Kallitype Stain?

Discussion in 'Alternative Processes' started by philldresser, Dec 20, 2006.

  1. philldresser

    philldresser Subscriber

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    Here's another version of the Cathedral door detail printed with the kallitype process.

    [​IMG]

    This one is dev'd in Borax/Rochelle Salts and cleared in Citric Acid. No toners applied. The Paper is Arches Aquarelle HP 300g

    My question here is why am I getting the stain most noticable at the top of the image? Is this incomplete clearing? It is clearly where the sensitizer was applied.

    I have printed this before with just Borax dev and dont remember the stain on the same paper.
    Any ideas?

    Cheers

    Phill
     
  2. sanking

    sanking Member

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    Phil,

    There are several possibilities. You may have coated the top of the print with more of the sensitizer than the bottom.

    On the other hand, I am not sure how much of the bottome we are actually seeing. There also appears to be stain on the sides and bottom of the print. If this is so, then something is wrong with the basic procedure, i.e. either your paper may be one that does not clear well, or your developer is base and the iron stain started then, and if not then, in an ensuing wash.

    The Borax/Rochelle Salts are not good developers for kallitype, IMO since they work at a base pH which encourages the formation of iron stain. Try one of the devopers used for Pt/Pd such as ammonium or sodium citrate, or potassium oxalate.

    But I really like the photo.

    Sandy King




     
  3. Paul

    Paul Member

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    Cool photo.

    Looking at the step wedge, it would appear that you have a clearing problem. You seem to have the same tone in steps 18-21 that you do at the top and I would expect paper white by that end of the wedge (at some point at least). You could verify a clearing issue by masking part of the coated surface during exposure.

    -Paul
     
  4. philldresser

    philldresser Subscriber

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    Sandy, Paul

    Thanks for the replies. I have some sodium citrate now so I wiill try it with the acid dev. Cheers

    Phill
     
  5. sanking

    sanking Member

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    Phil,

    Just make sure the developer acidic after you mix it up. There are acidic and base types of sodium citrate and if you have the base type you will need to add a bit of citric acid to make it acidic.

    The staining may also be happening in the water baths. If your water is alkaline this is highly likely. I just skip the water bathes and go directly to the clearing baths.

    Sandy
     
  6. philldresser

    philldresser Subscriber

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    Sandy

    My water supply is very alkaline and high in calcium deposits. I use a water bath between dev and clearing which I will omit as well. I also did not know that sodium citrate could be base. Fortunately I have lots of citric acid.

    Thanks for the help

    Phill
     
  7. Jim Noel

    Jim Noel Member

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    I eliminated a similar problem by making my first rinse slightly acidic. I follow Sandy's procedure of utilizing a single tray. This enables me to mix 500 ml of dilute citric acid and use about 30-50 ml to acidify the first rinse. When I follow this with a running water wash prints are 70-90% cleared prior to placing in the clearing bath.
     
  8. philldresser

    philldresser Subscriber

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    Thanks Jim

    I'll give it a try. I do an acid rinse for cyanotypes just never put 2 and 2 together :rolleyes:

    Phill
     
  9. philldresser

    philldresser Subscriber

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    I have been trying the Sodium Citrate dev tonight (on Arches Platine) and still see some of this stain. Whats more is when I pour in the developer I get a grey/black precipitate forming over the image. I assume this is the silver being removed! The preciptate gently floats off, but its this that leaves the stain. So I have come to some half baked conclusions
    1. that I may have an agitation problem and I'm not removing the precipitate fast enough and it stains. My trays are about an inch bigger than the paper which does not leave much room for movement of the paper and chems. I will try the next image with a bigger tray.
    2. the dev volume is not enough (I use 300 ml for a 5x4, which I use for 5 prints max). First print tonight did not have stain, all subsequent prints using the same dev solution have go it.

    Other observations :
    The colour of the Sodium Citrate deved image is very cocoa in colour. Nice for some images but toning will be needed for others
    I lose about 1.5 stops of contrast by using Platine and Sodium Citrate compared to Aquarelle and Borax/Rochelle salts. Is this possible?

