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Tuesday, 22 March 2022

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...rolls of unexposed film had expiration dates...

They still do. :-)

...What I learned is that the latent image on black-and-white film is at peak integrity for about six hours after exposure. Then it goes through an initial period of deterioration lasting days or weeks; then it tends to mostly stabilize again, and further deterioration becomes slower and more gradual...but continues...

What I've learned is that much of what was true about commercially available silver halide imaging products in the 1980s no longer holds today. Both the deterioration mechanisms and their associated times might or might not still be applicable. Testing is the only way to find out, and there's not sufficient market volume to support such rigorous experimentation. Thus, a practical strategy is to simply "process promptly after exposure."

From the New York Times, By John Durniak, June 20, 1993: In Summer, Film Needs Special Care.

Thank you for reminding me I have (exactly) 3 rolls of HP5 waiting. I usually catch up within 3 months or so. I am more guilty of not looking at the developed films, other than a quick inspection whilst storing in sleeves. Save for some rolls I was eager to check, my backlog goes back a few years.
Same goes to my digital files I'm afraid...

Didn't Garry Winogrand leave behind a ton of unprocessed film when he passed away? I'm trying to remember what became of it all, and how it looked if it was processed.

Ack, you reminded me of a single roll of Tri-X from January I have neglected to develop. And you cost me $1.29 several times over for alternate versions of "My Back Pages". But a small price for your trenchant insight!

I read that story before seeing it linked here, and I thought of that documentary on Vivian Mayer where sadly she was gone before the windfall of previously unseen film was found. If they don't delay, they can actually get some context from the photographer which can be useful.

Hope they don't put off getting the film processed too long. The shooter has made some chronological errors when naming his gear used, so maybe remembering the events and rough dates might be less that accurate.

Allow me to put on my (retired) chemistry professor hat and respond to this:

“(When testing the pop hypothesis that "fixer is heavier than water and sinks to the bottom of the print washer," a canard promulgated by a prominent snake oil salesman at the time, Phil mixed stock fixer and water 1:1 and let the bottle sit for a year before very carefully removing samples with pipettes from the top and bottom of the bottle and testing them. He tested and measured everything, even when theory alone was more than robust. He was patient that way.)”

First and foremost, using the word “heavier” in this context is nonsensical; the correct term is “denser”. This is because the relevant property is not mass but rather density. One gram of silver and one gram of water both weigh the same, i.e. neither is heavier than the other. However, silver has a density of 10.5 g/mL and water has a density of 1 g/mL. Note the difference in units… mass (weight) is measured in grams while density is measured in mass per volume (grams per milliliter in this example).

Secondly, fixer (minimally a solution of sodium thiosulfate/hypo in water) necessarily has a greater density than does water. If you add a non-zero mass of anything to water and (as it is in the large majority of cases) the increase in volume is small then the density of the solution will be greater than that of water. To put some concrete numbers to this, if you dissolve 10 g of anything in 100 mL of water and get 101 mL of solution the density of that solution is 110 g per 101 mL or 1.09 g / mL (i.e. greater than water).

Furthermore, if you carefully (i.e. minimize turbulence/mixing) add a solution that is denser than water to water, it will tend to sink to the bottom of the container and form a distinct layer there. You can test this for your self take a long narrow glass and add some colored (with food coloring) water to it. Then carefully drip some corn syrup down the side of the glass and watch what happens.

How does this relate to fixer and print washing? Well, if you place a not particularly well drained print into a static container of water, I can imagine that the bulk fixer (i.e. the solution) clinging to the print might possibly fall to the bottom of the container.

However, most of the hypo than needs to be removed from the print is contained within the emulsion and must diffuse into the water from the paper rather than dripping off the paper like the bulk solution. The portion of the hypo diffusing out of the paper will not have any tendency to settle out at the bottom of the container.

