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The placement of Iodide in emulsions

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This action takes on many forms that I hope to cover in this brief description. We often put Iodide into the beaker (kettle) when we start to make a bromo-iodide emulsion. This is usually in the range of 0.3% to 3.0 Mole % in published formulas. In many modern formulas that I am familiar with though, this can range up to 10%. I’ll get back to this!

Due to the huge difference in solubility between Bromide and Iodide, the Iodide ends up in the center, or core, of the emulsion that is made when it is used at the lower range. After all, the approximate ratios of their solubility in water is about 6000:1 in favor of Silver iodide precipitating. So, you end up seeing only a tiny effect from Iodide if used in the kettle from the start of the precipitation. If used on the surface, you are limited in use do to the fogging effect of Iodide if used at high concentration. In either case, you see a tiny increase in speed and contrast. The contrast effect is more pronounced if you add it to the emulsion after precipitation, as it adsorbs to the finer grains (which have more surface area) and these gain speed, thus increasing contrast. This latter method is used to control contrast in many photographic products. An example was Brovira paper.

However, adding Iodide smoothly during a precipitation could give us much more in both speed and contrast, but it is harder to do.

You can add it in a stream with the Silver, side-by-side and you can either keep the Iodide flow rate constant, ramp it up, or ramp it down. This has the effect of producing constant Iodide, increasing Iodide, or decreasing Iodide in the forming crystals. You can also add it with a stream of Bromide or mixed with the stream of Bromide. Doing this requires either 2 or 3 delivery systems, either pumps or syringes for example.

This can produce a high Iodide content AgBrI emulsion giving very high speeds.

The highest speed though, might be obtained as follows: Run AgNO3 into pure Iodide, thus giving AgI nuclei, and then, when you have run just enough Silver, stop and dump in Bromide and continue running Iodide. This way you get a core-shell emulsion with a smooth gradation of iodide out to the surface. This method is very complex in actual practice but produces some very fine grained, high speed films with ISO values of 800 or higher.

Perhaps the most interesting method of addition of Iodide, is based on the fact that KI is soluble in concentrated AgNO3. This allows the precise placement of the Iodide in the forming crystals. Unfortunately, this method cannot be used in production, because the equipment cannot be cleaned. Once you add water, AgI precipitates all over the surfaces of the equipment. AFAIK, no method has ever been found that allows one to use this unless the equipment is considered to be expendable.

It also limits one to a fixed maximum Iodide amount, and a fixed amount of Iodide placement in the emulsion.

I hope that this stimulates some of you to try some new things.

Have fun.

PE
 
The highest speed though, might be obtained as follows: Run AgNO3 into pure Iodide, thus giving AgI nuclei, and then, when you have run just enough Silver, stop and dump in Bromide and continue running Iodide. This way you get a core-shell emulsion with a smooth gradation of iodide out to the surface. This method is very complex in actual practice but produces some very fine grained, high speed films with ISO values of 800 or higher.

By 'dump', does that mean that the bromide goes in all at once/ over a very short period of time?

And, I know this is very arcane stuff, but does this method offer significantly faster/ more efficient (cost effective) emulsion making than more traditional methods? Or in other words, does this method have major similarities to the way that the most up-to-date emulsions are made?

It all sounds like something that would be fascinating to try out, however, is this the methodology that needs very high speed turbine mixers, or am I getting it confused with another type of emulsion making technique?

Anyway, another fascinating tutorial - thanks! :smile:
 
Thanks for the write-up. Very interesting!
 
By 'dump', does that mean that the bromide goes in all at once/ over a very short period of time?

And, I know this is very arcane stuff, but does this method offer significantly faster/ more efficient (cost effective) emulsion making than more traditional methods? Or in other words, does this method have major similarities to the way that the most up-to-date emulsions are made?

It all sounds like something that would be fascinating to try out, however, is this the methodology that needs very high speed turbine mixers, or am I getting it confused with another type of emulsion making technique?

