problem with Palladium toner in Kallitype

good morning! today I did the first palladium toning and it gave me a problem, that is, it stained my paper as you can see in the photo I am attaching. What could it be? it is normal? the print has no significant highlights, but it gives me the idea that it stains them anyway. The toner is new at 17% and has a turbid gray color. I kept the printing toner about 7 minutes. The print was developed in Ammonium citrate / sodium Acetate for 10 minutes after that 4 min. clearing baths with 3% citric acid in distilled water, another minute in tap water and fixed in alkaline TF3, washing 20/30 min. The paper is the Bergger cot320. Anyone have any idea what may have happened? Thanks in advance!

anyone have any idea? maybe because Palladium toner maybe because the toner has to be done before fixing?
thank you!

Is this back of the paper or the front?

nmp said:

Is this back of the paper or the front?

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Back. I attached the front
It seams to me toned enough well, it only has yellowed highlights cause the paper is yellowed. Don’t see stained in front

stefano_ber said:

Back. I attached the front
It seams to me toned enough well, it only has yellowed highlights cause the paper is yellowed. Don’t see stained in front

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Sometimes in salt prints I saw similar things when the sensitizer (AgNO3) seeped in too far into the bulk of the paper which became difficult to wash/fix out turning into stains in the back of the paper later either with ambient exposure or with toning. In your case, those stains might have been there before toning which only made them more visible. It's a possibility.

nmp said:

Sometimes in salt prints I saw similar things when the sensitizer (AgNO3) seeped in too far into the bulk of the paper which became difficult to wash/fix out turning into stains in the back of the paper later either with ambient exposure or with toning. In your case, those stains might have been there before toning which only made them more visible. It's a possibility.

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so for you it is the fault of too weak clarification? can't it also be because the toning was done after fixing?

stefano_ber said:

so for you it is the fault of too weak clarification? can't it also be because the toning was done after fixing?

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If this is what is happening (it is still a conjecture on my part at this point,) what you want is make sure that your sensitizer is not getting absorbed too far in the paper. Once that happens, it gets very difficult to wash it out Check your paper after coating/drying and see if there is any sensitizer visible in the back, may be against light. In my case I think I was just using too much sensitizer, so I backed off a bit and the stains disappeared.

nmp said:

If this is what is happening (it is still a conjecture on my part at this point,) what you want is make sure that your sensitizer is not getting absorbed too far in the paper. Once that happens, it gets very difficult to wash it out Check your paper after coating/drying and see if there is any sensitizer visible in the back, may be against light. In my case I think I was just using too much sensitizer, so I backed off a bit and the stains disappeared.

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it might as well be that, but in theory that should be removed from a good clarification. If I put less of it I risk spreading it irregularly. Generally for an 8x10 I put 25 + 25 drops which corresponds with my dropper to about 2 / 2,5ml. In your opinion can be the toner done after fixing?

stefano_ber said:

it might as well be that, but in theory that should be removed from a good clarification. If I put less of it I risk spreading it irregularly. Generally for an 8x10 I put 25 + 25 drops which corresponds with my dropper to about 2 / 2,5ml. In your opinion can be the toner done after fixing?

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In theory, you can tone with palladium both before and after fixing. One of the reasons it is recommended before is to minimize any density loss that might occur during fixing. After fixing it should not hurt the image per se. Unless there was any left over ferrous oxalate for some reason that didn't get to react to silver nitrate which will then reduce the palladium salt to palladium metal. Of course, if that was the case, the problem will occur even in toning before fixing.

By the way, if there was free silver nitrate you would get stains during fixing as well - it is the basis for residual hypo test.

:Niranjan

thanks Niranjan!
that was what I believed too. But after this test I had doubts about the before and after. These stains come out only during the toning. As I may have already written, the clarification is obtained with 4 minutes of distilled water and 3% citric acid, then a minute of tap washing. I don't use EDTA because I use Sodium Citrate or Sodium Acetate as a developer. In this case I used Sodium acetate / Ammonium Citrate and if I'm not mistaken with these developers EDTA is not needed. When I used it I got heavy fading (I had also written a post a couple of week ago). However, I believe this problem, it seems more a chemical reaction between toner and residual iron or the toner is not good!

Stefano:

You can check if the toner is not good by treating a piece of the bare paper and see if there is any staining. If you had suspended metal in it, it would presumably settle in the paper and be a source of stains. Are you reusing the toner, by the way, or using it as one shot?