    Phill
     
    Last edited by a moderator: Dec 27, 2006
  10. Dana Sullivan

    Dana Sullivan Advertiser Advertiser

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    Hi, Phill. I see you're busy printing away!

    A yellow stain is always going to be ferric oxalate trapped in the paper. I'm not sure how this would effect the kallitype process, but I might suggest adding a small amount of EDTA to the ferric oxalate solution. About .5 g per 25ml would be more than enough. I would suggest trying it with a very small amount of ferric oxalate in case the EDTA precipitates the silver nitrate from solution.

    We find that many papers are difficult to clear completely, so adding a small amount of the EDTA to the sensitizer means there is already clearing agent in the image. The EDTA is also a chelating agent and aids in the solubility of iron compounds, so it's used in many fertilizers to help the plants absorb iron from the soil.

    I've only had experience using Borax and Sodium Acetate as developers for Kallitype, but I'm suprised to read that Sodium Citrate is causing the silver to precipitate.

    It's a silly question, but have you tried developing your images upside down? Many gum printers I've talked to will do that to limit staining. Perhaps it could work as a fix for you.

    I'm always a little skeptical of using acids as clearing agents. I've seen Daivd Michael Kennedy pulling his hair out using HCl as a clearing agent. Acids are used as hardeners in silver fixers. The literally harden the gelatin on the surface of the print. Starches, gelatins and gum arabic are all used as sizing agents in modern papers. These compounds can harden when exposed to acids and trap you emulsion in the paper. This leads the printer to harsher methods of clearing.

    I recommend to my 'hard luck' cases a combination of potassium metabisulfite and sodium sulfite to clear the most stubborn prints. 20-50g of each per liter of water will clear a tattoo off the back of your hand! Not really, but almost!

    A funny anecdote, and then I'll leave you alone: My wife bought a very nice, and extremely expensive set of sheets for our bed. About six months after she bought them disaster struck.

    One afternnoon I hear a scream and whimper from the laundry room. I run in expecting to find her bleeding on the floor. Instead, she's holding her sheets in one hand, and a red sock in the other. She had left the sock in the washer from a previous load and had missed it when loading the whites. There were streaks of red on her sheets and she was nearly in tears.

    "I'll be right back, I'm going to work, you find grab the mop buck from the garage and wash it out!" I yelled, as I grabbed my car keys and ran out the door.

    I returned home with 250 g of pottasium metabisulfite, 250 g of EDTA and 250g of sodium sulfite. I filled the bucket with about 6 liters of hot water from the tap. I stirred in the contents of each container I procured from work. The sheets then soaked for about 2 hours, after which I dumped the whole contents of the bucket into the washing machine. I set it on HOT and punched start. "Just you watch, honey, you can clear the worst pigments out of a gum print with the stuff I brought home!"

    "Huh?" Was her reply.

    45 minutes later I was a hero. My wife lifted the sheets from the washer and gasped in amazement.

    "Wow! Not only did it completely remove that stain, but I've never seen these sheets come out SO WHITE!!" She said, with an incredible sigh of relief.

    I decided at that point that someday you'd see me hocking Sullivan's Super Miracle Laundry Cure on late night TV. Maybe when advertising rates get cheap enough?

    Thanks for reading.
     
  11. Lukas Werth

    Lukas Werth Member

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    Phil,

    very shortly: as I said in another thread, I would just about forget Arches Aquarelle for metal salt prints.

    The combination of Sodium Citrate and Arches Platine should be unproblematic. In about four minutes, the margin stain should have very nearly gone, then, after a short rinse in slightly acidified water, a citiric acid bath of a a few minutes should clear all. Agitation and developer volume are no reasons for concern in my experience.

    This precipitate is something I have not seen with Kallitypes, so let me make two suggestions:

    1) have you taken care the developer is acidic, as Sandy wrote?

