respect to the support, the difference in emulsion sensitivity among the layers and the sensitivity, contrast and D-max of each layer are preferably those described in said U.S. Pat. No. 4,619,892.

    Any of the various types of photographic silver halide emulsions may be used in the practice of the present invention. Silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, and mixtures thereof may be used, for example, dispersed in a hydrophilic colloid or carrier. Any configuration of grains, cubic, orthorombic, hexagonal, epitaxial, or tabular (high aspect ratio) grains may be used. The colloid may be partially hardened or fully hardened by any of the variously known photographic hardeners. Such hardeners are free aldehydes, aldehyde releasing compounds, triazines and diazines, aziridines, vinylsulfones, carbodiimides, and the like may be used, as described, for example, in U.S. Pat. Nos. 3,232,764, 2,870,013, 3,819,608, 3,325,287, 3,992,366, 3,271,175 and 3,490,911.
     
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  8. Photo Engineer

    Photo Engineer Subscriber

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    AFAIK, there are no examples of dry plate, wet plate or Daguerreotype plates in the literature. I know that they were worked on at EK and at RIT many many years ago.

    I'm not saying it is impossible, I'm saying that some concerted work by a lot of people was not successful. It may be that with more modern dyes, it might work.

    PE
     
  9. Mustafa Umut Sarac

    Mustafa Umut Sarac Member

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    PE,

    Who produces these more modern dyes ?

    Umut
     
  10. Hexavalent

    Hexavalent Subscriber

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    H.W. Sands Corp www.hwsands.com manufactures many types of imaging dyes and chemicals.

    Be prepared to part with a LOT of money ($ hundreds/gram). Some dyes are very costly, and there can also be a "convenience fee" attached to small orders.
     
  11. Mustafa Umut Sarac

    Mustafa Umut Sarac Member

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    Ian,

    In your experience , how many wet plate could be sensitized per one gram of dye ? How it is being calculated ?

    I am asking in behalf of the OP because he thought I was trying to block his posts.

    Umut
     
  12. Hexavalent

    Hexavalent Subscriber

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    Off the top of my head, typically 10-100mg of dye is required for 1 mol of silver (in the form of a silver-gelatin emulsion) The actual figure depends partly upon the size and surface area of the grains.
    Therefore, it's not a simple matter to say x grams of dye will sensitize y number of plates.

    When it comes to wet-plate, it may be a totally different number, or it might not work at all.

    In the early days, plates were spectrally sensitized by soaking them in a dye solution.

    "The Photographic Emulsion", Carrol & Hubbard, Ch11 touches upon the mechanisms and variables of dye sensitization.

    A search on "dyes" and "spectral" on APUG should reveal greater detail.
     
  13. Photo Engineer

    Photo Engineer Subscriber

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    AFAIK, Sands does not list many (if any) photographic spectral sensitizing dyes used in classic systems. Kodak and Fuji make their own. I have posted a list of dyes that Kodak sells (or sold via Eastman Chemicals).

    PE
     
  14. Mustafa Umut Sarac

    Mustafa Umut Sarac Member

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    Thank you PE and Ian.

    Ian , can you tell me what is mol of silver ? Does 1 grams of dye make a solution enough to plate be able to soaked ?

    How many mols of silver does wet plate 8x10 single needed ?

    Umut
     
  15. Mustafa Umut Sarac

    Mustafa Umut Sarac Member

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    I have just googled and learned 1 mol of silver is 107 grams. We can sensitize 1 kilogram to 10 kilograms of silver with 1 grams of sensitizer.

    It makes the sensitizer dye economical , no need to experiment with large quantaties I guess to determine the formula.

    What is the minimum order quantity of EK order PE ? Can we order miligrams ?

    And How many grams of silver one 8x10 wet plate uses ?

    Umut
     
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  16. Photo Engineer

    Photo Engineer Subscriber

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    Umit;

    What if the first dye is wrong, or what if the amount is wrong. Then the experiments start.

    And the cost of a dye runs between $100 to $300 / gram of dye.

    PE
     
  17. R Paul

    R Paul Member

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    I am also interested in increasing the light response of colloidion emulsions. Could you use an inexpensive dye like eosin or erythrosine first and see if you get a better spectral response? My guestion is whether the dye goes into the colloidion mix ,the silver bath,or a seperate bath altogether. My guess would be the colloidion, since the dye may react with the silver
    You could add the dye to the pouring stock to save the main stock. About 2ml of a 0.1% dye solution in alcohol per 100ml sounds right from my gelatin work.

    Any thoughts guys?
    Rob
     
  18. falotico

    falotico Subscriber

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    Wall has a good discussion about sensitizing collodion emulsions with commercial dyes. His book, "The History of Three Color Photography" is available online--the collodion discussion starts about page 222. Here is the link:

    https://archive.org/stream/historyofthreeco00ejwa#page/238/mode/2up

    There is also a book from 1905 by Oscar Klein which is also online, "Collodion Emulsion and its Applications..." which deals with making collodion emulsions color sensitive using common dyes. That link is:

    https://archive.org/details/collodionemulsi00kleigoog

    In addition there are various Kodak publications from the 1920s which deal with sensitizing collodion, as I recall. Search the topic through Google Books.
     
  19. R Paul

    R Paul Member

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    Thanks-this is a big help
     
  20. Frank Gosebruch

    Frank Gosebruch Member

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    Thanks as well and regards
    Frank