"Golden Tetras" or Cubic Grains and the Tetradecahedral

[wildbillbugman]

Ray,
Thank you for confirming that the statement was not one of my hallucinations.
Bill

 

[Ray Rogers]

Where and when did this comment by Mitchell come about?

I'm curious because it really might have been true in the 80s in universities but no longer. In fact, as you know, most of Chiba and other universities are doing almost all digital work. It was not true regarding EK and Fuji until about the late 90s when they both started cutting back. And, the decisive year was about 2005.

PE

Hi Ron.

I believe this comment was made to Keith directly by Mitchell before he died. Timewise, I am not sure. It may well have been late 80's to mid 90's but as I said, I am not really sure at this moment.

 

[Photo Engineer]

Thanks Ray. I would have to seriously doubt Mitchell's comment then. (Not the reporting of it but the seriousness of his comment)

Kodak R&D in the 60s to 80s was about 20 years ahead of the pack from what we could discern in patents and the other literature. R&D was moving forward at a rapid pace, but was being kept as trade secrets for the most part. I wonder where Mitchell got this from? What gave him the idea?

PE

 

[Ray Rogers]

PE,
Someone said(it may have been you)that they were told to go to Japan if he wished to continue doing film research. Are there Japanese companies still doing commercial research in film?
If the internal cumbustion engine had not caught on, where might we be with steam today?
Bill

Ron, Bill;

I turned up this from Keith:

"Apparently, by the 90s, his [Jack Mitchell's] relations with Fuji were better than with Kodak and he told me that he felt that Japan was the place to be, for his research."

There may have been other comments but I guess this will suffice.

These comments by Keith are also noteworthy:

"I haven't researched the extent of his relationships with the companies, he gave me the impression that he was strongly opposed to any reporting embargo that is often imposed if we take corporate money to fund academic research. As such, Jack once told me that some of the money to support his research actually came from his family's own personal funds."

If this "sense" that Jack was opposed to reporting embargos has it's roots in the latter half of the last century, then it must have been a very significant and enduring issue to Dr. Mitchell, as it was his empassioned plea to Dr. Mees that the important work of Dr. Lowe was brought to the public, and that was in the very early 50's.

Ray

 

[Photo Engineer]

Interesting.

Well, even Mees says in the introduction to his book that he is unable to disclose certain pieces of information given him in confidence. This is, of course, the manufacturing technology that is confidential regarding emulsions. The same is true of Fuji. Neither company will discuss many trade secrets.

I know that Kodak had an ISO 400 film in 1965, as I was one of the internal testers. But, an ISO 400 film was not released until the Fuji release in the early 80s or late 70s. The technology was on the shelf, but was not used until there was some urgency attached as in this case, Fuji released their film before Kodak did. This type of example might be what Mitchell referred to. But, I know of no advantage at Fuji over what Kodak knew regarding couplers, emulsions and coating. In fact, until the 60s, Fuji was using extrusion coating, and Agfa type couplers along with Konica and both companies were doing hard R&D to catch up with EK. We had reports that some of their organic chemists and emulsion makers were sleeping at the plant and working double or triple shifts to do the R&D work that would enable them to catch up quickly.

So, I think that this is an "outsiders" opinion based on a "feeling" not on fact. Maybe based on emotion as well. A frustrated person. IDK for sure.

You know that I know Tadeki Tani and have had lunch and dinner with him along with Paul Gilman many many times over the last 30+ years, and yet we avoid this type of trade secret stuff and just hint back and forth. I also know Yasuo Wakabayshi of Konishiroku and yet we avoided this type of discussion.

We were working on catalytic imaging in the 70s and Fuji and Konica were dying to know where the R&D stood and whether we were ready to commercialize the products under development (and which products), but we could not tell them anything. They pumped us very hard for information but we were not allowed to even direct them to a specific patent, and the same would be true of Mitchell.

OTOH, Byrd often came to EK to consult and was given a lot of information under an NDA.

PE

 

[Ray Rogers]

I don't really know enough about it to speculate... but there is the Publish or Perish dictum and most scientists probably do want their name to carry weight. The whole thing of how and with what strings attached individual companies (as well as governments) are supporting research at institutes of higher learning, and manipulating free access to the knowledge gained is beyond the scrutinity of my vision.

I imagine the system of providing grants to researchers is source of the influence.
How much University level research is supported by private industry?

Perhaps someone reading this has some first hand experience they could share?

What does a NDA agreement actually look like?
Are they enforceable? Has Kodak ever had a NDA go bad?
What are the consequences of breaking a NDA?

As far as Mitchell feeling like an "outsider", you may be right. But I think Mees shared Mitchell's understanding of the importance of publishing... I think Eastman may have wanted to close the door compleatelly, but IIRC, it was Mees who saw to it that Kodak scientsts' work should be published. Perhaps as a compromise, the publications were first published as individual papers, and only later as a collection. Presumably, being published individually made it harder for Kodak competitors to benefit from Kodak Research than had the work been published under a single title.

