Washing Film - Best Environmentally Friendly Way to Do It?

[namke]

I've just looked in my copy of Monochrome Darkroom Practice by Jack Coote (1982), which has the following about film washing:

It is often mistakenly assumed that efficient washing can only be achieved by using large quantities of water for long periods of time. But, as G. I. P. Levenson has pointed out, it would be possible to wash 1000 feet of motion picture positive film to archival standard in one litre of water, provided that the water was used efficiently. He has also reported that: "Excellent washing of a processed roll-film was achieved in a spiral tank by giving just three half-minute changes of cold water and agitating well during each period. The tank was just emptied after each wash with no attempt to drain thoroughly. After the third wash, the film was wiped before hanging it up to dry."

Now, without looking at the original material, I can't offer any advice about what excellent washing might be, but Coote goes on to mention that Levenson proposed that there be two levels of 'safe' washing - one for archival, and one for commercial use.

As his target for adequate commercial (my emphasis) washing of film, Levenson aimed at diluting one hundredfold the concentration of thiosulphate solution in the image layer when it left the fixer.

 

[namke]

I've also just found (there was a url link here which no longer exists), where this site is referenced, which appears to go into some detail about the 'Ilford Wash'.

The FP4 datasheet states the Ilford way too - Page 5 of this PDF

 

[Photo Engineer]

The Kodak Hypo test kit gives a standard reference in color and in quantity of retained hypo and silver halide in a coating for archival wash. Early Kodak manuals give in the range of 1 hour washing in running water to achieve this level for film and some FB papers.

I won't suggest that this is needed for modern papers or films, but I know this, that single wash baths are not efficient. Here is the reason:

Wash 1 can only remove 1/2 of the chemicals from the coating. This is a law of science shown by Mason.
Wash 2 can only remove 1/2 of the remainder using the same math.
Wash 3 can only remove 1/2 of #2.

And etc. You approach zero but never get there because the wash water you use never has zero chemistry in it. It always equillibrates with what was in the film from the past condition.

Now consider running water. It is always zero in chemistry and as it passes over the film, the exchange is roughly double that in single baths and it can get to zero in the film (or a very very tiny amount).

This latter wash can be quicker and more economical when done properly, but you must not overdo the wash.

Simon is right though. Today we must conserve our resources and this is why Ilford and Kodak both came up with the other method in hopes that it would conserve water, but misused it can result in underwashed photo materials. So, I suggest that in the final analysis, you use the silver halide retention test for rate of fixing, and the hypo retention test for rate of washing whatever method you choose for washing your film and prints.

And, don't chance it to water from rain or from dehumidifiers. Both of these contain atmospheric contaminants and bacteria that are not present in distilled or tap water.

PE

 

[Barry S]

PE-- I think you're only partially right about single wash baths because you're not taking into account the relative volumes of emulsion and the wash water. I've purified proteins and other materials using dialysis, and the concentrated side and the dilute side will reach an equilibrium when the concentrations are equal, *but* with a relatively larger volume of wash water--the initial concentration of the solute can easily drop to less than 5% with a single wash after the system reaches equilibrium. Imagine washing 1 ml of emulsion with 1 ml of water vs. washing with 1000 ml of water. If the washing bath is sufficiently large, it performs nearly as well as running water with no solute.

 

[Lee L]

Here's a study of the Ilford wash method that you might like to read:

http://www.largeformatphotography.info/unicolor/ilfwash.pdf

Lee

 

[Photo Engineer]

Barry, Lee;

See Mason. Barring that, see my previous post in another thread on washing which gives the equations and data from Mason. The article that Lee refers to is correct to a point. The amount of hypo approaches an equillibrium value, but that value is far lower with flowing fresh water according to the same type of math as in the article.

You see, the bath has to be sufficiently large, and by that time you are sometimes passing the break even point in water conservation.

Well, read Mason or the other post.

PE

 

[Lee L]

Well, read Mason or the other post.

Couldn't find the 1979 Mason edition that you recommend in another thread as having the wash info. There is only one copy of the 1975 edition in paperback on Amazon for $499.00 plus $3.99 shipping.

Also couldn't find a thread here searching on "Mason" that had the equations you posted. Will keep looking and post back here if I find it.

Lee

P.S. Found the 1975 Mason for $120 + shipping on Abe Books. No 1979 edition found. Still can't find the thread with Mason's equations.

 

[CBG]

... of the sequential dump and fill showed ... that this method was not as effective as a stream of continuously running water for washing film or paper.

The best wash is a stream of constantly flowing water which is kept up until the photomaterial tests free of hypo residue and silver halide using the appropriate tests ...

