Pinholes with 35mm HP5 from Pyrocat-HD?

[sanking]

I did further search and found the following thread on the Ilford forum.

http://www.ilford.com/html/us_english/ILFOPRO/forum/topic.asp?TOPIC_ID=5634

As you can see from the thread it appears that some people are also having a problem with pinholes with other developers, including Ilfosol S and PMK.

I was especially intererested in the comment at the end of the thread the problem might also be caused by taking the film from an alkaline condition, say developer or stop bath, into an acidic stop bath with an insufficient stop bath that that has not removed all of the developer. This is something I had not thought of, but it makes a lot of sense.

If the problem is indeed pinholes it is most likely caused by abrupt transition from acid to alkaline state so to be on the safe side one should probably process with all of the solutions alkaline if this kind of problem pops up. However, I have never had the problem and I use an acetic stop bath of about 1/2 normal strength.

Sandy

 

[erikg]

Brad, I agree with Lee, your problem sounds like "air bells." Pyrocat is my developer of choice for most applications. I aways use a water presoak with pyrocat and gentle torus inversion agitation (with a small tank) (or continuous rotational agitation - with BTZS type Tubes). I never see the problems you described.

If only it were so easy All of the HP-5 that I have processed to date was done with a presoak. Brad's film too, I believe. He didn't use a presoak in the current test in order to eliminate one variable. I also use the torus inversion agitation as well.

That does give me the thought that if agitation were at play (although mine is about as normal as anybody's) then stand or semi-stand agitation might show an effect--or lack of defect as the case may be.

Having said that, I think Sandy may on to something with the pinhole theory. For one thing, these specks have sharp edges, and air bells that I have seen have been both bigger, and have had softer edges.

I have test film that I will run tonight. Any suggestions as to what I should try? Acid stop bath-- no stop bath? semi-stand?

Solving this would be worth the effort, I think. I agree with Brad's comments about the developer, It has been great for me these last two years, and I would love to have it work in all formats. If anything, I'll switch films.
Thanks to all for their insights.

 

[sanking]

Having said that, I think Sandy may on to something with the pinhole theory. For one thing, these specks have sharp edges, and air bells that I have seen have been both bigger, and have had softer edges.

I have test film that I will run tonight. Any suggestions as to what I should try? Acid stop bath-- no stop bath? semi-stand?

.

Here is what I would suggest for the Ilford films. I am going to suggest eliminating the pre-soak since Ilford recommends this for their films anyway.

So, follow one of two patterns.

Either this,

1. Film directly into eveloper
2. weak acid stop bath, say at about 1/2 normal strength.
3. fix in base or acidic fixer

Or this

1. film directly into developer
2. water stop bath, at least one minute and minimum of five complete changes of water.
3. Fix in alkaline fixer

Either sequence should eliminate the abrupt transfer from base to alkaline or alkaline to base state that could cause the pin holes.


Sandy King

 

[gainer]

Perhaps I am crazy. Some others have implied as much. I do not, or very seldom do, use any kind of stop bath. I dump the developer out and dump in the fixer. Also no presoak. I have also, in order to make the developing time a little more consistent (I tkink), poured out enough developer to make room for 1 oz (30 ml) of TF4 concentrate per 16 oz. I have not seen any pinholes or other artifacts. I have used many different films with many different developers. The early TMax 100 gave me airbells that were quite good sized. I cured that with a tiny bit of wetting agent in the developer.

 

[don sigl]

Perhaps I am crazy. Some others have implied as much. I do not, or very seldom do, use any kind of stop bath. I dump the developer out and dump in the fixer. Also no presoak. I have also, in order to make the developing time a little more consistent (I tkink), poured out enough developer to make room for 1 oz (30 ml) of TF4 concentrate per 16 oz. I have not seen any pinholes or other artifacts. I have used many different films with many different developers. The early TMax 100 gave me airbells that were quite good sized. I cured that with a tiny bit of wetting agent in the developer.

Interesting procedure. I would have thought that contaminating the fixer with developer would have created chemical fogging.

 

[erikg]

Here is what I would suggest for the Ilford films. I am going to suggest eliminating the pre-soak since Ilford recommends this for their films anyway.

So, follow one of two patterns.