Anyway, another fascinating tutorial - thanks! :smile:

Yes, the Bromide goes in all at once.

It does not make things more efficient, it improves speed and grain along with possible improvements in sharpness.

Turbine mixers? Where did you get that? Mixing is critical with some of these but I am curious about where you connected this.

PE
 
Yes, the Bromide goes in all at once.

It does not make things more efficient, it improves speed and grain along with possible improvements in sharpness.

Turbine mixers? Where did you get that? Mixing is critical with some of these but I am curious about where you connected this.

PE

Meant a homogeniser... - as per: (there was a url link here which no longer exists) & I had remembered 'turbine' without the specific phrase 'shrouded turbine'... A very good case of why I should not write a question at 2 in the morning...
 
Thanks for this information, its very interesting.
I am no chemist but I am tempted experiment. I do feel a bit unsure of where to start. Lets say I modified Mark Ostermans basic formula so that I precipitated the iodine into the crock like you suggest, rather then mix it in at the start.

----------

Marks is 3g of gelatin dissolved into 85ml distilled
Added to this 10.5g KBr and .4g KI

Then 12g AgNO3 is dissolved into 85ml distilled water then is precipitated into the gelatin-bromide-iodide mix.

-----------

I would need to dissolve the .4g of iodide with some distilled in order to precipitate it into the crock, but Im worried about adding too much water into the mix weakening the emulsion.

So would you suggest borrowing the water from the gelatin-bromide solution or borrowing it from the silver nitrate solution? Or maybe a bit of both?

Thus maybe:
----------------------
3g of gelatin dissolved into 56ml distilled
Added to this 10.5g KBr

.4g of KI dissolved into 56ml of distilled water, then is precipitated into the gelatin-bromide mix along with the AgNO3.

12g AgNO3 is dissolved into 56ml distilled water then is precipitated into the gelatin-bromide-iodide mix.
-----------------------

I hope that makes sense?
 
Meant a homogeniser... - as per: (there was a url link here which no longer exists) & I had remembered 'turbine' without the specific phrase 'shrouded turbine'... A very good case of why I should not write a question at 2 in the morning...

Generally, homogenizers will not work due to the shearing forces which can crack grains and cause fog. See my description there in your reference. We used what we called a PEPA or Planar Emulsion Precipitation Device. It has little hard contact with grains and no shearing force at all. You see, even prop mixers have a slight shearing force at the edges of the blades. I have described the PEPA elsewhere and included drawings in my book.

PE
 
Thanks for this information, its very interesting.
I am no chemist but I am tempted experiment. I do feel a bit unsure of where to start. Lets say I modified Mark Ostermans basic formula so that I precipitated the iodine into the crock like you suggest, rather then mix it in at the start.

----------

Marks is 3g of gelatin dissolved into 85ml distilled
Added to this 10.5g KBr and .4g KI

Then 12g AgNO3 is dissolved into 85ml distilled water then is precipitated into the gelatin-bromide-iodide mix.

-----------

I would need to dissolve the .4g of iodide with some distilled in order to precipitate it into the crock, but Im worried about adding too much water into the mix weakening the emulsion.

So would you suggest borrowing the water from the gelatin-bromide solution or borrowing it from the silver nitrate solution? Or maybe a bit of both?

Thus maybe:
----------------------
3g of gelatin dissolved into 56ml distilled
Added to this 10.5g KBr

.4g of KI dissolved into 56ml of distilled water, then is precipitated into the gelatin-bromide mix along with the AgNO3.

12g AgNO3 is dissolved into 56ml distilled water then is precipitated into the gelatin-bromide-iodide mix.
-----------------------

I hope that makes sense?

Yes, you can do this, and no, you cannot! Sorry, but this is true. You risk making huge foggy grains due to the higher concentration of ingredients. And here you have mentioned a KEY problem with Iodide addition to an emulsion without causing over dilution. Of course you need not worry about dilution if you use an ISO wash or Ultrafiltration. Both of these can remove the extra water.

