Malde/Ware crystal formation in Palladium print

Dear Platinum/Palladium Printers,

I have the following issues with my prints:

1. All prints show tiny crystal-like shapes all over the print.
2. The blacks are fibrous and rather dark-brownish.
3. The negative base can’t be “printed through” regardless of the exposure time.

The prints where made under the following conditions:

• Method: Malde/Ware Print-out FE1/Pd 1:1
• Negative used: Delta 100 8x10 developed in Tanol Speed (Staining developer by Wolfgang Moersch)
• Coated area: 8x10 inch
• Sensitizer volume: 1.5ml
• Tried the following additives each 0.05ml
  • Tween 20 15% v/v
  • Glycerin 15% v/v
  • Tween 20 & Glycerin
• Ambient Condition: 35% RH at 20° C
• Tried these three different Pre-coat Hydration methods:
  • Humidity Chamber at 52% RH for one Hour
  • Hanged in a cabinet for 10 minutes over a tray of boiled water
  • Hanged in a cabinet for 60 minutes at 40% RH
• Tested Papers: Arches Platine on both sides and Hahnemuehle Platinum Rag on both sides
• Coating Method: Glass Rod in 4-6 passes
• Ambient drying time: 5min
• Post coating humidification: Humidity Chamber at 52% RH for 60min - 120min
• Exposure time around 40 minutes with 16 UV LED Banks (30cm length, spaced out 5mm, distribution angle 120°, 15cm distance to print surface) 9W each with a wavelength of 390nm-400nm

Since the three issues show up regardless of additive added to the sensitizer, humidification times and paper brand I assume the issue must be related to the way I prepared the chemicals. When I made the palladium solution, I added 30% of the ammonium chloride to the palladium chloride after I had mixed the palladium chloride already with 70% of the ammonium chloride because of a calculation mistake. Also, the sensitizer (Palladium solution mixed with FE1) shows tiny crystals in the bottle that I have to dissolve before every use despite a constant ambient temperature of around 20°C.

Question: Is this batch of Palladium Solution lost because of my mistake in the sequence of mixing the solution or did I oversee a potential mistake in coating the paper that would explain my three issues above?

Any advice would be greatly appreciated!
Maximilian

Disclaimer: I am not a Malde/Ware practitioner.

It might help if you can show some pictures of the defects.

In any case, I would doubt that your addition of ammonium chloride in 2 portions would have any effect on the final solution.

Are you filtering your solutions? In the instructions I saw, they all recommend filtration before storage and use, particularly the FAO. So I am thinking there could be a known issue with un-dissolvables. Even if you think you are dissolving the crystals before use some might still be left behind that you may not be able to identify visually.

Welcome to Photrio, by the way.

:Niranjan.

Hi Niranjan, thank you for taking the time! I uploaded an image of the print border with a piece of black cardboard on the left side to compare the rendering of the blacks. If you zoom in you should be able to see the tiny white spots allover the print border.

I have filtered both the Palladium and Ferric Oxalate solution through a Whatman grade 1 filter before combining the two as a sensitizer. I will try re-filtering this sensitizer before I use it next time.

Maximilian

Maximilian0322 said:

Hi Niranjan, thank you for taking the time! I uploaded an image of the print border with a piece of black cardboard on the left side to compare the rendering of the blacks. If you zoom in you should be able to see the tiny white spots allover the print border.

I have filtered both the Palladium and Ferric Oxalate solution through a Whatman grade 1 filter before combining the two as a sensitizer. I will try re-filtering this sensitizer before I use it next time.

Maximilian

View attachment 301356

Click to expand...

hmm....most what I see by way of defects is the paper texture which is fairly comparable to that on the cardboard. I am guessing the image is already magnified some, considering the papers you are using are quite smooth. If there were substantial crystalline defects they should be evident at 1X, I would think. May be I am overlooking something - please correct me if I am wrong.

Secondly, isn't a black cardboard a rather high bar to achieve in terms of Dmax? Actually it does not look too bad at all on the print from my perspective, particularly in the bottom zone. Not sure some density loss as you go up along the border is coating uniformity problem (end of the stroke?) or simply an artifact of the image-capture (as the cardboard shows a similar pattern.) Regarding the way to improve upon what you have, I noticed you are only using 52% RH in post-coating humidification which is on the low side of what is recommended by Malde/Ware. Perhaps using a saturated NaCl chamber at 76% RH will help - both with Dmax and the printing speed.

:Niranjan.

Hi Niraanja,

I have re-filtered the Palladium Ferric Oxalate sensitizer and caught a substantial amount of particles in the filter (See image below). However, the re-filtered solution produces a somewhat weaker image and had no influence in cleaning out crystals. Just ordered a bottle of pre-made Ammoniumtetrachloropalladate solution and hoping it will solve the crystal and Dmax problem.

Sorry for the bad image quality, don't have a decent digital camera or scanner. The grainy crystals are pretty evident in mid and low values on the print in glancing light. The black cardboard I used for comparison is super washed out and definitely reflects far more light than the blacks I have seen on decent Platinum/Palladium prints. Increasing the RH might be interesting to test though! Will do that if the new Palladium solution produces similarly inferior results.

Maximilian

Hi, Maximilian:

That does look like you have some insoluble crystalline material in your sensitizer. I guess the filtering results in loss of expensive material as well - given how absorbent those Whatman filters can be. Not something one would want to have to do routinely.

Once this filtered solution that presumably has no crystals is coated, somehow they are formed again on the paper. Actually that is itself is not unusual - as all sensitizers when they are dried form particles, but they are usually small enough to escape notice. If I remember correctly my crystallization kinetics from way back, slower drying should result in bigger crystals than faster drying. Is there something that can be done in how you are drying the paper after coating that might affect the results?

I wonder why Malde/Ware process calls for such a high solids content in the sensitizer - seems 60% FAO is close to its saturation point- may be to maximize the Dmax, don't know. But that is also asking for trouble as there would be greater propensity for precipitates with small variations in temperature and weights/volumes. In any case, it seems you are making a combined sensitizer by mixing all of the the FAO and palladium together and store. Perhaps a better way might be to not do that and only mix drops of the two when you are ready to coat. One, you are not messing up the whole quantity of palladium in case something goes wrong. Two, by coating the mixture right away, perhaps there is not enough time to form crystals in the solution itself. I don't know, but that might be the safer thing to do before the root cause of the problem can be figured out.

Just as a philosophical aside: why would one prefer this process over the conventional tried-and-true developed-out process that is far more straight forward. This seems to me a bit too complicated with all its preparations and various conditions that need to be controlled just to eliminate the necessity of a developer.

In any case, good luck....

:Niranjan.