Large Format photography group - From "zero to hero!"

[Peter B]

I'm not sure that this is much help, but from the Ilford Monochrome Darkroom Practice manual:

 

[StephenM]

You can download a pdf that might be useful if you click on this link. It will immediately ask where to store the pdf when you click. Edit to add - it's from a museum's Department of Conservation and lists chemical treatments tried.

I assume you've also seen this site. I've left the name visible in case you already found it to save you clicking on it if you have.

https://chestofbooks.com/arts/photo...es-And-Prints-Their-Cause-And-Their-Cure.html

 

[Asha]

I'm not sure that this is much help, but from the Ilford Monochrome Darkroom Practice manual:

View attachment 295128

The final paragraph has me wondering if the deterioration is more prone to "modern" films. ( Perhaps different manufacturing materials and/or chemicals?)

I've been fortunate to have had access to very old negatives and glass plates that may have had sections of emulsion missing due to handling but I can't say that I've seen deterioration like what seems apparent on Woodsy's negs.

Many old products were "better" ( designed to last) than modern alternatives .......Perhaps film and associated chemistry follows the same chemin?!

 

[Woodsy]

It’s odd though, at least so far from what I’ve seen in my negs, the damage is sporadic over the age of the negs. For instance, of say 4-6 negs taken on a single trip that were very likely processed in the same tank/process, only one shows signs of damage or degradation (I’m still not 100% sure what’s going on in my case). If it were a bad batch of film, I’d expect to see a more convincing correlation in what frames are damaged. I’d expect to see similar damage on multiple frames from the same development though, if indeed the process is at fault - unless my technique is on the verge of fault, and in which case just a single frame being damaged from a single development is just bad luck (Especially after so long)?

 

[Peter B]

It’s odd though, at least so far from what I’ve seen in my negs, the damage is sporadic over the age of the negs. For instance, of say 4-6 negs taken on a single trip that were very likely processed in the same tank/process, only one shows signs of damage or degradation (I’m still not 100% sure what’s going on in my case). If it were a bad batch of film, I’d expect to see a more convincing correlation in what frames are damaged. I’d expect to see similar damage on multiple frames from the same development though, if indeed the process is at fault - unless my technique is on the verge of fault, and in which case just a single frame being damaged from a single development is just bad luck (Especially after so long)?

Possibly a red herring here Woodsy, but Barry Thornton has views on hardening fixer if you happened to use one?

 

[Asha]

Is it at all possible that the negs in question were stored in their sleeves before being 100% dry?

I'm clutching at straws here but in attempt to offer a reason, I wonder what, if any damage could occur long term if water ( from the final rinse) was trapped between the two materials of negative and sleeve.

I'm thinking on how water/ dampness can cause mildew on clothes and pages of books/ magazines.

 

[StephenM]

Ilford make both hardening and non hardening fixers - I just checked. I may choose to switch, at least when using modern films. My understanding is that older emulsions have more need of hardening.

As a thought on this, is it possible that, in line with Asha's suggestion, modern films are actually more difficult to wash thoroughly than older emulsions? Chemicals can be absolved insofar as it's still possible to use the same formulations used 100 years ago.

None of this really explains the actual results, except as random variations.

The discolouration suggests sulphur to me. I would a priori have expected older negatives and plates to be more heavily damaged, on the grounds of more sulphur in the atmosphere years ago due to coal fires, and more time for damage to occur. Which is contrary to Asha's observation, unless he is basing it on a selected sample - all sulphurated negatives and plates having found their way into landfill.

I assume that there are two real questions here - how to fix (pun intended) the affected negatives, and how to prevent a recurrance.

 

[StephenM]

For what it's worth, the way I washed my negatives back in the 1960s, was 6 changes of water at 5 minute intervals. First wash at processing temperature, then dropping a little until I finished with water from the cold tap.

I used other methods over the years, now using Ilford's water saving method, but as the 1960s negatives are still OK after 50 years, it seems best to cite how they were washed.

 

[Woodsy]

Really, really appreciate your responses chaps, it's hugely appreciated.

