washing negatives - Does the fixer leach out?

[billtroop]

In this kind of forum someone presents a problem and you expect experts to respond, not for the sheer joy of responding, but with thoughtful information that they may spend a few minutes gathering and expressing -- perhaps even a few hours, onerous as that may be. I would like to see a little more respect for the value of words per se. For example, dichroic can only mean two-colored. The prefix di- means two, although OED allows that in scientific usage it can mean 'two or more'. However, it can never mean one. The prefix for one is 'mono'. But all this haste! Has it never occurred to anyone to spend some time in a technical library before responding? That a response should have value?

 

[Dietmar Wolf]

Hi All,
In response to Thomas asking for how long Ilford gave this advice, I must say that I learned B&W process in the early seventies and this was the way I was told to wash film.
Last but not least, a German guy (I think he is German) had done a nice test job on washing. He confirms the Ilford washing procedure. You'll find the results here :
http://www.geocities.com/ResearchTriangle/Thinktank/5693/photogra.html
Last but not least, I had a print course given by a renowned French printer running a comercial printing lab in Paris. In order to be sure to deliver archival prints to his customers, he had it's process checked by scientists and improved by them to reduce water consumption (water is metered in France and paid at a premium price now because production has gone from public to private).
He does print washing by transfering prints sgeeged from an emptied tray to a full tray of fresh water repeat the process after the emptied tray is full of fresh water for an half an hour. He let the less skilled assistant process them ......

Thank you very much for the link.

 

[billtroop]

>Last but not least, a German guy (I think he is German) had done a nice test job on washing. He confirms the Ilford washing procedure. You'll find the results here :
http://www.geocities.com/ResearchTri.../photogra.html

Does anyone seriously suppose that this piece of diligent but amateurish research by 'a German guy' (he thinks) is of more value than the professional research of one of Kodak Harrow's most senior scientists?

 

[Roger Hicks]

>Last but not least, a German guy (I think he is German) had done a nice test job on washing. He confirms the Ilford washing procedure. You'll find the results here :
http://www.geocities.com/ResearchTri.../photogra.html

Does anyone seriously suppose that this piece of diligent but amateurish research by 'a German guy' (he thinks) is of more value than the professional research of one of Kodak Harrow's most senior scientists?

Dear Bill,

Who in Harrow were you thinking of? I am not aware of any research that contradicts Ilford's assertions, though of course this is sheer ignorance on my part. Nor was Mike Gristwood aware of it, as far as I know.

Cheers,

R.

 

[billtroop]

I'm sorry but I can't resist:

... "a German guy (I think he is German)" ...

this is to be our new index for scientific authority in photography?

I think I can say that there is not a scintilla of professional, peer-reviewed scientific evidence in support of any water-saving washing system other than Levenson's/Kodak's. Issues like this are of enormous practical complexity and are not to be solved in home darkrooms by amateur scientists.

Just one other footnote, regarding the potassium thiosulfate fixer patent referenced by Ryuji. I think it is generally agreed in the _scientific_ community that the literal procedure described in the patent _does not work_; the purpose of the patent may be to sneak in something else. This points to the whole problem of doing research by reference to the patent literature. As Grant Haist said to me several years ago, 'the purpose of a patent, for Kodak, since the late 1950s, has, by corporate edict, largely been to conceal, not to reveal, the scope of the invention.' There are only very few exceptions to this rule of thumb, one of which is the 'teaching patent' by Zawadzki et al. which describes the Xtol film developer.

 

[Photo Engineer]

Dear Bill,

Who in Harrow were you thinking of? I am not aware of any research that contradicts Ilford's assertions, though of course this is sheer ignorance on my part. Nor was Mike Gristwood aware of it, as far as I know.

Cheers,

R.

Roger;

In Bill's previous post and mine, we both refer to a thread on Photo Net in which there is an exact reference to Levinson's work.