Interesting. Whenever PE writes, I listen, and now he has me thinking about the washer he must be using. I guess if I had a film or print washer I really trusted to flow fresh water across the surface, sure, I'd be all for the continuous flow model. But, in my little world, I have no trustworthy washer, and in that little world the fill and dump method is the rock solid dependable proceedure. I never have fully trusted the minimalist Ilford sequence, as stated, and have always washed using many more complete changes of water than Ilford's recommendations.

PE, what you write makes me wonder where one goes to know one's getting a really good washer. It seems every washer comes festooned with happy verbiage that proclaims it's "archival" credentials, but how many really get you there expeditiously? I suppose almost any washer would eventually bring fixation by-products down to some given level. How does one find a washer that is dependably efficient? With the high cost of what appear to be well made washers, I don't want to end up with a million dollar dog.

C

 

[dancqu]

... but I know this, that single wash baths are not efficient.
Here is the reason:

Wash 1 can only remove 1/2 of the chemicals from the coating.
This is a law of science shown by Mason.
Wash 2 can only remove 1/2 of the remainder using the same math.
Wash 3 can only remove 1/2 of #2.

And etc. You approach zero but never get there because the wash
water you use never has zero chemistry in it. It always equillibrates
with what was in the film from the past condition. PE

That is not correct. Common sense itself dictates other wise.
The volumes of fresh water each wash vs the remaining volumes
of contaminants is very lopsided in favor of the fresh water and
the more lopsided with each succeeding wash.

A somewhat typical example: A tank is drained of fixer. Within
remains only that fixer which adheres internally to tank and
film; perhaps 20ml +/- remains.

Add 500ml of fresh water then let soak with some agitation.
As a matter of practice the first soak need not be any more
than a rinse; 2 minutes will do. The great bulk of the
remaining fixer is removed.

With the second 500ml dose of fresh water we are primarily
cleaning the emulsion itself. Perhaps a 2ml equivalent of full
strength fixer remains. As a matter of practice the second
soak should be protracted and with some little agitation.
Fresh water diffuses inward, fixer outward. Good thing
emulsions are of gelatin and very thin.

The third soak with some little agitation should be yet
more protracted. Dan

 

[Curt]

Now consider running water. It is always zero in chemistry and as it passes over the film, the exchange is roughly double that in single baths and it can get to zero in the film (or a very very tiny amount).

How long would you suggest for a complete film washing time?

 

[Photo Engineer]

Well guys, I'll post it again. BTW, I have re-read Mason and Jacobsen along with the Kodak technical manual. And Dan, your common sense is not correct here. Common sense told mankind that the earth was flat too, and the sun revolved around the earth!

Here are the equations for washing:

Diffusion rate governed washing dX/dT = k(a - X) where a = thiosulfate in the emulsion, X = loss in concentration over T which is time. This is read as the change in concentration per unit time.

This is an exponetial when integrated as in:

k = 1/T * Ln( a / a - x) where Ln = Log base 2

So, if 80% washes out in 4 minutes, then 20% remains and 80% of that will take another 4 minutes. No matter what method is chosen, the residual silver complexes and hypo must have fallen to a level that gives the best image stability. Now, this equation only works at the instant of immersion when there is NO fixer or complexes in the wash water such as in freely running water with agitation.

As washing proceeds in still water or agitated non running fresh water, the equation becomes:

dX/dT = k[(a - x) - w] where w = the amount of salts built up in the wash water at any given time! The larger w becomes, the slower the wash becomes and in standing water (say any of the 5 or so changes you use) it becomes larger with time and is NEVER zero. In running water it can be made equal to zero.

In addition, with FB paper, this equation does not apply at all due to the cellular nature of FB paper and the washing is very sluggish and can take up to several hours. So, this works only with film and RC paper.

Mason goes on (as does Jacobsen) to describe the ideal wash being fresh water introduced into a final tank which overflows into the preceding tank and soforth for a series of tanks connected together. Jacobsen gives the diagram of this countercurrent wash which has been used for years by commercial photofinishers.

Kodak simply says "wash the film in running water for 30 minutes..... at a rate sufficient to achieve about 12 turnovers / hour...". For FB paper it is 1 hour.

Refernces: L. F. A. Mason of Ilford "Photographic Processing Chemistry"

C. I. Jacobsen of Pavelle "Developing"

Kodak B&W Darkroom Dataguide (2 suggestions - one for normal and one for archival use. I have quoted the archival above)

PE

 

[Nicholas Lindan]

the second soak should be protracted ... The third soak with some little agitation should be yet more protracted. Dan

It seems it should be that way on the surface (no pun intended).

But the time for the emulsion to come to equilibrium with the wash water is independent of the amount of fixer left in the emulsion. Once the emulsion has the same fixer concentration as the wash water then it is time to change the water - soaking any longer won't improve matters one whit.