Either this,

1. Film directly into eveloper
2. weak acid stop bath, say at about 1/2 normal strength.
3. fix in base or acidic fixer

Or this

1. film directly into developer
2. water stop bath, at least one minute and minimum of five complete changes of water.
3. Fix in alkaline fixer

Either sequence should eliminate the abrupt transfer from base to alkaline or alkaline to base state that could cause the pin holes.


Sandy King

I just ran a test following Sandy's first option, using the half strength stop bath. I see several of these defects, almost one every frame. They are very small, and some are like doughnuts, a sharp clear ring around a speck of density. The other half of the roll I ran in Sprint Standard. That film shows none of these things.

I may try two things, as it seems that basically Brad has followed Sandy's second option, I will test the slow introduction idea that was presented in the link to the other forum that Sandy cited, and, seperately, perhaps I will add a hardener to either the stop bath or fixer.

 

[Brad Dow]

Here is what I would suggest for the Ilford films. I am going to suggest eliminating the pre-soak since Ilford recommends this for their films anyway.

So, follow one of two patterns.

Either this,

1. Film directly into eveloper
2. weak acid stop bath, say at about 1/2 normal strength.
3. fix in base or acidic fixer

Or this

1. film directly into developer
2. water stop bath, at least one minute and minimum of five complete changes of water.
3. Fix in alkaline fixer

Either sequence should eliminate the abrupt transfer from base to alkaline or alkaline to base state that could cause the pin holes.


Sandy King

My test run followed the second sequence exactly (no pre-soak, water stop, alkaline fixer), and the results were 93 spots visible with a 10x loupe on a light table per 15 frames of 35mm. I'm convinced the problem with my negatives is not pin holes due to pH shock. The blemishes I'm seeing are clearly due to very, very tiny bubbles adhering to the emulsion, capturing enough developer to darken the center, but excluding developer at the intersection of bubble and emulsion, producing a clear surrounding rim quite regular in shape. These appear in print as black spots the size of a pin point.

I checked in with the friend whose recommnedation prompted me to try Pyrocat. He reports that when he first began working with Pyrocat, he had the very same problem, but the problem vanished when he extended his pre-soak to 5 minutes and omitted the 5th roll in a 5-roll Kinderman tank. His typical films were Tri-X 400 and FP4 (although my roll of Tri-X in Pyrocat was clean.) I plan to repeat my test with the extended pre-soak. I'll let you know how it goes.

Brad

 

[erikg]

Yes, interesting. I think you are right, it is happening during development, that is why they have the donut shape. However, not to dampen all hope, but my normal presoak is 5 minutes. I have never seen quite so many spots as you report, but one per roll is too many, I have enough reasons to loose confidence!

 

[sanking]

Yes, interesting. I think you are right, it is happening during development, that is why they have the donut shape. However, not to dampen all hope, but my normal presoak is 5 minutes. I have never seen quite so many spots as you report, but one per roll is too many, I have enough reasons to loose confidence!

I wonder if you and Brad would be willing to send me a few samples of the exposed and developed negatives, and perhaps a roll or two of the HP5+ film. I would be very much interested in testing this in my environment to see if the phenomenon repeats itself here. Contact me by email if interested.

Sandy King

 

[Brad Dow]

Yes, interesting. I think you are right, it is happening during development, that is why they have the donut shape. However, not to dampen all hope, but my normal presoak is 5 minutes. I have never seen quite so many spots as you report, but one per roll is too many, I have enough reasons to loose confidence!

That does dampen my hopes a bit.

I have a test roll washing now. I won't give up hope until I see the result later tonight, but even if the results are not perfectly clean (and I do agree that one spot on a roll is too much, because it will invariably occur on the very frame you care about), switching to another film may be the answer. I mentioned before, but it's worth repeating, my test rolls of TMY and Tri-X 400 were completely free of spots. Perhaps something in the Ilford manufacturing process makes HP5 it especially sensitive.

I did make one additional change in my most recent test roll (bad experimental practice, I know, but for a patience challenged person...), I used 7.5g/l anhydrous sodium carbonate in place of postassium carbonate. In a private message, Rowland Mowrey was most emphatic that even trace amounts of potassium ion poison fixer. Based on his delcaration, I decided I would use sodium carbonate going forward. In addition, (and this is something Rowland refuted, by the way) I read somewhere on the Net that potassium carbonate had a greater tendency to effervese than sodium carbonate. If the roll is clean, I may try a test run with no presoak and sodium carbonate, since the presoak is a nuisance if it's not really the critical change.