Grant Haist quotes this study by GIP Levinson of Harrow in his textbook. Levinson describes 3 or more 5' rinse baths (with agitation) as being best for washing other than running water. It is backed up by extensive data, and essentially adds the safety factor needed for all conditions of pH, film thickness, film formulation, fixer formulation and etc..

As for Potassisum salts in fixer. If it could be made to work over a broad range of conditions, there would be potassium fixes. As is, it is well reported that potassium ion above trace amounts virtually poison the fixing reaction. This is also true of Calcium and Magnesium to a certain extent. Again, see Mees and Haist for other information.

PE

 

[Roger Hicks]

Come on, Bill. Everyone knows amateur scientists are no good. People like Niepce, Talbot, Herschel, Goodwin (Godwin?) -- what did they know?

Cheers,

R.

 

[billtroop]

Dear Bill,

Who in Harrow were you thinking of? I am not aware of any research that contradicts Ilford's assertions, though of course this is sheer ignorance on my part. Nor was Mike Gristwood aware of it, as far as I know.

Cheers,

R.

Hi Roger, I guess you didn't read my reply when you raised this issue over two years ago, in Feb 2007, here:

http://photo.net/bboard/q-and-a-fetch-msg?msg_id=00Arzw

Just have a look at that page and let me know if you have any further questions, comments, or nit-picks.

In case that seems too onerous, I'll just paste in the admittedly somewhat sharp response I then wrote:

'I would like to respond to Roger Hicks who writes,

"Do not automatically trust Anchell and Troop. There are a lot of unsupported assertions that are not widely accepted by other authorities; many opinions masquerading as statements of fact: and some flat errors, such as their strictures on film washing on page 108 where they state that the film must be left to soak five minutes between sets of inversions. I know the people at Ilford who did the original research -- one of them is or was on the ISO standards committee -- and the five minute assertion is pure fiction. It would not be quite so bad if A+T did not say that the way without the wait 'is an error'."

Roger, for my five-minute statement, why don't you have a look at the following three papers?

1. G.I.P. Levenson (Kodak, Harrow), "The washing powers of water", J. Phot. Sci., 15: 215 (1967).

2. A. Green and G.I.P. Levenson, "The washing of thiosulphate from gelatin layers", J. Phot. Sci., 18:1 (1970).

3. G.I.P. Levenson, "The economics of photographic washing", Brit. Kinemat., 30:95 (1957).

There is also a fourth and very well-known paper by Levenson if memory serves me (all of this research was done by Kodak, Harrow, not Ilford which simply incorrectly appropriated it) from the mid-1970s for which I do not conveniently have the reference.

Then you may want to glance at Haist, Modern Photographic Processing, vol. 1, p. 668:

"For efficient washing of photographic materials a complete change of water in the vessel should be made every five minutes .... Five or six 5-min changes of water are sufficient to insure permanence of images on film or glass supports."

If you have any other "unsupported assertions that are not widely accepted by other authorities; many opinions masquerading as statements of fact: and some flat errors" that you suspect I have fallen into, I would be delighted to address them here or anywhere else. I am one of the world's most accessible people. Please feel free to email or phone me anytime. Sincerely, Bill'

I would just like to add that the manuscript for my book was read by and annotated by Grant Haist, Silvia Zawadzki, Dick Dickerson, Geoffrey Crawley, and T.H. James. I incorporated all of their comments into the final text. I don't know what more could be expected from me! These were the people I knew who were willing to put in countless hours helping me. I don't think I could have found better collaborators in the 1990s.

 

[Michel Hardy-Vallée]

Bill, without putting into question your results, I am curious to know if you have spoken with the Ilford people: they are after all the ones who popularize the 5-10-20 method, and if they are wrong to omit the waiting time, what are they doing about it?

 

[billtroop]

>Come on, Bill. Everyone knows amateur scientists are no good. People like Niepce, Talbot, Herschel, Goodwin (Godwin?) -- what did they know?