In case it's relevant, I use Ilford Rapid fixer. Reading the point about temperature, I do simply wash with water from the cold tap. I assume that this is around 15-20 degrees depending on the season? In general, I tend to fix for about 12-15 mins in 1:4 (fix:water) solution rather than 1:9. I don't know why, it's just what I've always done. I also agitate by inversion for approximately 10s per minute - the same as I do during the developing stage.

From what I can get my head around, it seems the issues are likely to be (ignoring atmospheric sulphur for a moment):

developer remaining in the emulsion,
Incomplete fixing
inadequate washing post fix.

In light of these three, what do you chaps think to me doing the following on all my B&W negatives (first on the damaged negs, so as to assess if it makes things worse):

Quick wash with water to remove dust,
Stand in fixer solution 1:4 at room temp for 10 mins,
Thorough wash in water,
Then leave to dry.

Is there any risk to any negatives, new or old, in doing so?

Thanks so much again @Asha, @StephenM, @Peter B

 

[Peter B]

What brand of film is it Woodsy, or are there different brands? If there are any affected Ilford negs it would probably be worthwhile dropping an email to their tech people as the're very helpful.

There's an email contact link on this page for when the FAQs don't have the answer.

 

[Asha]

Quick wash with water to remove dust,
Stand in fixer solution 1:4 at room temp for 10 mins,
Thorough wash in water,
Then leave to dry.

Is there any risk to any negatives, new or old, in doing so?

No risk that I'm aware of.

I've actually done that exact process myself with no problems.

May i suggest however that as none of us can 100% confirm the cause to the stains on the negs, that you do this initially with one "lesser important" neg and wait say a minimum of 24hours after drying to ensure that there is no ill side effect.

Perhaps take a photo of the neg before you begin so as to have a record that you can compare against.

 

[Asha]

For what it's worth, the way I washed my negatives back in the 1960s, was 6 changes of water at 5 minute intervals. First wash at processing temperature, then dropping a little until I finished with water from the cold tap.

This is pretty much my washing procedure too although I try and maintain the same temperature ( within a degree or two.)

I have found that if the temperature of the water is too low, it is actually less effective at absorbing / removing the residue chemicals.
I presume this is same when washing prints, hence i try and maintain a fairly stable wash temperture.

Just out of curiosity, do you guys agitate throughout the rinse cycle or not.?

Initial rinse for me is generally very quick, like a half minute or so with continual agitation....this i feel removes the bulk of the residue sat on the negative and in the tank.

After that I follow Stephens 5 minute ( aprroximative) method but folowing the first or second change of water, I reduce the amount of agitation, instead leaving the negative to 'soak' .

I learnt from somewhere / somebody, yonks ago that agitation doesn't actually offer any real benefit to the removal of chemical residue, it is simply the duration of contact with water that has the effect of diluting, thus removing the chems.

Like most methods, it is open to debate......

 

[Peter B]

I use a slightly modified version of the Ilford wash method with inversions of 7, 14, 21 & 30 times with water very close to 20C

Films Spiral tank processing method For minimal water usage the following method is well tested;
• After fixing, fill the spiral tank with water at the same temperature, +/- 5ºC (9ºF), as the processing solutions. Invert the tank 5 times.
• Drain the water away and refill. Invert the tank 10 times.
• Once more, drain the water. Invert the tank twenty times and drain the water away.
• Finally rinse with a few drops of ILFORD ILFOTOL Wetting Agent (1:200) added to the rinse water

 

[Asha]

I use a slightly modified version of the Ilford wash method with inversions of 7, 14, 21 & 30 times with water very close to 20C

What about with the orbital processor , do you agitate all the time through rinse?

 

[Peter B]

What about with the orbital processor , do you agitate all the time through rinse?

I've got the motor base ............. I actually take the lid off for washing and make sure that the sheets aren't sticking to the Orbital, so that the chems are washed off the rear of the sheet as well as the emulsion side. I wash for 1 minute, 2 mins, 4 mins and 6 mins.,

 

[StephenM]

Tap water temp- I'm Farhrenheit throughout, using 68 degrees for all the processes. Apart from anything else, I only have thermometers that use that scale. Water temperature probably varies by region and season, but on the one occasion I measured, it was 54 F. Which just happens to be the temperature below which a common developing agent doesn't work.