    2) what sort of ferric oxalate do you use? Is it yellow or green? Do yoiu use any additives?
    FO for kallitypes i.m.e. should be yellow, with no EDTA or oxalic acid added.

    Did you perhaps acidify he paper prior to coating?
     
  12. doughowk

    doughowk Subscriber

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    I'm using 20% solution of Sodium Citrate as developer. I pour the developer over the print & image appears almost immediately (between prints, pour developer back in bottle). The developer is almost opaque black from ferrous iron. Sandy King says in article to replenish developer with about 20% fresh - decant from top leaving the ferrous iron on bottom to be discarded. He says that, unless replenished, difficult to clear. I've had trouble decanting - seems that the iron remains suspended instead of settling to bottom.

    Btw, I tried Selenium toning before fixing, and did not see any Selenium stain; and it did stop the shadow solarization.
     
  13. philldresser

    philldresser Subscriber

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    Lucas

    Developer (20% Sodium Citrate) was acidified with Citric Acid as recommended by Sandy. The Ferric Oxalate was purchased ready mixed (liquid) from B&S so I don't know the original powder colour. The liquid is yellow.

    I develop for 3 mins which sounds like it might not be enough (but will increase to see if this removed the problem). The dev liquid was very grey and murky after the 4 prints I made last night and was discarded. I will make up a larger batch over the weekend.

    The paper was not acidified. Sensitizer was applied directly onto the paper

    Thanks for the comments

    Phill
     
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  15. philldresser

    philldresser Subscriber

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    Doug

    Thanks for the comments. My dev also discoloured after 4 (5*4) prints(I only mixed up and used 300ml purely for the session).

    I will try dev'ing the image face down, using more dev in a bigger tray and see what happens.

    Cheers

    Phill
     
  16. sanking

    sanking Member

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    Arches Aquarelle is definitely not a good paper for metal salt processes so you should start by trying a new paper. The problem with Aquarelles is that is has a lot of buffering to make it alkaline and this intereferes with the formation of good shadow density and also contributes to the formation of iron stain.

    Time of development is not particulary important in kallitype, except for the fact that the print continues to clear in the developer. However, I normally not develop for more than two minutes, and then take the print directly to the first clearing bath. A rinse in alkaline water between the developer and the clearing bath could cause stain.

    Replensihment of the developer is absolutely necessary with kallitype. If you don't replenish your prints will stain. For most consistent results you might even consider using the sodium citrate fresh every time and then discarding it. You don't need a lot to develop a print, maybe about 500ml for a 16X20 print and if bought in volume sodium citrate is not very expensive. In any event, I expect to see the print come out of the developer about 95% clear. It is always a bad sign if after two or three minutes in the developer there is a lot of stain because it will be difficult or impossible to clear.

    The native color of kallitype and sodum citrate is not attractive, but that does not bother me because for permanence kallitypes should be toned, and when you tone them they take on an entirely different color, warm black with platinum and pallaidum toners, blue black with gold.

    Sandy
     
    Last edited by a moderator: Dec 28, 2006
  17. Jim Noel

    Jim Noel Member

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    since adopting Sandy's one tray method fro processing kallitypes, and other alt processes, my problems with stain have been essentially eliminated. The fresh developer for each print is a big help, and they come out of the first acidified water rinse almost clear.
     
  18. Gustavo_Castilla

    Gustavo_Castilla Member

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    My 2 Cents
    I am with Dana on this I do my fair share of Kallitypes and stain = Ferric not cleared I use one heavy spoon fool of ETA per gallon and It seems to work for me for the record I use 10grms of silver for 250 ml water
     
  19. philldresser

    philldresser Subscriber

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    Sandy
    The latest batch was with Arches Platine and I am still getting the stain. The stain occurred only on the second developed image onwards so I am convinced that its due to the 'dirty' developer. I will make a larger batch and use it as a one shot and see if this makes a difference. I have both PT and PD toner chemicals (Thanks Dana :smile:) but have yet to use them as I want to get the pre-toned images correct first.