Roger, you're both making and missing the point. Amateur scientists were great for photography in the 19th century. They were even great for photography in the early 20th century (think of the astonishing feat of Mannes and Godowsky with Kodachrome). But they are not good for solving problems like how long do you have to wash photographic materials for? This is illustrated by the fact that it took 150 years to get from Talbot to Levenson's research. It is further illustrated by the recent research of Nishimura and his associates. Getting authoritative answers to these fundamental questions is not easy. Ron Mowrey has hinted at some of the problems that have to be considered before a recommendation can be made when he mentions 'the safety factor needed for all conditions of pH, film thickness, film formulation, fixer formulation and etc.' If that isn't clear, perhaps we could ask Ron to more explicit?

 

[Ryuji]

Roger, Michael, et al.,

I don't want to get involved with others' arguments, but I have tried many variations of Ilford washing methods myself, partly for my own practice, and partly to double check the accuracy of information that was put together as the user instruction of Silvergrain products.

All Ilford fast washing techniques, when executed properly, gave residual thiosulfate level below archival limit for residual thiosulfate. The archival standard changed over time, and if you use today's standard, the Ilford method way exceeds the requirement for archivalness, for the residual thiosulfate value. I have no relation to Ilford except I occasionally accept freebies

Some of the recommended procedures in Silvergrain instruction sheets (anyone can download the pdf file from digitaltruth.com) are same as or modified versions of Ilford method. Some are modified Kodak method. There are a wide range of Clearfix and Clearwash users today, and one of the frequent questions we get is "I learned such and such at John Sexton workshop but can I use Clearfix in this workflow?" and Digitaltruth and I agreed to include several popular processing sequences as options, rather than presenting one option rather dogmatically. Of course, when I started my darkroom work, I started with Kodak method, and I have my trajectory of tinkering with all sorts of techniques, so it was rather refreshing to test them all once again. If I didn't test them myself to confirm that there are significant safety factors, I wouldn't allow to put them on there.

Also, I'm very familiar with the work of Levenson, Green, et al. at Kodak Harrow Lab, as well as Aelterman and others at AGFA-Gevert Mortsel lab. There is nothing that negates Ilford recommendation. Quite frankly, the era of blowing whistles on residual thiosulfate is over. The ANSI standards have been on the conservative side, and we have a range of easy ways to meet or exceed them.

Regarding the article that was once printed on Photo Techniques magazine and also published on the web. What a respectable and knowledgeable person should say when he finds a report with a couple of technical problems? I think it is to simply point out the problems, and if possible, suggest how to avoid the problems, and if at all possible, run his own tests and share the results with the original author and his audience. Yes that report is probably an amateur work, but trying to discredit his work by claiming he is an amateur will only lead to fallacious arguments.

 

[Photo Engineer]

Roger;

In the early days of every 'science' there are people who make empirical discoveries and each one compounds on the other to accelerate growth. Suddenly they connect the dots and create structure and are 'scientists' who work as 'engineers' in the field. Our understanding of fixing is far greater today than Herschel, and our understanding of Kodacrhome is far better than that of Mannes and Godowsky.

As for the Ilford method, I think that you will find that all of the work by Levenson (I spelled it right finally), has a safety factor which will encompass fixers that are hardening, non-hardening, acidic, alkaline and also will work for thin films such as Panatomic-X and thick films like Tri-X (going back to his time). The Ilford work may, by the nature of Ilfords R&D, be more oriented towards minimizing wash for conservaton purposes and may involve ilford products. I know that at Kodak we were lectured on the fact that not everyone used Kodak chemistry and films and therefore we cross tested materials. I expect this of Levenson as well.

So, to get the best results in every possible condition of water, film, fixer etc... I believe Levenson, as no one else has done as extensive work as he has on the subject of the fix-wash interaction. I posted some of that information earlier here regarding diffusion inward and outwards of chemistry. That is important here.

PE

 

[Michel Hardy-Vallée]

Ron, thanks for your thoughtful summary.

