New Products

[David A. Goldfarb]

As I recall the patent that described the precursor to Type 55 used amidol. I think I've posted a reference somewhere around here, and maybe the full formula. It might be in Haist's _Monobath Manual_. As to whether any actual version of Type 55 used amidol, I don't think we know.

 

[Ian Grant]

David, I think there was something in that Monobath article I sent you. I'll try and find it.

Ian;
My published SuperFix is as far as I would go right now. Perhaps you have some suggestions?

PE

There seemed to be another avenue, something I saw in some Japanese Patents, I need to go back to them & re-read. A clue was that the type of stop-bath could aid the solubility of transitional silver/sulphur complexes helping shorten effective fix times substantially.

Ian

 

[Photo Engineer]

As I recall the patent that described the precursor to Type 55 used amidol. I think I've posted a reference somewhere around here, and maybe the full formula. It might be in Haist's _Monobath Manual_. As to whether any actual version of Type 55 used amidol, I don't think we know.

I will have to look it up as well.

Amidol goes bad pretty fast in solution regardless of addenda. It may take the super high pH of the pod goo and the inert prep. atmosphere to make it work.

If that is so, then no real tray or tank developer could use this method. The pH of the goo is about 12 - 14 depending on product.

PE

 

[nighthawkjw]

A replacement for Kodak's HIE-135 infrared film! PLEASE!!! My supply in deep freeze is running out!

 

[Photo Engineer]

Said it before and I'll say it again.

NO IR!!!

PE

 

[keithwms]

haha, yep, IR is brutal. Nobody wants to market that stuff. Even for Kodak, quality control was very difficult with HIE.

Why not use superpan or efke or such and figure out how to make it halate more. Maybe put foil behind it.

 

[David A. Goldfarb]

A monobath for silver diffusion transfer from Haist's Monobath Manual (136-37) from BP 987,764 (1965), assigned to Polaroid for use with "a fine grain, silver iodobromide film, said to be substantially similar to Kodak Panatomic-X Film but with an emulsion thickness of about 0.002 inch"--

Water--180 cc
Sodium carboxymethyl cellulose (high viscosity)--6 g
Sodium hydroxide--9 g
Sodium thiosulfate (penta)--10.8 g
Amidol--7.2 g
Ascorbic acid--1.8 g
Sodium sulfite--6.5 g

Processing time of the neg in contact with the image-receiving sheet about 10 sec.

Sound familiar?

 

[Photo Engineer]

Yep.

It does not keep very long though in a bottle or tray. Amidol goes bad fast, and the Goo is especially bad.

PE

 

[David A. Goldfarb]

If that was the formula for Type 55, I guess it depended on the pod being reasonably airtight. Once it went through the rollers, it only had to last for 10 sec.

 

[Photo Engineer]

The pods were airtight and sealed under an inert atmosphere.

PE

 

[msdemanche]

Is there anything paper wise that is like Protiga number 3 grade? I have tried many fiber papers and still no cigar. I know that it was never a Kodak product but it is like my old love lost.

 

[Photo Engineer]

Portriga, Brovira and Kodabromide were somewhat similar. It might be possible to reproduce it given the Agfa published formulas.

PE

 

[Ian Grant]

Portriga, Brovira and Kodabromide were somewhat similar. It might be possible to reproduce it given the Agfa published formulas.

PE

Portriga and Brovira were very different, like chalk and cheese.

Portriga can't legally be made again because of it's high level of Cadmium. No company has been able to make a warm-tone paper remotely similar to the now banned emulsions & paper that incorporated Cadmium. Only Forte with help from Bergger got close with Polywarmtone.

It is possible the same know how might have gone to Foma & EFKE.

Ian

 

[Photo Engineer]

Ian, I have seen warm Brovira formulas with and without Cadmium and I have seen warm Portriga with and without Cadmium. The Brovira mostly used Rhodium and Ammonia while the Portriga were very similar but used no Ammonia or used Ammonium halide salts rather than Ammonium Hydroxide. I have also seen Lead salts used to yield warm tones as well as Cupric salts. Therefore, I maintain that the formulas are rather similar, ie. single run Chloro/Bromo/Iodide with either a lot or just a tad of Ammonium salts added.

