Pyrocat HD & HP5 undeveloped white spots on negative

Tony Egan · Apr 24, 2018

Hi - looking for advice on cause of these white spots of no development on HP5 negatives in Pyrocat HD. (i.e. black spots on print) I have previously developed from same batch of HP5 film in XTol with no issues.
Development steps:
- No pre-wash
- 2+2+100 dilution in highquality mains water
- 10 minutes on continuous agitation roller at 22-23 degrees C
- water rinse stop bath
- 4 minutes in Ilford Hypam rapid fixer
- 15 minute wash

The attached photos are scans of adjacent negatives. Interestingly, the shape is circular on one negative and more oval shaped on the other. Appreciate your insights as to most likely cause and recommended adjustments to development steps - otherwise the Pyrocat HD goes down the drain and I return to trusty old XTol! Thanks.

John Wiegerink · Apr 24, 2018

Tony Egan said:
Hi - looking for advice on cause of these white spots of no development on HP5 negatives in Pyrocat HD. (i.e. black spots on print) I have previously developed from same batch of HP5 film in XTol with no issues.
Development steps:
- No pre-wash
- 2+2+100 dilution in highquality mains water
- 10 minutes on continuous agitation roller at 22-23 degrees C
- water rinse stop bath
- 4 minutes in Ilford Hypam rapid fixer
- 15 minute wash

The attached photos are scans of adjacent negatives. Interestingly, the shape is circular on one negative and more oval shaped on the other. Appreciate your insights as to most likely cause and recommended adjustments to development steps - otherwise the Pyrocat HD goes down the drain and I return to trusty old XTol! Thanks.
View attachment 199546 View attachment 199547

They look awful small to be air-bells, but don't rule that out. I wouldn't think you could get air-bells with rotary processing, but I don't rotary process. Maybe your fixer and Pryocat don't like each other. I only use my own homemade Alkali fixer and not a rapid acid base fixer with my pyro-developers as has been suggested many times. Other than that I can't guess why you have this. I have never had a problem like this with the three variations of Pyrocat that I have used. JohnW

Alan9940 · Apr 24, 2018

I have processed many rolls and sheets of various films on my Jobo with both Pyrocat-HD and -MC for many years and have never seen this issue. I have used both a water rinse and a very dilute acid stop for the stop bath. Fixer has been one of TF-5, homemade rapid fix, or homemade F-24 style fixer. I have, also, used the 2:2:100 dilution when developing for pt/pd prints. I do use a water pre-rinse, but I can't imagine that step would have any affect on your results.

The only things I can think of is some contamination of the drum used to process the film or, as John suggests, the Pyrocat doesn't play well with the Hypam Fixer. But, IMO, the fixer idea is a real long shot.

You might want to contact Sandy King (the creator of Pyrocat) and see if he has any suggestions.

John Wiegerink · Apr 24, 2018

Alan9940 said:
I have processed many rolls and sheets of various films on my Jobo with both Pyrocat-HD and -MC for many years and have never seen this issue. I have used both a water rinse and a very dilute acid stop for the stop bath. Fixer has been one of TF-5, homemade rapid fix, or homemade F-24 style fixer. I have, also, used the 2:2:100 dilution when developing for pt/pd prints. I do use a water pre-rinse, but I can't imagine that step would have any affect on your results.

The only things I can think of is some contamination of the drum used to process the film or, as John suggests, the Pyrocat doesn't play well with the Hypam Fixer. But, IMO, the fixer idea is a real long shot.

You might want to contact Sandy King (the creator of Pyrocat) and see if he has any suggestions.

Allen,
I agree with you on the fixer being a long shot, but in this case long shots are about all we have. The thing that strikes me it the uniformity of the white spots. From the picture they look almost perfectly round. I my experience with contaminates (yes I've had them) the imprint they leave is "usually" all different sizes and shapes. I have seen stop bath/fixer pinholes look like that, but stop bath isn't used. So, yes it's a long shot for just about anything. JohnW

Peter Schrager · Apr 24, 2018

Tony I can't answer your question but I sometimes make 2 negatives one in pyro for alt process and one in xtol for silver..the pyro ones has a tendency to scratch while xtol nearly never..dont ask me why...if you are doing straight for alt process undiluted good old D76 works,very well...i have times if you need them

Peter Schrager · Apr 24, 2018

And I never use drums..only tray..

Ian Grant · Apr 24, 2018

It's unlikely to be the developer. I've processed many hundred sheets of HP5 in Pyrocat HD over the past 12+ years along with other films and fixed in Hypam or Ilford Rapid fixer.

I've seen this when minute particles of insoluble Iron salts in the water lodges on the emulsion, it forms a bleach during fixing.

Ian

Raghu Kuvempunagar · Apr 24, 2018

Recently I faced a similar but more severe case of white spots in the negatives (Orwo UN54). Some interesting possible causes were suggested: https://www.photrio.com/forum/threads/how-to-get-rid-of-spots-on-the-negatives.159211/

Andrew O'Neill · Apr 24, 2018

Try developing with stock A and B in distilled water, if you've been using tap water....

RauschenOderKorn · Apr 24, 2018

Is the entire film affected or only the two frames you are showing us?
The scans look extremely enlarged, what is the real size of the problem? Can you show us a few complete frames?

Just asking, because: I have had one case of an Ilford manufactured film (rollei rpx400 120) , which was identified by a competent authority to have a manufacturing defect showing as one small oval shaped white spot in the middle of the negative.

Alan9940 · Apr 24, 2018

Peter Schrager said:
Tony I can't answer your question but I sometimes make 2 negatives one in pyro for alt process and one in xtol for silver..the pyro ones has a tendency to scratch while xtol nearly never.

Wow, this surprises me because pyro developers harden the emulsion during development.