Going back to the bulk fixer that might be dripping off the paper, one would need a very poorly constructed print washer, with essentially no turbulence/mixing of the water in it to get any settling out of the fixer solution. You can see this if you try the experiment I outlined above. You will find that it actually takes great care in adding the corn syrup to the water in order to end up with two distinct layers.

Lastly, Phil’s experiment (which is, again, chemically nonsensical) and the whole canard is based on the fact that “fixer” (even in narrow photographic terms) is used sloppily and has two distinct meanings: “Fixer” can refer to both the solution of hypo in water, as well as to the chemical entity thiosulfate/hypo.

Phil’s experiment is nonsensical because of Brownian motion/diffusion. This keeps molecules/ions (such as hypo) in solution from settling out as Phil hypothesized. In fact, if you take a two-layer system (such as the water/corn syrup experiment), cover it, place it in an out of the way spot and observe it periodically, you will find that over time (months) that the boundary between the two layers will become “fuzzy” and that if you wait long enough you will end up with a single uniform layer.

In conclusion, my chemist’s view is that the “settling out” of fixer (i.e. the bulk solution dripping off a print) in a print washer is possible, but unlikely. In the end this is irrelevant because the “important” fixer is the thiosulfate which had soaked into the emulsion and which cannot “settle out”.

Loved the homage to Dylan.


I was taught that about lightened image deterioration as well, but also that Kodak designed some films to be more resistant to it than others. Verichrome Pan was the most famous for being designed to take that sort of abuse.

I didn't know about your involvement with T-max. That would be an interesting story. My experience with T-max was that it was so different from earlier films that I found it to be disturbing and really wondered what Kodak was trying to do when they designed it.

If I don't have time to develop the exposed film, I put them in the fridge, hoping to slow down any degradation.

[As I recall, that doesn't actually help. --Mike]

Hoo-wee. Wish I'd known this a long while ago....so now all I can do is hope some of the degradation is "artistic"...

I am in Boston and saw this article in the Globe last week and it is fascinating. The gofundme was raising $30,000 to get the film processed. With that amount of film and the subjects he had access to, there are certainly some diamonds in there. I'm actually very surprised that an entity like the R&R Hall of Fame, Rolling Stone, Getty and the like did not just swoop in, offer $100k, promise to scan it all and credit him, but assume ownership. The photographer is very old and sounds quite ill. Money is not really the goal - clearly. But having a guarantee that an interested party with the means to do the scanning and archiving properly would seem to satisfy the primary motive? Looking forward to seeing the yield from this stash of film. Hopefully it gets done well.

Now, how come I never heard of the fast immediate degradation back when it could have done me some good? Not that I could have gotten film developed that fast very often (I mean, if I'm off at a convention for 4 days and shoot a dozen rolls of film, ain't nothing getting developed until Monday or Tuesday at the very earliest!).

Wait, and refrigerating doesn't help? I'm not believing that one; it's a chemical reaction, all chemical reactions are temperature-sensitive. Maybe it doesn't help much. (Of course going down even to freezer temp, 0F, isn't that much of a decrease in actual thermal energy, from room temperature of about 300K; so maybe it helps in theory but it's not measurable, or something.)

Also, you developed 3 rolls at once? I had 2-roll tanks and 4-roll tanks, I know 1-roll and 6-roll existed, but I've never heard of 3-roll stainless steel tanks (for 35mm film; I guess the 6-roll would take 3 reels of 120 nicely). And of course nobody serious developed 35mm B&W in anything other than stainless steel tanks and reels (perhaps that is where we diverged? but you're not THAT much younger than me).

The longer-term degradation was well-known of course (if not exact details), and there were even some ways to attempt to compensate for it (anti-fog agents, and pushing just a bit, as I recall). Also...the Winograd old rolls were probably developed using some of those techniques, plus the printer probably compensated as much as they were able. So, the differences visible in the book are after best efforts to hide them!

The degradation in decades-unprocessed Kodachrome is even worse -- since you now have to cross-process it :-) .