On agitation in washing, when using the six changes method, I worked on the assumption that removing the chemicals was like washing anything else off - new water, lift and lower the reel a few times to force the water through and make sure the chemical carry over in the water from the previous wash that remained behind was thoroughly diluted.

Chemically, all you have to do is achieve an equilibrium where there's so much in the water that no more will come out of the film, and then swap the water again.

Using the Ilford method, I do agitate a little more than specified, using water at 68 degrees. After washing, there's a final rinse in distilled water and wetting agent, so another chance to remove chemicals.

Over fixing can remove some of the silver image, but we're not measuring this in minutes, more hours. In fairness, I've only ever observed this once, and that was with a print, not film. I left it in the fixer while making more prints...

Fixer dilution is an interesting one. As far as I know, it shouldn't have any deleterious effect if it clears the film. Which reminds me, I always go by the double the clearing time, and when the clearing time doubles, throw the fixer. I haven't used the films that require longer fixing though.

 

[Asha]

Tap water temp- I'm Farhrenheit throughout

That's me stuffed then!

 

[StephenM]

Back on water temperature. I was taught that low temperatures shrink the emulsion, making it harder for the water to get in (and chemicals to get out).

Presumably, if you want hardened negatives, and still want to use non hardening fixer, you finish with a formaldehyde bath. I'm pretty sure formulae are all over the place for one.

 

[Woodsy]

What brand of film is it Woodsy, or are there different brands? If there are any affected Ilford negs it would probably be worthwhile dropping an email to their tech people as the're very helpful.

There's an email contact link on this page for when the FAQs don't have the answer.

It's a mixture. I started shooting Adox CHS 25, then moved to Acros, and now I'm rationing my remaining Acros, and hence shooting Delta 100. So far, the damage is only to the adox and acros, but I suspect this is due to their respective ages more than anything else, if all else is constant.

No risk that I'm aware of.

I've actually done that exact process myself with no problems.

May i suggest however that as none of us can 100% confirm the cause to the stains on the negs, that you do this initially with one "lesser important" neg and wait say a minimum of 24hours after drying to ensure that there is no ill side effect.

Perhaps take a photo of the neg before you begin so as to have a record that you can compare against.

Excellent, thanks for confirming. Yep, the plan was to only test a few of the damaged ones to begin with, and I was indeed going to take before and after photos

This is pretty much my washing procedure too although I try and maintain the same temperature ( within a degree or two.)

I have found that if the temperature of the water is too low, it is actually less effective at absorbing / removing the residue chemicals.
I presume this is same when washing prints, hence i try and maintain a fairly stable wash temperture.

Just out of curiosity, do you guys agitate throughout the rinse cycle or not.?

Initial rinse for me is generally very quick, like a half minute or so with continual agitation....this i feel removes the bulk of the residue sat on the negative and in the tank.

After that I follow Stephens 5 minute ( aprroximative) method but folowing the first or second change of water, I reduce the amount of agitation, instead leaving the negative to 'soak' .

I learnt from somewhere / somebody, yonks ago that agitation doesn't actually offer any real benefit to the removal of chemical residue, it is simply the duration of contact with water that has the effect of diluting, thus removing the chems.

Like most methods, it is open to debate......

So at work, I do a little bit of wet bench work in the cleanrooms, as we have to etch off semiconductor substrates to release our sample structure of interest. I appreciate an etch process is different from a diffusion or dilution process, but in order to achieve uniform etch rates, we have to use magnetic stirrers. This acts to strip away the layers that have reacted, revealing fresh substrate material to the etchant. I appreciate this example is not perfectly analogous, but if the process of removing a (relatively) highly concentrated chemical from a material relies on a diffusion mechanism, I would ere on the side of agitation being effective until such a time that the relative concentrations in the material and water are slowing the progress to the desired result.

I use a slightly modified version of the Ilford wash method with inversions of 7, 14, 21 & 30 times with water very close to 20C

Tap water temp- I'm Farhrenheit throughout, using 68 degrees for all the procrsses. Apart from anything elsr, I only have thermometers that use that scale. Water temperature probably varies by region and season, but on the one occasion I measured, it was 54 F. Which just happens to be the temperature below which a common developing agent doesn't work.