For some reason this has been the subject of many threads lately (HCA or not? sodium vs. ammonium sulfite? alkaline vs acid fix? hardener or not? FB vs. RC vs film, etc).

Perhaps one contribution of APUG to the world should be a decision tree that takes into consideration these multiple factors, and which would help someone to figure out an adequate silver gelatin post-development sequence? For example:

SUPPORT
* Film
* RC paper
* FB paper

STOP
* Use an acid stop
* Use a water stop

FIX
* Acid fix
** Traditional Sodium thiosulfate
** Ammonium thiosulfate rapid fix
* Alkaline fix

HARDENER
* Yes
* No

FIXING BATH
* Single-bath
* Two-bath

TONER
* Selenium
* Sulfide
* Gold
* Blue
* Copper
(...others...)
* None

WASH
* Hard water
* Soft water

WATER ECONOMY
* Yes
* No

You check the boxes that apply, and then a decision tree calculates whether 1) you messed up something 2) you need HCA, and 2b) when, if you are toning and 3) how long to wash, following which procedure depending on your water supply and economy needs.

Hey, anybody still codes in PROLOG? Just kidding.

 

[Photo Engineer]

OMG, PROLOG? All parentheses IIRC.

But, Michel, I agree. Your idea is great.

And, thanks for the nice comment.

PE

 

[Michel Hardy-Vallée]

Parentheses, square brackets, and underscores too! The only language which uses underscores as part of its syntax!

 

[billtroop]

Michel, if Ilford scientists had credible evidence of washing techniques that overturned the bedrock findings of Levenson, they would have published them. They have not. They thus don't have credibility -- by my standards.

Ryuji, you have made a rather imperial statement when you say 'The archival standard changed over time, and if you use today's standard, the Ilford method way exceeds the requirement for archivalness, for the residual thiosulfate value.' Would you care to discuss exactly what the archival standard was at the time of Levenson's publications, when it was changed, and why? If you would further care to publish your results in some appropriate journal, we might then be able to take seriously what must, until then, remain baseless presumptions on your part. I remember when you went into a raging tizzy because Beveridge, et al. at Ilford, in their work on archival fixing techniques, actually seem not to have published their paper, but merely read it at an SPSE conference organized by Hendriks. (It may have been published subsequently; I simply happen not to have the reference; or perhaps it wasn't.) You might try yourself to meet some of the standards you impose on others. You don't; you never do. That's why your credibility, despite your unquestionable virtuosity, is low. Enough with these unsubstantiated opinions. Let's see some science!

 

[Photo Engineer]

Just FYI, the current ANSI and ISO standard for image stability was adopted in 1996 and they are working on a revision at the current time. I don't recall when the previous standards went into effect, and could not find them in any of my texts. I would have to do an extensive search on-line for that data.

Many of the revisions in the recent changes involve the introduction of digital paper standards and the use of atmospheric pollutants in the test methods. Currently under consideration are light intensity standards (discussed in my posts eleswhere on APUG) and image spread of digital images (also mentioned by me elsewhere on APUG).

In our work at Kodak, most of which is unpublished, the stability data were supplimented by analysis for silver metal and silver haldies, silver sulfide and retained process chemistry. Some of this is alluded to in reporting by Haist as well as the well known and acknowledged (to us at least if not Ryuji) work of Levinson. The suggestions by Ilford are what we term 'apocryphal' until they are peer reviewed and then published in a journal. I don't doubt that they are suitable, just that they are not of as much generalized use as that of Levinson which were designed with the safety factors I mentioned previously along with reasoning.

Some of the most outstanding recent work on B&W image stability is the work of Beveridge of Ilford that Bill Troop mentions above. Ryuji has not accepted that work even though it was accepted for delivery at a major photographic conference.

For that matter, I gave a major talk at an ICIS meeting many years ago but was not permitted to publish the paper itself although several patents were issued covering the work. Does this make my work invalid? I think not! Although, by Ruyji's definition, patents are useless, so maybe in his eyes the work is invalid. I think we have to keep our heads on straight here. The Ilford work is valid but limited from what I can see, and less broad than that in the 3 publications cited by Levinson. It does have a place, but perhaps only under certain conditions and with careful testing.