According to the quoted Kodak statement (I cannot access the cited publication), refrigeration slows degradation of exposed film, but best just to develop promptly.

https://photo.stackexchange.com/questions/60822/can-i-store-exposed-film-in-the-fridge-when-it-was-stored-before-shooting-too

Here is my old film story:
Back in November of last year, I was given a couple of boxes of 4x5 black and white sheet film that looked to be from the 1980s. One box contained 19 sheets of Kodak T-Max 100 and the other was a box of Kodak Graphic Arts film. Inside the box of Graphic Arts Film was 12 sheets of Kodak Tri-X, I could tell by the notches while in the dark.

On a hunch, I figured that maybe the Tri-X might have already been exposed at some point so I developed one sheet. Low and behold there was an image on the Tri-X film. So I processed the rest of the Tri-X using Kodak HC-110 film developer that I normally use with an extended development time that I would normally use. All 12 sheets of the Tri-X had some images on them of various quality.

Someone had made some close-up pictures of a rock within a wireframe and of plastic flowers against a black background. I had no idea when they were originally exposed or why. The pictures were well lit and sharply exposed. However, as you mentioned in your post the pictures on the negatives once developed had low resolution, mostly from fog, developing spots, strange bloom patterns.

I ended up scanning two of the better negatives as the rest were too under-exposed to really show much and they were of the same subjects anyway. I thought it was interesting that someone made some pictures way back when and stuck the undeveloped film away and never bothered developing the film. I contacted the fellow who gave me the film and he said he got it from someone else.

Oh yes, I also exposed and developed the old T-Max film using my Ebony 4x5 view camera and that film also had low resolution due to fogging, plus the bloom patterns.

Mike—Perhaps it might be of benefit to your readers to point out that all of this talk about color film processing pertains only to color negative film—not to color reversal film. Many serious film photographers—and a majority of the pros that shot for magazine and periodical publication—seldom used color negative films; they predominantly shot "slide" film. The latter exhibited widely varied characteristics with respect to pre-processing stability. Kodachrome films were especially stable; some rolls that were later recovered after decades of pre-processing storage still looked quite excellent. Of course, deferred processing always invited undesired risk; storage temperature and the presence of moisture was generally a more significant determinant than time alone.

From 1947 (at age 16) until ~ 2008, I personally shot reversal ("slide") films almost exclusively. I began with K10, then came K25. The "fast" Kodachromes (to ASA 32, 50, & 200) and Fuji's superb Velvia slide films all came later. Ektachromes and Agfa slide films were, in my opinion, vastly inferior. They also faded much more rapidly.

My personal interest was in nature and wildlife (mostly birds) photography. Viewing was normally done on a light table, with display by projection, using 50 and 60 inch portable screens. The projected images were sometimes magnificent; far superior to any amateur digital projection that I've seen to date.

Mike,

That last line is a corollary to the film knowledge. A good song isn't always ruined by a bad voice. :>)

I don't remember where I read that film should be developed promptly, but I think the Kodak film boxes had such a warning. There were probably many such sources of that kernel "back in the day".

On the other hand, Vivian Meier's photos don't look bad -- at least not in the books I've perused. (Although, I wasn't paying very close attention to the image quality compared to the terrific "photo scenes" in the prints and I don't know which prints were made with film that had sat a while before developing.)

The book prints might not have shown any obvious degradation (to my uncritical eyes), while prints on photo paper would have.

From the Library of Congress ...

Care, Handling, and Storage of Photographs
https://www.loc.gov/preservation/care/photo.html

**For color photographs and film negatives, temperature is the controlling factor affecting stability. Storage at low temperatures (40°F or below) is recommended. For more information on cold storage see National Park Service.

And from the National Park Service ...

What Cold Storage Is and Why We Need It
A long term preservation strategy for Film-Based Photographic Materials
https://www.nps.gov/museum/coldstorage/html/intro1_1.html

[Yes, but that's "for color photographs and film negatives." We're talking about a different subject. I'm not saying your citations might not be useful. --Mike]

Many years ago I read about an Arctic / Antarctic expedition in the first half of the 20th century in which the participants died.
30-40 years later, their remains were found by another expedition, including the exposed B/W films. These negatives, developed decades later, had supposedly shown surprisingly good quality, ostensibly because they had been frozen in the snow all that time.
Of course, I don't know if they would have passed a densitometer test ...