Brad

 

[Brad Dow]

I wonder if you and Brad would be willing to send me a few samples of the exposed and developed negatives, and perhaps a roll or two of the HP5+ film. I would be very much interested in testing this in my environment to see if the phenomenon repeats itself here. Contact me by email if interested.

Sandy King

I'd be glad to. I have a roll of HP5 of the same batch number, exposed in exactly the same way I exposed my test roll. I can send that along with a strip of the developed test roll demonstrating the problem. I'll communicate offline to arrange...

Brad

 

[Brad Dow]

That does dampen my hopes a bit.

I have a test roll washing now. I won't give up hope until I see the result later tonight, but even if the results are not perfectly clean (and I do agree that one spot on a roll is too much, because it will invariably occur on the very frame you care about), switching to another film may be the answer. I mentioned before, but it's worth repeating, my test rolls of TMY and Tri-X 400 were completely free of spots. Perhaps something in the Ilford manufacturing process makes HP5 it especially sensitive.

I did make one additional change in my most recent test roll (bad experimental practice, I know, but for a patience challenged person...), I used 7.5g/l anhydrous sodium carbonate in place of postassium carbonate. In a private message, Rowland Mowrey was most emphatic that even trace amounts of potassium ion poison fixer. Based on his delcaration, I decided I would use sodium carbonate going forward. In addition, (and this is something Rowland refuted, by the way) I read somewhere on the Net that potassium carbonate had a greater tendency to effervese than sodium carbonate. If the roll is clean, I may try a test run with no presoak and sodium carbonate, since the presoak is a nuisance if it's not really the critical change.


Brad

The results are in from my second test roll (5-minute presoak, sodium carbonate), and it's just as bad as the previous test roll (no presoak, potassium carbonate). I was particular careful to rap the tank rather violently several times between agitation cycles. Now I'm really out of ideas. Damn!

I've communicated with Sandy, offline, and will send him some test materials. Perhaps he can shed some light.

 

[erikg]

Brad, sorry to hear about your latest results, but I hadn't had my hope up too high. I had a thought about adding a few drops of photo-flo to the developer. I'm thinking harder about switching films, have you had any issues with delta 400? I will also get in touch with Sandy and send him some of my processed film. At the very least he can confirm that we are seeing the same things. It's hard to believe that no one else has seen this on their own negatives. Damn miniature films!

 

[Valerie]

Thanks for looking into this guys! I have also had the same problems with HP5 (120) and PCatHD. I do use a 5 minute presoak, stand or semi-stand development, and a very dilute stop. I do not know a thing about chemistry so I cannot contribute to that discussion. BUt know that you are not the only ones experiencing this.

 

[erikg]

Just for informations sake this is the batch number of HP-5 that I'm currently working with: 08AHE1C03/01. I'd bet that I have used other batches as well, but I can't say for certain. I do buy film bricks at time, so I could be using the same stuff for a good while.

And just so people can have a look at what we are talking about, here is the link to my previous thread with an image attachedthere was a url link here which no longer exists)

It is a scan from a neg and the jpeg makes it look softer than it really is. These defects are very small, this image is cropped from a neg shot with a 35mm lens, so I wasn't all that close to the subject, and you can also judge the size versus the grain size.

Thanks Valerie, although I'm sorry you have also had this trouble, It's nice to know it's not just a random thing that happens to decend on a couple of people.

Best,
Erik

 

[sanking]

Brad, sorry to hear about your latest results, but I hadn't had my hope up too high. I had a thought about adding a few drops of photo-flo to the developer. I'm thinking harder about switching films, have you had any issues with delta 400? I will also get in touch with Sandy and send him some of my processed film. At the very least he can confirm that we are seeing the same things. It's hard to believe that no one else has seen this on their own negatives. Damn miniature films!

I would very much like to look at the processed film with a microscope. Also if you can spare a roll of the film that is causing the problem I would like to expose and process it myself.

But this is definitely an enigma. I just looked back through some dozens of rolls of HP5+, both in 35mm and 120, and quite a number of sheeets of HP5+, that were developed in Pyrocat-HD, and can not find any sign of this problem. And this morning I exposed three rolls of 35mm HP5+ to a clear north sky. I just developed one of the rolls on a stainless steel reel in a stainless tank for 15 minutes, in a water mixed Pyrocat-HD 1:1:100 solution. 1/2 strength acetic stop bath, followed by fresh alkaline fixer five minutes, and wash. The first roll has dried and there is not a single pin hole of the type described.