You could easily start from one formulation in the kettle, one for the Silver Nitrate solution and then with a set of addenda go anywhere. I remember this, Brovira used Blei Nitrat (Lead Nitrate) to achieve a warm tone as an example. Much of the use of Cd salts goes to adjusting the curve shape as we found designing papers without Cadmium, and therefore there are many substitutes. A Cupric Ammonium Nitrate complex was often used.

PE

 

[Ian Grant]

Warm Brovira is an Oxymoron, there were variations but not remotely as far as Portriga

US papers were often quite different to European papers, The whole ethos of Photography was different between Europe & the US,particularly in the inter war period, 1918 - 1939.

Cadmium played a far greater role in European papers than it must have done, from your experience, at Kodak. It was critical in the rich & varied warm-toned papers made around Europe by a wide variety of companies. Agfa, Kentmere, Bergger all struggled to manufacture papers that were even close to their former Cadmium incorporating product. Ilford at that point weren't making a Warm tone paper.

Yes you can sometimes find Cadmium free versions of some of the papers incorporating Cadmium because it's not needed in every grade !

Ian

 

[Photo Engineer]

Nevertheless, there is a Warm tone Brovira which uses Lead Nitrate.

And this variation in formulas makes my point. You can find formulas that overlap so much that they are more similar across product lines than different.

Kodak used Cadmium in Cl/Br/I emulsions to mainly control curve shape.

PE

 

[Ray Rogers]

Ian,

What do you consider it to be the "ultimate" or "standard" warm tone emulsion, and Why? Which exact paper do you feel can/could not be duplicated without the Cd?

Can you specify exactly what qualities it is you feel are unattainable w/o cadmium? It is not clear to me what you are actually saying... some exact tone or hue could not be obtained? The toned end-result was never identical?

Also, to which paper are we comparing the Cd free emulsions to?
Portrigra? If so, which one and which grade?

I think you are thinking more of toning behaviour than anything else,
and while that certainly is one characteristic, perhaps it is not as fundamental as is the normally developed tone... I haven't decided yet.

Perhaps it was not so much that it couldn't be done as it was a case of not having the knowledge, or willingness to do sufficient research.

In any case, it would have been nice to discuss this with you at length in person when we (almost) had the chance... well, maybe next time.

Ray

 

[Photo Engineer]

I found my reference Ian!

Portriga Rapid Normal was a mixture of Brovira Braun Normal and Brovira Braun Weich. The Braun's were warm tones achieved by addition of a Farbstoffgemisch konstitution hier unbekannt. So, presumably a brown dye or warm dye was added to dye the image somehow to achieve very warm tones.

The blend of 2 emulsions would lower contrast of the Brovira to the level of the Portriga line. Also, the Portrigas were noted for long addition times just as the Broviras were noted for their shorter addition times. The use of the Broviras to make the Portriga Rapid was because the speed of Brovira was higher. Brovira was also green sensitive whereas Portriga apparently was not.

PE

 

[Ian Grant]

By the time I began using Agfa warm tone papers Portriga Rapid was down to one surface and a few grades, it did have an off-white creamy emulsion or base colour which may well have come from the addition of a brown dye. It was once common to sell variations of a paper, a good example would be Kodak Bromesko, which in 1961 was available in "Fifteen tint/surface/texture combinations." (Kodak advert B.J.Photography Almanac 1961, that's 2 more than in a similar advert for 1954.

The important word there is "Tint" because that was one way to give a richer looking warm-tone look. Some people try and emulate this by giving a print a short soak in dilute tea or similar.

Ian,
What do you consider it to be the "ultimate" or "standard" warm tone emulsion, and Why? Which exact paper do you feel can/could not be duplicated without the Cd?

Can you specify exactly what qualities it is you feel are unattainable w/o cadmium? It is not clear to me what you are actually saying... some exact tone or hue could not be obtained? The toned end-result was never identical?

Also, to which paper are we comparing the Cd free emulsions to?
Portrigra? If so, which one and which grade?

Ray

Ray, I've not had the chance to find the "ultimate" or "standard" warm-toned emulsion, that may have been something like Gevaluxe, manufactured by Gevaert, but the era of the rich warm-tone papers had passed by the time I became seriously involved with photography.