As far as working day and night to catch up there is little doubt about that... but that was not really unique to the photographic industry... the Japanese have long had a catch phrase "追い付く、追い越す" ("Oitsuku-Oikosu" or "Catch-up, Then Pass") that describes this very real desire to catch up with the west.

I guess it is a good thing dinner doesn't get too technical.

Ray

 

[Photo Engineer]

Ray, I would say that the published to unpublished ratio of work at EK is on the order of 1:100. That means that a lot of work is never revealed.

An NDA can be one page long. It can state simply that I will not speak to anyone about this, or the following things will happen. I have signed several for EK over the years. They are now expired. They do have time limits. Usually it is 5 years past the end of employment for any reason. That is just one example. It can be "upon disclosure of this item by the company" or "disclosure of this item by another company". These are all valid statements but they are wrapped up in legalese. Consequences vary including fines and sudden unemployment or both!

PE

 

[Ray Rogers]

Emprisioned Knowledge

Ray, I would say that the published to unpublished ratio of work at EK is on the order of 1:100. That means that a lot of work is never revealed.
PE

If Mitchell was aware this, keeping in mind he was an outside specialist, I guess we can hardly fault him for his frustration.

 

[Ray Rogers]

...you get a variety of shapes and sizes which we call K grains (Klunkers). PE

I was recently looking at some X-ray emulsions and noticed that the grains seemed pretty much spherical. Sort of like bubbles... Would this sort of grain (possibly octahedral grains prior to ripening) have been given a new name to describe the post ripened shape? (such as "potato grains" ?)

Ray

 

[Photo Engineer]

Those were probably made with an Ammonia digest and would be considered rounded cubes or rounded octahedra. My ISO 40 emulsion is in that category. You may want to look at the SEMs that I posted here on APUG.

PE

 

[Photo Engineer]

Ray;

I can find no definitive work by Mitchell by using Google. I was wondering if you have a reference. Also, to which Keith are you referring as there are several around here.

PE

 

[Ray Rogers]

Ray;

I can find no definitive work by Mitchell by using Google. I was wondering if you have a reference. Also, to which Keith are you referring as there are several around here.

PE

Sure. I will retrive a couple and post them shortly.
Ray

 

[keithwms]

I am The Keith, Ron

I'll read through the thread and add any info that I can, though I don't know much about the subject at hand. What I do know from our conversations is that Jack had major disagreements with somebody at EK regarding hole sensitization and directions for further sensitization improvements in general. Whether these things made it to press, I don't know; I think I do have his complete biography and publication list, if that is helpful. What I recall is that a great number of his publications were in journals that don't have open online access. It was a real headache for me to track them down.

 

[keithwms]

PE,
Someone said(it may have been you)that they were told to go to Japan if he wished to continue doing film research.

That is what Jack Mitchell told me. He said it very pointedly. He said it like a mentor speaking to a student, i.e. listen to me, I know what I am saying, don't deal with EK, go to Japan (with a finger waving!). But that was a few years ago, and I think Jack and EK parted ways in the late 80s or so.

When I was going through his stuff after he passed, I found a number of items related to trips to Japan. Boxes of slides, phrasebooks, Japanese photographic lexicons etc. My impression was that Jack had very strong relationships with researchers in Japan, and if I remember correctly he got some sort of commendation from Fuji. Anyway, in the late 90s or so, Jack began to get the effects of Alzheimer's and his research stopped.

 

[Ray Rogers]

Ray;

I can find no definitive work by Mitchell by using Google. I was wondering if you have a reference. Also, to which Keith are you referring as there are several around here.

PE

Ron,

That would be Keith Williams.
He is offline now but I sent him a note to let him know why he is doing so much sneezing...

There is a curious nomenclature problem, Jack or John.
Whichever, I think both names referr to the same person.

The first few are from his time at the U. of Virginia:

John Mitchell
Faculty Publications 1995-1999

J. W. Mitchell, “ON the Role of Silver Molecules in Photographic Sensitivity,” Imaging Sci J 45 (1), 2-7 (1997).

J. W. Mitchell, “Role of Dislocations in Silver-Halide Photography,” J Imaging Sci Technol 41 (1), 1-12 (1997).

J. W. Mitchell, “Nanoclusters of Silver and Gold Atoms,” J Photogr Sci 44 (3), 82-86 (1996).

J. W. Mitchell, “The Basic Concepts of the Photoaggregation Theory,”
J Imaging Sci Technol 39 (3), 193 - 204 (1995).

He also edited:
Fundamental Mechanisms of Sensitivity
Butterworth and London
1951

and was involved with several other publications on photographic sensitivity.

Ray

ps: Ok, So maybe Keith isn't offline!
Things change so quick around here!

 

[keithwms]

Ray, I would say that the published to unpublished ratio of work at EK is on the order of 1:100. That means that a lot of work is never revealed.

I think this is true of all major research-based corporations and many gov't funded projects. If you are working on something small, it gets published. If you are working on something big, it doesn't get published. At least not for many years.