Probably should add that I have not bought any HP5+ film in over two years, so most of what I looked at was made before Ilford modified the manufacturing process of HP5+ a few years ago. However, I used at least one box of 4X5 sheet film for testing purposes after Ilford changed the process and none of the sheets I developed from this box in Pyrocat-HD show any problem.

Just for the record, the Pyrocat-HD solution that I used was not from a PF kit in water, but from stock solutions mixed by me from scratch.

Sandy

 

[erikg]

I sent off some test films and a spare roll to Sandy. Much thanks to Sandy for taking this on.

I don't know if I mentioned it but my developer is the PF premixed liquid.

And just for the sake of some good news, I just ran some FP-4+ and some Forte 200 that I shot recently in P-Cat, and I do not see any of these defects, just as I never have with any other film than HP-5+. I'm drawn more and more to the conclusion that the issue isn't technique nor presoaks and stop baths but just some interaction between at least some HP5+ and this developer. Why? I don't know. For my part if this means I choose a different 400 speed film, that is fine. I'm open to suggestions if folks have a favorite, keeping in mind that the developer will be P-Cat.

What did we do before Apug? This is a great community.

Erik

 

[sanking]

I sent off some test films and a spare roll to Sandy. Much thanks to Sandy for taking this on.

I don't know if I mentioned it but my developer is the PF premixed liquid.

And just for the sake of some good news, I just ran some FP-4+ and some Forte 200 that I shot recently in P-Cat, and I do not see any of these defects, just as I never have with any other film than HP-5+. I'm drawn more and more to the conclusion that the issue isn't technique nor presoaks and stop baths but just some interaction between at least some HP5+ and this developer. Why? I don't know. For my part if this means I choose a different 400 speed film, that is fine. I'm open to suggestions if folks have a favorite, keeping in mind that the developer will be P-Cat.

What did we do before Apug? This is a great community.

Erik

Erik,

I have looked at the sample you sent me, and hope to get a sample soon from Brad.

Looking at the spots on the negative under a microscoop at 100X you can clearly see what looks like a donut, with a small oblong dark spot in the middle, and a surrounding light area. And on one of the negatives there is a much larger donut, with the same configuration.

How could this happen? Well, it looks like an emulsion defect to me, and I am suspicious that it is because there have been several reports of pinholes on the Ilford forum, and not only with HP5+, but with other emulsions and developers. However, since you tested against another developer and did not see the same thing, we can not rule out the role of the developer.

If it is a developer problem, there could only be one explanation, i.e. there are some very small particulates in the developer that settle on the film and immediately kill sensitivity in that area. And then, during development there is an area of zero development that takes place in an oval around the killing particulate. I don't think it possible to explain this as an air bubble, because logically an air bubble would probably change location during the second and subsequent agitation periods. I mention this because in stand development if an air bubble is on the surface of the emulsion and is not dislodged during initial agitation there is an area of zero development underneath it, that spread out and gets bigger and bigger with time.

I am very anxious to look at Brad's samples. Right now I am quite mystified. However, I can state for a fact that I developed hundreds of rolls and sheets of HP5+ film and can not find a single example of it on any of this devleoped film, so it appears to be a very rare and local problem.

BTW, Erik sent me a roll of the film and I have put it aside for the moment to determine how to best test it for the problem. I am thinking of cutting it into sections and testing against several different solutions of Pyrocat and at least one other develope.

Sandy

 

[Will S]

Just for the record, I had this problem with a roll of HP5+ that I purchased in a brick and pyrocat-hd from PF, but it was awhile back in October/November 2004. At the time I contacted Ilford just so they would have the lot film number in case others had the same issue.

I suspected at the time that it was due to the water I was using out of my tap or to the acid stop bath. I refilled the water softener and got a filter that clamps onto the facuet, switched to water only stop, and the problem went away. I was using a pre-soak of 5 minutes already.

May or may not be related to this issue, but it is suspiciously similar. Lots of little black dots all over the prints....

Best,

Will

 

[Dave Krueger]

My experiences

Ok, so I'm a couple years late...