The closest paper was Agfa Record Rapid, in the 80's. This was an extremely flexible paper, it exhibited all the classic features of an old fashioned warm-toned chloro-bromide emulsion. It has a good white base, gave clean whites, so had no dye incorporated.

Those features were:

Excellent tonal range.
Very responsive to different types of developer, cold tone, warm tome, soft working, etc.
Capable of a very wide shift in image colour without toning
Responds well to use of exposure/development to change image colour
Predictable, repeatable results.

Perhaps the most important of those was the degree of control using exposure & development time. If you look at a developer Formula like Ilford ID-4 or Gevaert.262 times are listed for Warm black, through Sepia, Red-brown to Red but exposures had to be increased substantially, development times cut, or developers heavily diluted and often additional bromide added.

So what these papers had was flexibility. That changed at the end of the 80's when Cadmium had to be removed from the papers. Record Rapid was re-formulated, Agfa did a good job in getting relatively close to the old version but a part of the flexibility was lost.

The new version wasn't capable of the very wide colour shifts
Was less responsive to exposure and development controls
Prints on the new version couldn't reproduce the same tonal range/image colour.
Overall the paper was less warm-toned.

The new Record Rapid was good but subtlety different, put two prints side by side one made with the old version and the other with the new (final) version and there is a perceptible change in the balance of tonal range/image colour, a slight richness is lost. The differences really have to be seen they are quite difficult to describe.

Agfa finally replaced Record Rapid with Multicontrast Classic (MCC) which was an excellent variable contrast replacement. No longer called a warm-tone paper it still had a reasonable degree of flexibility.

Other warm-ton papers I used occasionally like Kentmere Kentona also changed significantly after the removal of Cadmium.

There are still people out there with the right knowledge trying to keep good papers on the market and bring out new ones. Guy Gerard of Bergger for instance, has the expertise from his time at Guilleminot and used this in conjunction with Forte to produce excellent papers, which lead to improvements in Polywarmtone making it a very popular paper. Bergger are now working with Ilford. Others like Wolfgang Moersch and Mirko Böddecker have worked closely with a number of companies including Ilford/Harman Technologies. Mirko in particular with EFKE, Forte (before closure), Ilford and also with equipment bought from the liquidators of Agfa resurrecting papers and films previously made by Agfa.

There are currently 3 key coating facilities in Europe, Ilford, Foma and EFKE all with flexibility and and the ability to make great B&W papers. This years has seen the introduction of new warm tone papers:

Adox Fine Print Variotone, (made for Adox by Ilford)
Bergger Prestige fibre based papers - warm tone (made by Ilford for Bergger)
Fomatone Natural 532 II, a replacement for a discontinue paper
Adox MCC - first test batch - replace Agfa MCC (coated in Germany)
(Adox MCP - RC paper Neutral/Warmtone - coated in Germany)

These join a variety of other warm tone papers currently produced by Ilford, Kentmere, Foma and EFKE.

Ultimately we have to use what's now available, all these modern papers are different. You have to adapt your techniques and move on.

Ian

 

[Ray Rogers]

Thank you Ian for that informative post.

I think I am beggining to see what you are saying...

You are not really sure what might be the "King" of warm toned papers, not having been here on Earth when they were in common use, but think it might have been something like Gevaert's Gevaluxe, possibly. In anycase, after its demise, and during the period of your active interaction with warmtoned paper (the 1980's) the closest paper to that "ideal" may have been "Agfa Record Rapid". You note that it's post Cd version was much less responsive to exposure and development controls and were less warm-toned.

In summary, what you are saying is that these papers:

1.
Had more flexibility.

2.
Were warmer.

3.
Became less flexible and less warm when the Cd was removed.

If this is what you are saying - Well, Yes.

But, the flexibility you refer to here is not a characteristic of warmtone papers but slow bromochloride papers, of which there are I imagine cold, neutral and warm examples.

Your claim that the orginal, older emulsions are warmer than the post Cd emulsions is important but the loss of flexibility you point out, if true, may really be the key here.

I suggest that it was not the removal of the Cd, but a reformulation of the basic emulsion that caused the loss of both the flexibility and warmth of the older emulsions.

In a nutshell, they wanted to eliminate the Cd for environmental reasons, but when they did, the contrast (grade) spacing got screwed up and in order to fix this, they changed other things in the formula, which introduce the changes in flexibility and tone that the world noticed.