What about putting a lot of potassium bromide in the developer?
My favorite developer, in fact the only film developer I used from about 1980 on was D-19 which among other qualities worked wonders with government surplus aerial photography film that was 29 years out of date.
I suppose highlight degradation is the opposite of shadow fog but I imagine Charles Daniels rock and roll photos might actually be enhanced by the noise in the process. When you think of D-day photos which are the ones that are stuck in your memory?

Mike—Re. your response to Richard Man, I think that your recollection might relate to batteries, rather than film. After all, we do know that virtually every major photography equipment retailer selling film to the public always stock their color reversal films in refrigerated cabinets. Perhaps (?) they stow B/W and color negative films on shelves subject to ambient exposure, but I do know that slide film is always refrigerated, presumably per the Kodak and Fuji guidelines. There's some 70+ years of adherence in support of this practice, so it must stem from solid research.

[But that's unexposed film. We were talking about latent image stability. --Mike]

"Latent Image Stability",Basic Photographic Materials and Processes, p202.

Mike—If cold storage is beneficial in retarding film emulsion degradation in the pre-exposure state, it's quite likely to be of benefit in post-exposure storage.

(I think my initial comment did not come through, I must have missed the captcha box a few times, so here goes...)

Thank you for reminding me I have exactly 3 rolls of HP5 waiting to be developed. My tank takes 4 rolls so I tend to leave them. I usually catch up within 3-4 months, but then again I'm no Master Blaster.

Gosh Mike, this post hits too close to home. Dick (and Sally) Dickerson are very close friends of my mom and dad. My dad would certainly be happy to regale you regarding stability of latent images in silver halide emulsions, but since his stroke from a couple years ago, it would likely be a hard slog for him. As you mention, that gray matter storage medium doesn't take kindly to aging; in the case of my dad his output device interface is pretty screwed up as well. I'm hoping to get to visit my folks in a couple weeks--they were both in the ER last week (at ages 94 and 93). I'll at least print out this article and let dad read it--I doubt I'll get a very verbose response but I do think I'll get a huge smile. He loves your writing, and this stuff is what he did for 40+ years.

Cheers!

I strongly suspect that deteriorated image quality (as we use those words) is a plus in this kind of thing.

These stories of long-buried photo gold always fascinate me, and Mr. Daniels’ sit is a peach. But the longevity of film emulsion, an unknowable answer, seems beside the point. Given Mr. Daniels’ age and apparent health he should seek someone willing to buy the whole set of undeveloped rolls as a single undeveloped archive. It could be a real win-win. Daniels gets a block of cash to ease his last chapter and the buyer might get a real deal on this unseen work for a relative bargain.

But this can’t drag on. The market for photos of mid-century early rockers is already near saturation…and shrinking daily!

Good to know. Thanks!

Weren't many of Vivian Maier's pictures bought as undeveloped film?

I should have researched a little longer before hitting "post" on my last comment ...

From a Kodak article titled, "Storage and Handling of Unprocessed Film" ...

Maintaining Film Quality with Refrigeration

Exposed Unprocessed (sealed in cans), Short Term (less than six months), -18 to -23C, RH below 60%. Long Term (more than six months), Not Recommended,

https://www.kodak.com/content/products-brochures/Film/Storage-and-Handling-of-Unprocessed-Film.pdf


See this from filmphotographyproject.com:

https://tinyurl.com/2wpjsw8m

"... Storage at a low temperature after exposure will retard latent-image changes. You can keep exposed, unprocessed film in a refrigerator for a few days when necessary. Put the film in a sealed container, and allow the unopened container to reach room temperature before removing the film for processing."

Maybe you could invite them to write about this a little more.

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