In any event, having not tested the Ilford method, I cannot recommend it for all conditions.

PE

 

[Richard Jepsen]

Good Grief!! Once I thought I knew and now I am unsure. In plain English, what are the two or three authoritive recommendations for fixing? I fix FP-4 and Tri-X in TF-4 and wash for 12-15 min to ensure dye removal. I fill and dump 5 or 6 times with 15-20 inversion cycles between dumps. Does this meet archival standards?

 

[Photo Engineer]

Depends on film, water and fixer.

Use 5' holds between and you should be ok, dump after the quick inversions and probably not ok. Levinson says 5'. He is the only published source with analytical data.

Or, use the regular continuous wash.

PE

 

[Ryuji]

Good Grief!! Once I thought I knew and now I am unsure. In plain English, what are the two or three authoritive recommendations for fixing? I fix FP-4 and Tri-X in TF-4 and wash for 12-15 min to ensure dye removal. I fill and dump 5 or 6 times with 15-20 inversion cycles between dumps. Does this meet archival standards?

I bet that is way more then sufficient, provided that you gave fixing time of 2x tje clearing time or longer, and didn't allow the fixer to go near exhaustion.

 

[dancqu]

Levinson says 5'. He is the only published
source with analytical data.PE

I wonder how dated that information might be?
Six cycles, 5 minutes twixt each. Over doing it I'd
say what with todays thin emulsions and fixers without
hardener and perhaps alkaline at that.

I myself trust to a little protracted Ilford 5 - 10 - 20
inversion three waters wash. The fresh each roll very
dilute fix I use helps assure. Dan

 

[Photo Engineer]

Dan;

This kind of data has no real valid lifetime. Diffusion rates stay the same, but film thickness does vary as does the level of silver and fixer formulas.

His data may be out of date by your measure, but when you consider safety factors, I think he is right. In any event, use what pleases you. It is your film.

PE

 

[Cor]

Using a JOBO for film washing

I use a JOBO to wash my (4*5) film, I use the slowest rotation speed, and wash for 4 times 5 minutes (this is with plain, hard water, I finish with a destilled water/photo-flo/ iso-propanol step of 2-3 minutes). I wonder if these steps count a 5 minutes hold time, ie does "hold" mean standing still?

Best & thanks,

Cor

 

[Photo Engineer]

Hold best includes agitation for the reasons I gave in a previous post here.

I remove my reels from the Jobo and wash them in an archival film washer.

PE

 

[Ryuji]

I wonder how dated that information might be?

Is the reference citation info included in the post? Don't believe whatever is stated unless you can confirm the original report, and interpret whether the test conditions and archivality criteria are same as yours.

In reality, Green of Kodak Harrow Lab published the time course of residual thiosulfate over washing time, and the washing time of film (with the usual caveat) can be greatly accelerated by various factors, including vigorous water flow or agitation. Aelterman of AGFA lab also published very analogous findings. Their findings closely parallel mine as well.

The usual caveat is to use neutral ammonium thiosulfate fixer without hardener, fix for at least twice the clearing time, never let the fixer get exhausted, and use tap water to wash.

If you are concerned about the different chemicals, materials, etc., there is nothing better than test your own material. At the end of the day, that's all that matters.

In my own testing, when I take a reel of film out of my fixer (either Neutral Rapid fix or Clearfix), rinse it in water for 10 seconds and then immerse it in a big bucket of water and vigorously shake it for 1 minute, the residual thiosulfate level is already ridiculously low and below the archival standard for camera negative emulsions today. Doing the same in a small tank will require a change of water a couple of times. That's exactly the point of Ilford system. Total washing time of less than 2 minutes can meet or exceed today's archival standard for residual thiosulfate, if the fixing and washing procedures are correctly performed.