Now this is just speculation on my part, but I think it is plausable.

Ray Rogers

 

[Ian Grant]

But, the flexibility you refer to here is not a characteristic of warmtone papers but slow bromochloride papers, of which there are I imagine cold, neutral and warm examples.

Chloro-bromide papers were always sold as Warm tone papers, Bromesko, Gevaluxe, Record Rapid, Portriga Rapid etc. Colder more neutral tones could be achieved by choice of developer, or using the manufacturers bromide paper.

Many Bromide papers are actually Bromo-chloride papers, but the chloride level is usually low & often with a small amount of Iodide as well. Others may have a higher level of Chloride so can exhibit a very slight warmth but they won't have the flexibility of a true Chloro-bromide paper.

It's very apparent in all the paper manufacturers brochures and adverts that they sold Bromide papers for Cold & neutral tones and Chloro-bromide papers for warm tones.

I suggest that it was not the removal of the Cd, but a reformulation of the basic emulsion that caused the loss of both the flexibility and warmth of the older emulsions.

In a nutshell, they wanted to eliminate the Cd for environmental reasons, but when they did, the contrast (grade) spacing got screwed up and in order to fix this, they changed other things in the formula, which introduce the changes in flexibility and tone that the world noticed.
Now this is just speculation on my part, but I think it is plausable. Ray Rogers

The Cadmium seems to play an important in the papers behaviour to over exposure and subsequent development in dilute developers, it's here it appearss to be having the greatest effect on helping maintain contrast.

Of course the effect of removing the Cadmium necessitated a reformulation, bringing with it the drop in flexibility. In this case Agfa were making a direct replacement for one of their best selling papers.

All the European warm-tone papers changed when the Cadmium was removed as part of an EU cCadmium free directive, this affected papers from Agfa, Kentmere, Forte, EFKE, & Foma, although the former Eastern block companies kept using cadmium a little longer until closer to their countries joining the EU. Ilford weren't making a Warm-tone paper at that time.

Users of all the warm-tone papers complained about the post Cadmium papers compared to the old versions

Lith printers exploit exactly the same properties of over-exposure and under development to bring out the image tones and colours they require in the highlights & mid tones, and they will tell you the same about a wide variety of papers, once the cadmium was removed the paper ceased to behave as well for lith printing.

Ian

 

[Ray Rogers]

Chloro-bromide papers were always sold as Warm tone papers, Bromesko, Gevaluxe, Record Rapid, Portriga Rapid etc. Colder more neutral tones could be achieved by choice of developer....
Ian

I cannot agree with the 4th word in the above statement.
First of all, I have seen Gevaluxe and the images I saw were not what I would call warm, but were rather neutral IIRC.

In addition, it is I think useful to keep in mind that among other things, it is really the size and shape of the silver filaments produced that is responsible for the tone, not the halide per se.

You hint at this when you point out that colder tones could be achieved by dev choice and yes, this could explain the neutral examples I mention above. Then again, Gevaluxe may have been a bromide emulsion.

Secondly, I have made Bromochloride and Chlorobromide emulsions in which the tone was, on casual inspection, essentially the same.

Thirdly-

It's very apparent in all the paper manufacturers brochures and adverts that they sold Bromide papers for Cold & neutral tones and Chloro-bromide papers for warm tones.
Ian

Yes, while the papers you listed above may all be described as Chlorobromide, that by no means precludes the existence of neutral or cold tone Chlorobromide emulsions.

BTW, I notice that we may be using our terms differently... just to clarify, when you say chloro-bromide which halide are you indicating is predominate?
The Cl or the Br?

The Cadmium seems to play an important in the papers behaviour to over exposure and subsequent development in dilute developers, it's here it appearss to be having the greatest effect on helping maintain contrast.

Lith printers exploit exactly the same properties of over-exposure and under development to bring out the image tones and colours they require in the highlights & mid tones, and they will tell you the same about a wide variety of papers, once the cadmium was removed the paper ceased to behave as well for lith printing.
Ian

This is where the converseation becomes interesting!

Ray

 

[Photo Engineer]

I think that you should both be aware that Cadmium salts could be added either during precipitation or after the emulsion was washed. This gave the maker control over a whole variety of emulsion features. Also, the range of addition could be from about 100 mg / mole of silver, which was very low, up to about 14 grams / mole of silver which is on the very high side. This range also brought several different features of Cadmium into play.