:Niranjan.

nmp said:

Stefano:

You can check if the toner is not good by treating a piece of the bare paper and see if there is any staining. If you had suspended metal in it, it would presumably settle in the paper and be a source of stains. Are you reusing the toner, by the way, or using it as one shot?

:Niranjan.

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Hi Niranjan!
I did the test you suggested for 7 minutes and dried the piece of paper. As you can see from the attached photos, anyway the toner stains the paper and makes it yellow.
There are no red stains typical of iron and it is much less stained but still releases stains. I noticed that in the first couple of minutes the paper still looked clean, then it began to absorb well. Is this the color of the toner? dense gray...
does he behave this way to you too?
Thanks again!

stefano_ber said:

Hi Niranjan!
I did the test you suggested for 7 minutes and dried the piece of paper. As you can see from the attached photos, anyway the toner stains the paper and makes it yellow.
There are no red stains typical of iron and it is much less stained but still releases stains. I noticed that in the first couple of minutes the paper still looked clean, then it began to absorb well. Is this the color of the toner? dense gray...
does he behave this way to you too?
Thanks again!

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That does look bad. I do not have a lot of experience with palladium toning....just played around a little bit with some salt print test strips. I was making my own toner from the palladium solution used in palladium printing. I don't remember seeing it gray like in your picture and there was no staining in the back of the paper like you are seeing. If this is a new toner that you bought, you might want to check with your supplier. I was using it only once (in a very dilute form.). Is that what you are doing or are you reusing it several times?

May be someone with more experience will chime in...

:Niranjan.

Have you tried toning before fixing?

Andrew O'Neill said:

Have you tried toning before fixing?

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no, but it also stained with just the blank paper. But in the end it was the toner that was incorrect! sent back to the reseller.

Your palladium toner should never be gray like this ! It should be yellowish.

I'm reviving this thread because I have a question about this palladium toner that -in my case- actually dyes the paper (just like if I was using a tea toner)

As you see in this picture :
- on the left side, the unprocessed Bergger COT 320 paper color
- on the right side, the paper strip processed for kallitype (with Pd toner)



My workflow is as follows (I use Sandy King's workflow):

- Bergger COT 320 paper
- coating with 20% ferric oxalate + 10% silver nitrate sensitizer
- drying time : 4 hours
- exposure
- developer : Sodium acetate 20%, 10 minutes
- clearing agent: citric acid 3%, 2 baths of 5 minutes
- toning 5 minutes in :
- 5g citric acid
- 5ml Sodium tetrachloropalladate (aka sodium chloropalladite) 20%
- in 1L of water
- then fixing
- then Hypo clearing
- eventually final wash for 30 minutes

With this process, the paper takes on a yellowish tint, which I don't have with the platinum toner at all...

What I observed is that :
- toning in palladium was very fast (in about 15 seconds the image was fully toned)
- the palladium toner solution had a yellowish tint
- although toning was done in 15 seconds, I left the paper for 5 minutes in the toner bath...

On the other hand:
- toning in platinum was much slower (3 minutes needed at least)
- the platinum toner solution was almost clear, very very slightly yellowish
- I use a Platinum Toner for Kallitype I bought from Moersch Photochemie, the recommendation is to dilute it in a 1+20 proportion. This is potassium tetrachloroplatinate for sure, but I don't know the concentration...

So I suspect a palladium toner solution that was way too strong (although I followed Sandy King's recommendations ...?) and the fact that I left the print too long in the toner bath to be the causes for the base paper being dyed with a yellowish tint...

What are your thoughts ?

Thank you in advance for your help !

largo said:

So I suspect a palladium toner solution that was way too strong (although I followed Sandy King's recommendations ...?) and the fact that I left the print too long in the toner bath to be the causes for the base paper being dyed with a yellowish tint...

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If that was the case should it not come out in the wash? As far as we can discern, there should be no permanent physio-chemical interaction between COT 320 and palladium salt - otherwise wouldn't we end up with the same problem in the conventional palladium printing where the paper comes in contact with much greater concentration of Pd salt?

What happens if you take the bare paper, skip the sensitizer/exposure steps and do the rest from developer onward. Or even just treat a small piece of paper for 5 minutes in Pd toner followed by the usual washing?

Finally I wonder if the step between citric acid and toning requires more thorough washing - in case some of the CA-chelated Fe(2)'s are still sticking around in the paper that can cause Pd metal precipitation.

More questions than answers, I know....

:Niranjan.