One never waits for things to go all the way to equilibrium, 90% of the way there is plenty good enough. I use 5 - 10 minutes for each water change for no particular reason other than it feels right, is convenient, and yields zero color on the residual hypo test.

4 or 5 changes of water - assuming a generous ratio of water to prints and some agitation and shuffling - is all that is needed for fiber base w/ KHCA.

A word on residual hypo test: the solution is silver nitrate, and unless all the silver nitrate is then washed out of the print it will stain as the print dries - this doesn't indicate there is fix left in the paper - turning brown in the light is what silver nitrate does.

 

[David A. Goldfarb]

I'm making this one a sticky, since this is a question that we've all thought about, and there are some good posts here.

 

[Photo Engineer]

I've thought about this a bit more.

Look at "w" above in my post as "waste products" and then consider a bacterial culture that becomes self limiting due to production of waste. This is what happens. The wash becomes self limiting as "w" increases with time and the wash water is agitated but not changing. Therefore, the diffusion outward is slowed. If the water is running, "w" can be kept at close to zero.

Now, this does not mean that it cannot work. As I said above, there are two levels, "good enough" and "archival". Kodak and others recognize both. Your negatives should always be made archival, but prints are optional depending on use. Also, hypo eliminators and wash aids enter into this.

In the final analysis, I repeat "trust but verify".

Thanks David, the other thread like this has apparently been lost in the mist of time.

PE

 

[Lee L]

Ron,

Thanks for re-posting the Mason and Jacobsen info and equations. That was very helpful.

My Summitek Cascade print washer works with a very low flow rate on a principle like that of the countercurrent flow wash you mention in your post. It does 12 changes/hour for sequential 11x16 compartments at a 250 ml/minute flow rate.

Lee

 

[Photo Engineer]

Lee;

Every single source agrees that 30 minutes for film, and maybe less for RC in that device will give archival washing. The RC papers have thinner emulsions. Also, the fixer is important, the use of hypo eliminator, toning.... All of this is crucial in making high quality prints.

The articles allude to 1 hour for FB.

PE

 

[Lee L]

Lee;

The articles allude to 1 hour for FB.

PE

That's also Steve Peterson's recommendation for FB. (The other times you mention also match his. For other readers, Steve is the owner of Summitek.)

He quit manufacturing for reasons of low volume, but his web page says that his fabricator may take direct orders on some items.

Lee

 

[dancqu]

I use the Ilford wash method, modified on three counts.
First, after the first wash, I give the film two minutes in a
hypo clearing agent. I know you don't need to do this for
film, but it can't hurt. Then I do agitation cycle, except
I usually agitate more (20, 25, 30 instead of 5, 10, 15),
and I let it sit for a 30 seconds or a minute after each
agitation cycle. During this period I start cleaning up
the bathroom a bit (wash funnels, etc.) Seems to
work so far (knock on wood).

At least you do not run the water for 5, 10, or more
minutes. A running water wash, film, RC, or FB, is a
Most Inefficient use of water.

The Ilford method, fill & dump, is very efficient and
comes with a considerable amount of agitation; 5, 10,
and 20 inversions. In effect the time of each soak/wash
is increased with each change of water.

The first wash is short, removing primarily surface
fixer. Five spaced inversions should be plenty. The
second and third washes, IMO, should be more soak
and certainly no more in agitations; the 10 and 20.
Spacing those 10 and 20 I believe to be a good
idea. Since the method uses so little water
there is no reason to use it other than
at Room temperature. Dan

 

[Photo Engineer]

Dan;

The wash you suggest may or may not be good depending on operator technique and water supply. That is why I have given the original suggestion by Kodak and others here of a use of continuous water washing. If you use your method, it is virtually mandatory that the person test for residual silver salts and hypo if they wish to get maximum permanence.

I have given the data from Mason earlier in this thread. I also suggest that you consider that most people refer to two levels of wash, normal and archival. You should give some information on the differences if you are to "approve" a given method.

I have found, over the years, that the so called Ilford method is much more intolerant of error. Sorry. I still have to disagree with you.

PE

 

[pesphoto]

So long story short...what is the recommended way to wash fiber prints for archival permanance?

 

[Photo Engineer]

You didn't read the entire thread? Post 41 summarizes part of it.

OMG, then why did we have 5 pages?

PE

 

[jim appleyard]

Me thinks Mr. Photo has a dry sense of humor. Naughty boy!

 

[pesphoto]

sorry, no offense meant at all. This is a great thread!
Sorry PE, I just couldn't resist.

 

[Andrey]

What is it that we're washing out of film anyways?

What's it more soluble in? Water or gelatin?

 

[Photo Engineer]

Me thinks Mr. Photo has a dry sense of humor. Naughty boy!

Jim;

Dry does not go with analog photography! (well, except for Polaroid)

PE