    One of the points I made earlier has not had any comments on yet is the fact that I lost about 1.5 stops (and I am getting a 5.5 stop final density range) of contrast using Sodium Citrate compared to Borax. They look like I have printed on the equivalent of a grade 4.5 silver paper . Is this a known attribute of Sodium Citrate?

    Jim
    I will try the one tray method and one shot chems this weekend.

    Gus
    I dont have EDTA at the moment so I will have to try other things first. There are a lot of variables to play with :sad:

    Phill
     
  20. Lukas Werth

    Lukas Werth Member

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    Phil,

    I admit I find this difficult to fathom. Did I understand you correctly that you used Arches Platine insterad of Aquarelle the second time?

    A yellow FO solution is what you want for kallitypes. I don't really think this is the reason, but you might test your FE by placing a drop of it in a ca. 1% potassiumhexacyanoferride (ferri) solution: if the drop turns blue, the FO is bad (containing ferrous oxalate).

    I have little to add to Sandy's contribution, as I am among those inspired by his excellent article on kallitypes at the unblinking eye. Just a word on developer: of course you don't want an opaque fluid with all the sludge swishing around. But I find it very easy to give the developer a rest overnight, and decant it again and again, just restocking side-by-side, and once in a while control the acidity.

    About EDTA: I presume Gustavo advises it to be added to the developer. Now I recently read in Mike Ware's book on chrysotypes that EDTA tetrasodium is alkaline and should therefore not be used in the first bath! (Neither, for Kallitypes, would I use it in the FO as for platinum.) One might try disodium EDTA, but I don't think it is necessary for kallitypes.
     
  21. Lukas Werth

    Lukas Werth Member

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    Sorry for this; I posted my comment before being able to read your last contribution. Maybe your problems are really due to overused developer. But checking the FO also will do no harm.
     
  22. sanking

    sanking Member

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    Do you mean that you lost 1.5 stops of printing speed or 1.5 stops of tonal range? If the former, I have never compared the printing speed of borax with sodium citrate. However, I have found that sodium citrate gives about the same printing speed as potassium oxalate and ammmonium citrate. I prefer sodium citrate because it is not as toxic as oxalate and is much less expensive.

    The tonal range I get with sodium citrate, with about 2ml of a 5% solution of potassium dichromate added per liter of developer, is about log 1.85, which of course is just slightly more than 6 stops.

    BTW, I have assumed that you were adding some dichromate to the developer. If you do not, it is almost impossible to completely clear the print.

    Sandy King
     
  23. philldresser

    philldresser Subscriber

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    Sandy

    I have not added any dichromate to the developer, seems like this maybe the problem.

    Phill
     
  24. philldresser

    philldresser Subscriber

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    Sandy

    I lose about 1.5 stops of tonal range. Print speed is about the same.

    Phill
     
  25. sanking

    sanking Member

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    How are you determining that you lost 1.5 stops of tonal range? Are you using a step wedge? If so, from where to where on the print scale are you counting? Just so we are on the same page, for in-camera negatives I count from about 90% of maximum black to paper white. For in-camera negatives, from maximum black to paper white.

    Sandy
     
  26. philldresser

    philldresser Subscriber

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    I have printed the same negative twice, both with step wedge and used different developers as discussed. The Borax print shows an increased tonal range compared to the Sodium Citrate developer between 1 and 1.5 stops. The range is measured (by eye) from first discernable non black to last discernable tone before white. This is 11 steps (3B - 14W) for sodium citrate and 13/14 steps for Borax/Rochelle (3B - 16/17W). The only other difference was dev temperature where the Borax solution was around 40C. Sodium Citrate was between 18-20C.

    Here is one of the 5x4 pics deved on Wed in Sodium Citrate showing the rich chocolate colour entitled ' Unfolding'. This is the image with no staining. The Tonal range on the original goes to step 14, scan does not reflect this as I haven't mastered scanning yet :sad:

    [​IMG]