On agitation in washing, when using the six changes method, I worked on the assumption that removing the chemicals was like washing anything else of - new water, lift and lower the reel a few times to force the water through and make sure the chemical carry over in the water from the previous wash that remained behind was thoroughly diluted.

Chemically, all you have to do is achieve an equilibrium where there's so much in the water that no more will come out of the film, and then swap the water again.

Using the Ilford method, I do agitate a little more than specified, using water at 68 degrees. After washing, there's a final rinse in distilled water and wetting agent, so another chance to remove chemicals.

Over fixing can remove some of the silver image, but we're not measuring this in minutes, more hours. In fairness, I've only ever observed this once, and that was with a print, not film. I left it in the fixer while making more prints...

Fixer dilution is an interesting one. As far as I know, it shouldn't have any deleterious effect if it clears the film. Which reminds me, I always go by the double the clearing time, and when the clearing time doubles, throw the fixer. I haven't used the films that require longer fixing though.

Back on water temperature. I was taught that low temperatures shrink the emulsion, making it harder for the water to get in (and chemicals to get out).

Presumably, if you want hardened negatives, and still want to use non hardening fixer, you finish with a formaldehyde bath. I'm pretty sure formulae are all over the place for one.

Ok, so it would appear that my washing using water straight from the tap may well be a big part of the issue. I've not measured it, but I imagine it's a fair bit colder than the 20 degree water I achieve for the developer. In degrees C, I would be surprised if it were much above 16-17 right now, though I shall measure it.

In light of all of this, I feel that my processing technique is really rather minimal in effort. Perhaps I should start taking it a bit more seriously, especially to avoid problems like this in the future!

 

[Peter B]

Ok, so it would appear that my washing using water straight from the tap may well be a big part of the issue. I've not measured it, but I imagine it's a fair bit colder than the 20 degree water I achieve for the developer. In degrees C, I would be surprised if it were much above 16-17 right now, though I shall measure it.

In light of all of this, I feel that my processing technique is really rather minimal in effort. Perhaps I should start taking it a bit more seriously, especially to avoid problems like this in the future!

I tend to process in the evening and dry the film overnight. As someone who feels the cold, my go-to temperature for the central heating is 19C, and mixing (coffee paper) filtered tap water to 20C takes minimal time. It pretty much maintains itself after that, plus it only needs 2 litres for 4 changes of wash water on a 120 film, so a suitably sized jug works for that. The stop and fix are already mixed and only need to be set out for a while in their bottles to reach room temperature. I'm not sure that it's any more effort than most, but domestic harmony may benefit from agreement on timing and frequency!

 

[steveo_mcg]

Well thats a worry, I'm also pretty lazy with the final rinse being straight out of the cold tap!

 

[ChrisR]

...
In case it's relevant, I use Ilford Rapid fixer. Reading the point about temperature, I do simply wash with water from the cold tap. I assume that this is around 15-20 degrees depending on the season? In general, I tend to fix for about 12-15 mins in 1:4 (fix:water) solution rather than 1:9. I don't know why, it's just what I've always done. I also agitate by inversion for approximately 10s per minute - the same as I do during the developing stage.

...
Incomplete fixing
inadequate washing post fix.
...

Stand in fixer solution 1:4 at room temp for 10 mins,
...

I'm amazed at these fix times! I've never fixed for more than 5 minutes; clearing time for an exposed leader in a saucer is usually about a minute (Ilford Rapid Fixer 1+4). But I do agitate (rotate in the Rondinax in my case) throughout.

I appreciate that you don't get a leader to play with using 4x5, but is it worth sacrificing a sheet to see clearing times? Maybe one you're pretty convinced got screwed up for some daft reason (assuming that ever happens to experienced LF users!)?

Oh, I also fill several jugs of water at the start and use them for 5 washes (well 4, the last one is de-ionised water), so the temperature is pretty close to 20C.

I may have missed it, but have you had a look through your back catalogue of home-processed BW images for similar occurrences? If none, that would suggest a temporary glitch of some kind...

 

[StephenM]

On fixing -

I use a CombiPlan tank which has comparatively long fill and drain times.

Developer doesn't start darkening film in a microsecond, and there is a latency.

Therefore, the old advice was to examine the film in the fixer at nominal half time; if not clear, put back and try agin shortly after. Having got the clearing time, double it. Job done. And that 's what I've always done.