NDAs are the bane of my existence. Well, those and MTAs (materials transfer agreements) which can be even worse.

 

[Photo Engineer]

Thanks all for the clarifications.

Given what Mitchell said, I believe it was due to the fact that he was not given a lot of information by EK researchers for one reason or another. I know that George Byrd was given all of the facts available though and I met with him several times with specific orders to disclose all! I'm not sure, but I believe that Byrd was with Princeton at the time.

PE

 

[wildbillbugman]

Those were probably made with an Ammonia digest and would be considered rounded cubes or rounded octahedra.

PE

RE,
Will the use of high levals of Br in relation to Ag also serve to round corners?I mean all of the Br in the batch prior to any Ag adition.
Bill

 

[wildbillbugman]

Another question about rounded corners:
Will speed and duration of mixing serve to round the corners? Reduce crystal size? Perhaps the relatively low shear of a magnetic stirring bar would do niether?
Bill

 

[Photo Engineer]

Bill;

High bromide will not help form cubes to allow rounding of corners, but if you add a lot of bromide after the cubes are made, then you have created the conditions that there may be some rounding due to solvency effects during digestion.

Speed and duration of mixing may or may not influence this effect. Generally, IMHO, it does not. Neither does addition rate. Addition rate affects size and grain size distribution. Of course, slow mixing will tend to create a greater mix of crystal types or even an unusable emulsion. I have done that with some makes with poor mixing at small volumes of starting materials.

PE

 

[keithwms]

Given what Mitchell said, I believe it was due to the fact that he was not given a lot of information by EK researchers for one reason or another.

That could be it. My understanding was that Jack had some results for new ways to sensitize that EK didn't want to invest, and ther was a particular person at EK with whom he had a falling-out over this. So Jack went to Fuji. Of course, higherups at EK and Fuji must have known already that the heydays for research on silver halide sensitivity were over. As you have noted elsewhere, there is a *lot* of fantastic research on the shelves that may never go to market.

Anyway, like I said, I know nothing of emulsion science. I would just guess that a crystal with well defined electron and hole migration paths would be advantageous. The surface mobilities of the electrons and holes on the crystal must be very important. If the particle is faceted then I guess there will be sensitization hotspots, and I imagine the sensitizers adsorbing preferentially in a number of clusters related to the number of facets (or perhaps facet boundaries).

 

[Photo Engineer]

You left out "twinning".

We have investigated just about everything you can imagine. Think about this... Maybe we had already done what Mitchell was proposing and either found it a dead end or were using it as a trade secret. In either case, we would not divulge anything about it. In fact, his going to Fuji in either case would have been an advantage to EK and we would probably have let him, if he ever threatened anyone that he would do it.

PE

 

[Ray Rogers]

You left out "twinning".

His going to Fuji... would have been an advantage to EK....

PE

That was an erie smile... (PE) and a critical omission (Keith),
since that is exactly where this research was put to use!

How did Kodak benefit by Mitchell's ideas being used by a competitor? !!

 

[Photo Engineer]

Ray;

I think you will find that Kodak used twinning as well. In any case, thin t-grains were a Kodak invention and a Fuji invention at the same time, then Fuji, IIRC, moved towards thicker t-grains. IDK the exact sequence, but this was a fast moving field. And, Anabelle was working on 2 electron sensitization while Paul was working on dye layering.

These latter two allowed Kodak to surpass anything anyone else was doing. It gave them at least 1 - 2 stops in speed with the same size grain (each method) and when combined it gave 2 - 3 stops. This has given them a commanding lead in Motion Picture films, just when no one needs it. And, you see, we are back to the original question - ie. what might we have seen in the absence of digital?

PE

 

[Ray Rogers]

Ray;

I think you will find that Kodak used twinning as well. In any case, thin t-grains were a Kodak invention and a Fuji invention at the same time, then Fuji, IIRC, moved towards thicker t-grains. IDK the exact sequence, but this was a fast moving field. And, Anabelle was working on 2 electron sensitization while Paul was working on dye layering.

These latter two allowed Kodak to surpass anything anyone else was doing. It gave them at least 1 - 2 stops in speed with the same size grain (each method) and when combined it gave 2 - 3 stops. This has given them a commanding lead in Motion Picture films, just when no one needs it. And, you see, we are back to the original question - ie. what might we have seen in the absence of digital,

PE

Yes, quite right. The nursing and pampering of tabular grains was a Kodak moment even though technically, the tabular grains themselves were not really invented, but had been formed inadvertenly many years earlier. (I would say that it was actually the emulsions that used tabular grains that was invented but anyway, getting back to the thread...)

I think the issue here was latent image dispersion and how to concentrate the electrons in, to use Keith's words, an optimum "hot spot".

I have not really looked at the work directly, so I am only guessing but if Anabelle and team was looking at Mitchell's work at the same time as they were working on 2 electron sensitzation, well, likely they would have been less impressed, but I think you are correct and we do come back to where we would be today (and tomorrow!), in the absence of digital.