Anyway, just to put my comments on here for anyone else who comes across this issue in a search, I have had two rolls of 35mm HP5+ that have had what are almost certainly air bells on every frame after developing in Pyrocat-HD in glycol. The spots are clear, small, but definitely round on the negative. On the larger ones, there appears to be a tiny dark spot in the center. I don't have a microscope, but am using a 15X loupe. The developer was premixed from PF and is from 2006. The two films were shot and developed several months apart, although it is from the same bulk roll. This may or may not be related to what others are reporting in this thread.

Developer was mixed 1:1:100 using distilled water. I did a double rinse with plain tap water between developer and film strength Ilford rapid fixer. No acid stop. Development time was 15 minutes at 72F with agitation at 30 sec intervals. All solutions were within 2 degrees of each other.

For the record, I've been using Rodinal with the same process with no such problems with HP5. I thought it might just be because the Pyrocat is old and in almost empty bottles, but I do not get the air bells using the same developer with TMY 35mm. With both HP5 and TMY, I get nice density which tells me the developer is still quite active even for it's age (which is what I would expect from what I've read on these forums).

Anyway, this is just for reference in case anyone else has this issue. I stuck a postit note on the developer data sheet saying not to use it with HP5+ 35mm. I may have some HP5+ 120 and I know I have some 4x5, but don't have the time to experiment at the moment. I don't plan to pitch the developer or stop using it because I'm not having any trouble with other films. I may experiment with it again when I get a new bulk roll of HP5.

-Dave

 

[gainer]

Anytime you have carbonate in the developer, you have the possibility of gas bubbles. Products of development are at first acidic, aren't they? A black spot in the center of one of these holes is generating acid which combines with the carbonate to generate CO2 which lowers the concentration of the developing agent around the black nucleus. This is an opinion, not a proclamation of doctrine.

HP5+ seems to have a thicker emulsion, certainly than FP4+ if drying time is an indicator. That would seem to me to be a factor.

Somewhere in this forum I posted a formula for a carbonate-free accelerator for the Pyrocat series that has the necessary pH and concentration. I don't remember the proportions, but it contained only borax and either NaOH or KOH in the proportions of the standard buffer as described in the CRC Handbook, but double the concentration. The pH of the resulting working solution was about 11. Practical results were quite good.

I will try to find my records and re-post the formula. If one of you finds it first, please give it a try and see if it affects the problem.

 

[gainer]

I found my recipe for carbonate-free B solution: mix 20 g borax and either 40 g NaOH or 56 g KOH with water to make 1 liter of B solution for the Pyrocat series. The pH of a working solution of Pyrocat MC is 11. Their will be no gas produced by acidic development products, nor any precipitation of CaCO3 by calcium hardness.

 

[erikg]

Interesting. I was just thinking about trying some fresh film to see if the issue still persists. Can't say I'm curious enough to try Mr. Gainer's alternate B solution, I have moved on film wise, getting great results from TMY and Tri-x. Selfishly I do hope someone will test it out, just to put this issue to rest. I have also gotten great results with FP-4 (just completed a two year project where we shot over 1200 sheets of 4x5 and no sign of these spots) and 35mm Pan-F+. I have never seen that film look so good.

 

[gainer]

I think grain size and emulsion thickness are factors. I use the borax-lye solution just to avoid having to buy distilled or demineralized water or collect rain or dehumidifier water. I seldom use the 4x5 or 5x7 cameras because my legs don't even like to carry me around. I suppose that if these doughnuts appeared on 35 mm, it would be at a spacing that 35 mm might only see 1 per frame or so.

 

[Dave Krueger]

I might give that a try. It always bugs me when I have to remember that some film-developer combinations don't work, although in this case my problem could be due to the age of the chemicals as well as possible contamination. I have a newer batch of pyrocat that's only a year old or so. haha! I do so little work these days that I really am gravitating toward developers that last indefinitely. I like the characteristics of pyrocat for some things, but I also have a lot of HP5. I like Rodinal, but HP5 has to be rated at a lower EI for low concentrations of Rodinal.

Anyway, I also noticed that there were zillions of smaller white dots in the print, so I obviously have something serious going on. Using the same developer with TMY I got no clear spots in the negative, but I did get the tiny white dots in the print, but only a few of them. Would the development times be the same?

I need to get some borax, but I have the NaOH.