The relevance of the first two statements? Well, I actually remove the tank lid to pour the stop out and the fixer in. I've never noticed a problem, whatever purists may say. This is just to illustrate that you CAN safely check clearing times by examining the film during fixing.

Edit to add. Yes, film will darken without needing any developer. But not to any visible extent in the combined time of stop and fix. A stop bath should pretty much stop development immediately, as the only developer that is available is that held in the emulsion, until it diffuses out.

I shall at this point take down and consult Grant Haist's two volume work on processing. I'll report back in due course.

 

[StephenM]

I'm still reading, but a few highlights - possibly relevant - are

Fixing.
Creates thiosulphates in the emulsion that must be washed out. Failure to do so leaves the sulphur in the emulsion, to create silver sulphide down the line (equals yellow stain).

Efficacy of fixing drops if the pH rises too much (by alkaline carry over from the developer).

Over fixing causes the thiosulphates to bind tightly with the gelatin, making removal impossible. Therefore fixing should not be prolonged.

Higher concentration gives shorter fixing times.

Does this mean that Woodsy's more concentrated than specified fixer strength plus longer than needed times - fresh rapid fixer probably does the job in 2 minutes at normal dilution - could have a bearing on the stains?

More to follow - it's close on 150-200 pages on fixing and washing.

 

[StephenM]

Very quick washing highlights. N.B. both sections have been skim read, so important points may be missed.

Chemical removal is exponential. If 50% is removed in x minutes, with fresh water the next x minutes will remove 50% of the remainder.

Hard water is better than pure water. Pure water is the least effective agent.

Sea water washing takes half the time of fresh water, but the sea water must be washed out afterwards. Two changes of water suffices.

Temperature. Higher temperature means a longer diffusion pathway for chemicals to leave the emulsion. But washing at 80F gives 30% shorter washes than 40 F.

And the 6 (Grant Haist says 5 or 6) changes of 5 minutes gives archival permanence.

As you'd expect, there are lots of facts and figures, including the effect of the various stages on the emulsion thickness (rises at each stage of processing), papers cited etc. etc. I recommend those interested to read it for themselves. All this material is in the first volume.

 

[Asha]

To think how lucky we are here on TP.

We have our very own ‘bibliothèque ´ with a built in auto search mode. LOL

We ask and it/ he searches!
Just excellent !

Thank you @StephenM
You have are such a wealth of information , I dunno how we ever managed without you

 

[StephenM]

And a quick check seems to indicate that it's not available - as in waiting list unavailable. You're looking for:

Modern Photographic Processing Grant Haist Wiley 1979

As far as I know, it was only reprinted on demand by the now deceased author. Cost will be around £90 per volume. Something to look out for in charity shops or car boot sales.

 

[StephenM]

I was actually rather good at literature searches. We had a third year project that was a lit search, and the lecturer who set and marked mine said the mark he gave had been reduced, so I only scored 91%. I recall that to this day, on the grounds of a rather good mark, and the only instance I heard of of a downgrading.

 

[StephenM]

A final thought before I return the book to the shelf - yes, this book has an accessible shelf spot, rather than being part of a pile. There is a lot about hypo clearing agents, and from a quick glance as I skipped through, it may be possible to use one to remove even the tightly bound thiosulphates.

I don't recall seeing a section on after treatment of faded or stained negatives, but I know other books cover this.

My first thought is always to go to a book, but I expect the information (together with its opposite) can be found online.

Edit. Well, that pushed my postcount up! Sorry for monopolising the thread.

 

[steveo_mcg]

Edit. Well, that pushed my postcount up! Sorry for monopolising the thread.

Could be worse, could have been Asha

Very interesting, didn't realise over fixing was a real issue rather than just something else to needlessly worry about.

 

[Woodsy]

Thanks so much for this info! So clearly I’m fixing for too long, and this is something I can change from now on. Sacrificing a sheet is a good idea, for sure.

in light of the above, do you think soaking negatives in fresh water - wash again properly, essentially - will be effective in stopping damage to negs that are not yet showing any signs of degradation?

 

[StephenM]

It's an interesting question, and one I would have given a "probably yes" answer to yesterday, before reading up on the question and seeing about the impossibilty of washing out thiosulphates after over fixing.