Tony Egan · Apr 24, 2018

Thanks for responses so far. I should have added this was HP5 120 roll film. Three rolls in the same tank. All negatives were affected. Of course it's on the clear blue sky where it is most irritating when things like this happen. Additional images added of full negative and positive views. The sky also has a mottled look to it which is also evident on the the highly magnified images and some bands of uneven development. I am generally quite careful with cleanliness and process in my darkroom. I will try another roll with the following changes.
- pre-wash
- distilled water
- fresh fixer
Any thoughts on continuous agitation versus regular inversion in tanks?

I really like the look of pyro negatives and how they print so hoping my lack of success to date with various versions of pyro can be overcome. Cheers.

.

Peter Schrager · Apr 24, 2018

Hand roll it...i gave up rollers 10 years ago and never miss them......and I've done hundreds of rolls of 120 and a few thousand large format negatives..both pyro and xtol
.theres no discussion when it comes to results...would you rather get spot on development every time so you can do photography or scratch your head when something unpleasant pops up??

RauschenOderKorn · Apr 25, 2018

That rules out a film defect ...

mnemosyne · Apr 25, 2018

I have no idea about the cause of the black (positive) oval/round artefacts, but the heavy mottling in the sky area (with spots in the positive) looks like some kind of interaction between backing paper and emulsion, possibly triggered by humidty/condensation and film beyond its expiry date. We had samples of this type of problem with 120 Ilford film before, including myself with a roll of FP4+ developed in Xtol or just recently:
https://www.photrio.com/forum/threads/would-moisture-on-a-film-do-this.158444/

Tony Egan · Apr 25, 2018

Round 2 Failure!

I tried another single roll of HP5 from the same batch as follows:
- no pre-wash
- 2+2+100 at 22-23 degrees C in distilled water
- continuous roller agitation for 10 mins in a different tank
- fix for 4 mins in freshly mixed first time use alkali fixer mixed in distilled water

If anything the spotting seems to be marginally worse on this roll. The only variable left seems to be to add a pre-wash or try intermittent agitation but I highly doubt this will be the solution. Pyro and I just don't seem to get along!

Tony Egan · Apr 25, 2018

mnemosyne said:
I have no idea about the cause of the black (positive) oval/round artefacts, but the heavy mottling in the sky area (with spots in the positive) looks like some kind of interaction between backing paper and emulsion, possibly triggered by humidty/condensation and film beyond its expiry date. We had samples of this type of problem with 120 Ilford film before, including myself with a roll of FP4+ developed in Xtol or just recently:
https://www.photrio.com/forum/threads/would-moisture-on-a-film-do-this.158444/

Hi - I developed three rolls from the same batch in XTol a few days before with perfectly smooth skies. Film expiry is 2020. All film subject to same loading and travelling conditions in three different Hasselblad backs.

mnemosyne · Apr 25, 2018

Tony Egan said:
Hi - I developed three rolls from the same batch in XTol a few days before with perfectly smooth skies. Film expiry is 2020. All film subject to same loading and travelling conditions in three different Hasselblad backs.

Film was stored in a refrigerator at any point between exposure and development?

RauschenOderKorn · Apr 25, 2018

This has been discussed before, by the way:

https://www.photrio.com/forum/threads/problem-with-pyrocat-hd.32124/

Tony Egan · Apr 25, 2018

RauschenOderKorn said:
This has been discussed before, by the way:

https://www.photrio.com/forum/threads/problem-with-pyrocat-hd.32124/

Thanks. I did a search before posting. Lots of discussion and multiple hypotheses but no definitive diagnosis that I could find.

Tony Egan · Apr 25, 2018

mnemosyne said:
Film was stored in a refrigerator at any point between exposure and development?

Hi, no, stored at room temperature in a cupboard in my study.

Ian Grant · Apr 25, 2018

There's something weird going on here, are you mixing the Pryrocat yourself or buying it pre-mixed. Each emulsion pin-hole and that's what I think they are has a higher density around it. That could indicate CO2 released when placed in an acid stop bath or fixer, but can't be explained when water stop is used and an alkali fixer.

I've found HP5 in Pyrocat HD is a superb combination, I think you need fresh Pyrocat.

Ian

Raghu Kuvempunagar · Apr 26, 2018

Before switching to fresh Pyrocat HD, you might want to develop a test roll of any film other than HP5+ with your current stock of Pyrocat HD and find out if you face the same problem.

Tony Egan · Apr 26, 2018

Ian Grant said:
There's something weird going on here, are you mixing the Pryrocat yourself or buying it pre-mixed. Each emulsion pin-hole and that's what I think they are has a higher density around it. That could indicate CO2 released when placed in an acid stop bath or fixer, but can't be explained when water stop is used and an alkali fixer.

I've found HP5 in Pyrocat HD is a superb combination, I think you need fresh Pyrocat.

Ian

Hi Ian - the Pyrocat was mixed from a 10l dry pack. I used distilled water at the recommended temperature and stored A & B in two new small brown bottles. There are no particulates I can see floating around in either bottle - clear and clean. Solutions were mixed about 2 months ago. Perhaps I will try a test roll again with a new batch of liquid concentrate and a new supply of HP5 120 before throwing in the towel!.

Thanks for your interest in my chemical mystery!

Tony Egan · Apr 26, 2018

Raghu Kuvempunagar said:
Before switching to fresh Pyrocat HD, you might want to develop a test roll of any film other than HP5+ with your current stock of Pyrocat HD and find out if you face the same problem.

Yes, perhaps a roll of TMY so I can also admire the Kodak branding and frame numbers as well! Unfortunately all that film hit the trash can after some serious mishaps with the notorious backing paper problems. Never again. It's hard being analog some days....

Pyrocat HD & HP5 undeveloped white spots on negative

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