PE
 
Thanks PE, I had a feeling the the extra distilled water needed to dissolve the iodide could present an issue. ISO washing and ultrafiltration sound more complex than I was hoping at this stage in my progress.
 
I show examples in the book and on the DVD. There are 25 books and about 5 sets of DVDs left.

PE
 
Does dumping the bromide all at once produce a more consistent grain size?
 
Probably. It actually starts precipitation of a Bromide shell over the Iodide core in this case. Therefore the crystals start by taking the form and size frequency distribution of the original Iodide core, modified by the Bromide preferred crystal habit. And that is why this one is hard to make.

PE
 
I show examples in the book and on the DVD. There are 25 books and about 5 sets of DVDs left.

For quite a while now Photographers' Formulary shows both the book and DVD as being sold out. Where can I buy it?
 
I'll check to see what is going on there. In the mean time, they are sold by Fotoimpex in Germany.

PE
 
I'll check to see what is going on there. In the mean time, they are sold by Fotoimpex in Germany.

PE

Thank you, Ron,
just ordered a copy.

Maybe some day I'll be able to make something like my favorite vintage films, the Perutz Silbereosin myself!?

Great having you here sharing your knowledge. :smile:

Greetings
Jens
 
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I've inquired at the Formulary and expect and answer soon.

I have some Perutz formulas here.

PE
 
...
I have some Perutz formulas here.

PE

Hi PE,

that's fine. Any information on making Perutz Silbereosin is very much welcome!
Especially on the dyes and the ripening process.
I'm doing photomicrography using a microscope from 1929 with vintage (mostly pre-war) 6.5x9 cm plates in the camera (Zeiss Miflex, 1930's). As the images are only 6 cm wide (and round) and I often use yellow-green filters, a fine grained ortho dry plate like the Perutz Silbereosin would be perfect, very low ISO is no problem.

Best wishes
Jens
 
In your initial post, PE, you’re describing, partly, what Edgerton, Germeshausen, and Grier sold to Eastman-Kodak in 1963-64. Extended Range Technology. Right?
 
Regarding EG&G, I am not describing this. It was well known in the industry AFAIK. Do you have a reference?

Jens, the formulas I have are not labeled as to product and are not slow in terms of the speeds of that era.

PE
 
...

Jens, the formulas I have are not labeled as to product and are not slow in terms of the speeds of that era.

PE

Hi,

... I see. I'll keep on looking for more informations. My J.M. Eder (Die Fabrikation der photografischen Platten, Filme und Papiere und ihre maschinelle Verarbeitung, 1930) doesn't tell much about this.

Greetings
Jens
 
Last edited:
I have two or three badly copied Perutz formulas from the '40s They appear to be incomplete to me. I'll check. They are put away in an avalanche of data here and will take some digging.

PE
 
I have two or three badly copied Perutz formulas from the '40s They appear to be incomplete to me. I'll check. They are put away in an avalanche of data here and will take some digging.

PE
That's very kind of You, many thanks!
Yours
Jens
 
I have your book now :smile: I'm on page 20, it's very good so far and looks promising. Ive learnt a few new things already. It may take me a while to get upto speed.
 
In your initial post, PE, you’re describing, partly, what Edgerton, Germeshausen, and Grier sold to Eastman-Kodak in 1963-64. Extended Range Technology. Right?

No answer from you on this, but I have been looking into it and the subject matter seems to be entirely different. The EG&G material seems to relate to deposited AgI crystals on various surfaces, done in a vacuum. The process I am discussing here is aqueous in a gelatin medium.

PE
 
What has led me to the assumption is the speed range EG&G had patented, ISO 0.004 to 800, three different layers at least.
Thanks for checking this, wasn’t aware of different technology. Gelatine-less films are an interesting subject like water-less
processing. Wasn’t a Japanese company engaged there?
 
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