That said, I don't recall seeing "over fixing" quantified, so this may not even be your problem, although remaining sulphur compounds may be the most likely source of the problem. It might also be the case that there is a chemical fix available. I certainly saw one a few days ago for sulphur staining.

What might be intructive is getting a hypo test kit, which I'm assuming are still available, and test a negative. If kits aren't made, I can supply a formula although I would expect formulae to be in all the standard texts.

There are still other books I can check, by the way.

 

[Woodsy]

Such as This?

 

[StephenM]

That's it. From memory, it's easy to make your own with a few basic chemicals, possibly basic enough to buy under different names in a hardware shop or chemist - as in pharmacy. I came across such a recipe for Rodinal a couple of days ago.

 

[StephenM]

If you can't get any, let me know as I think I might have some and I 'll take a look.

 

[RaglanSurf]

It's a mixture. I started shooting Adox CHS 25, then moved to Acros, and now I'm rationing my remaining Acros, and hence shooting Delta 100. So far, the damage is only to the adox and acros, but I suspect this is due to their respective ages more than anything else, if all else is constant.



Excellent, thanks for confirming. Yep, the plan was to only test a few of the damaged ones to begin with, and I was indeed going to take before and after photos



So at work, I do a little bit of wet bench work in the cleanrooms, as we have to etch off semiconductor substrates to release our sample structure of interest. I appreciate an etch process is different from a diffusion or dilution process, but in order to achieve uniform etch rates, we have to use magnetic stirrers. This acts to strip away the layers that have reacted, revealing fresh substrate material to the etchant. I appreciate this example is not perfectly analogous, but if the process of removing a (relatively) highly concentrated chemical from a material relies on a diffusion mechanism, I would ere on the side of agitation being effective until such a time that the relative concentrations in the material and water are slowing the progress to the desired result.





Ok, so it would appear that my washing using water straight from the tap may well be a big part of the issue. I've not measured it, but I imagine it's a fair bit colder than the 20 degree water I achieve for the developer. In degrees C, I would be surprised if it were much above 16-17 right now, though I shall measure it.

In light of all of this, I feel that my processing technique is really rather minimal in effort. Perhaps I should start taking it a bit more seriously, especially to avoid problems like this in the future!

I’ve been using the Ilford washing technique for the past few years, I fill three large jugs when I start developing and let the wash water come up to room temperature. I think gives me better results. Tap water, particularly in the winter, can be very cold straight out of the tap and despite me trying to regulate it with some from the hot tap it was never consistent. It also saves wasting a lot of water.

 

[ChrisR]

...
Does this mean that Woodsy's more concentrated than specified fixer strength plus longer than needed times - fresh rapid fixer probably does the job in 2 minutes at normal dilution - could have a bearing on the stains?
...

I don't think Jonathan's 1+4 dilution is "more concentrated than specified"... Ilford's document says:

"For all film fixing applications ILFORD RAPID FIXER is diluted 1+4 with water.
For use as a fixer in paper processing machines ILFORD RAPID FIXER is diluted 1+4 with water but for manual fixing applications it can be diluted either 1+4 or 1+9."

 

[StephenM]

Thanks for the correction. I didn't check the Ilford information and made an assumption based on the phrase "1:4 rather than1:9". I should never assume anything.

 

[Asha]

I don't think Jonathan's 1+4 dilution is "more concentrated than specified"... Ilford's document says:

"For all film fixing applications ILFORD RAPID FIXER is diluted 1+4 with water.
For use as a fixer in paper processing machines ILFORD RAPID FIXER is diluted 1+4 with water but for manual fixing applications it can be diluted either 1+4 or 1+9."

Thanks for the correction. I didn't check the Ilford information and made an assumption based on the phrase "1:4 rather than1:9". I should never assume anything.

fwiw I mix 1:4ilford rapid fixer for film. It’s a while since making solution for paper prints but iirc that is much weaker 1:9 ??

 

[ChrisR]

Thanks for the correction. I didn't check the Ilford information and made an assumption based on the phrase "1:4 rather than1:9". I should never assume anything.

Pedantry point sorry: 1+4 (20%) rather than 1:4 (25%). I'll go now....