One common method of making a warm tone paper, one which I could never really intellectually accept, was adding the salt to a kettle of Silver Nitrate in Gelatin. And, the salt in this case was doped with a witches brew of metal salts and complexes, but no Silver salt of any sort. The result was a warm tone emulsion, but to my way of thinking it should have been very foggy due to the presence of such an excess of silver at the start. AFAIK, this method was used at both Kodak and Agfa.

I guess that is why emulsion making is such a black art. Speaking of which, it is always easier to make an emulsion become more cold in tone than warm in tone. That is what we worked on so hard, was the organic (non-toxic) equivalents of Cadmium to control curve shape with no change in tone. You see, Cd was also used in color paper up to 1969 to control curve shape, and the tone of the image was unimportant in the case of color. But, the emulsions used, tended to give soft toes. So, color paper consumed a huge volume of Cd at EK. These organics changed curve shape without changing tone, so they could be used in B&W products.

I was told that at one time, the entire range of contrasts for B&W papers could be just about achieved by only varying the Cd salt level. I'm sure it took more than that, but nevertheless that was the given "wisdom" at the time and was put into practice in Ektacolor paper for sure. It was replaced in Ektacolor 30 and 37 paper in 1969, along with most B&W papers by the organic compound substitues. I remember how hard it was to get acceptable contrast in the toe in several products at that time.

I even put two of these organics into Kodacolor Gold 400 to adjust curve shape and keeping. Cd salts also had a beneficial effect on keeping IIRC. I know that the substitues did.

PE

 

[Ian Grant]

Thanks Ron (PE)

In our year or more of discussion this is the first time you've really addressed the Cadmium issue. It was used, it worked. We'd both agree we've not seen why in any research

I cannot agree with the 4th word in the above statement.
First of all, I have seen Gevaluxe and the images I saw were not what I would call warm, but were rather neutral IIRC.

Easy: Any Chloro-bromide paper will give neutral tones in the right developer. A print on a warm tone paper such as Gevaluxe can be neutral in tone that's the nature of a Chloro-bromide emulsion, and totally expected.

Secondly, I have made Bromochloride and Chlorobromide emulsions in which the tone was, on casual inspection, essentially the same.

If you used a standard developer like Dektol/D72 then that would be expected it's not a warm tone developer.

Thirdly- Yes, while the papers you listed above may all be described as Chlorobromide, that by no means precludes the existence of neutral or cold tone Chlorobromide emulsions.

Show me anything, where a company is selling a Chloro-bromide paper that isn't warm-tone, I've not seen anything in 40 years of reading & research.

This is where the converseation becomes interesting!

Lets clarify, a Chloro-bromide emulsion is predominantly Chloride. Bromo-chloride predominantly bromide. But once the chloride level reaches a significant level a bromo-Choride paper becomes warm-toned anyway.

Now to "your" comments about a chloro-bromide emulsion being warm tone. Yes it is with a Warm tone developer but with a cold/blue tone developer will give cold/neutral tones.

The type of halide is instrumental in the final grain size in a print, which is ultimately what produces the image colour and tone.

Ian

 

[Photo Engineer]

Ian;

First off, I have to agree with all you have said above in your last post.

IDK if any of this is in published works or not, but I remember that Hamilton and Brady studied the effects of Cadmium, TAI, and PMT on emulsions. They all were found to yield similar results by a similar mechanism but react at different levels and require a different halide balance for full functionality. For example AgCl/Br emulsions are more sensitive to Cd, whereas AgCl are more sensitive to PMT. All emulsions are stabilzed by TAI, but the curve shape control takes place during finish with Sulfur or Sulfur + Gold IIRC.

There are side effects as well, but basically Cd and PMT sharpen toe while Cd may or may not change tone depending on the time of day and phase of the moon or who you talk to . PMT seems to make the image silver shift more neutral or blue.

I have also found in my notes here that a Mercury MethIodide salt can also function in a similar fashion. In fact, an emulsion used in one of Kodak's papers was said by one company to be an Ag/Cl/Br/I emulsion doped with Mercury but it was really an Ag/Cl/Br with the Mercury Methiodide salt added afterwards. This rather amused us.

PE