New Products

[Ray Rogers]

Ian,
Is the following supposed to be an explanation as to why the Gevaluxe I saw were neutral rather than being warm toned?:

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.
Ian

If so then, uh...

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

I think you are wrong about the placement of Gevaluxe in the chlorobromide category!

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.

Lets clarify, a Chloro-bromide emulsion is predominantly Chloride.
Bromo-chloride predominantly bromide.
Ian

Hum, that is not the way I use those terms.

Frankly speaking, I am probably inconsistent in my own usage, mostly because I forget what Mees teaches, but also because I get influenced by the way others use the terms (who have also probably forgotten), and because of the way industry was inaccurate in their descriptions of their products, making the situation worse.

But whatever, it appears that you are using Lowe's classification and your Chloro-bromide would be my bromochloride which follows Mees; however, I admit it may be more common to call such an emulsion a chlorobromide... perhaps inaccurately.
(Which is nothing new to "emulsion" research!)

That said I can give you a list, unfortunately I am not able to independantly confirm the data so I will send it to you off list. Perhaps we can sort that out between ourselves. However, I will say that the question/issue is messy in the sense that the emulsions classification is
1. dependant upon the developing/processing given and
2. dependant upon the our knowing the actual emulsion fomula;
(product classification names can be misleading!)
3.　confounded by the different paper tints
4. confounded by age effects (when looking at old paper samples)
5. not quantified, and thus rather subjective.

I have samples of Bromesko that look neutral to me, and warm looking kodabromide etc., and I would much rather prefer to measure tone or hue more objectivly before I really could be confidant in anything here; perhaps I am a bit mono-chromaticaly color-blind? I don't know!

Bromo-chloride predominantly bromide. But once the chloride level reaches a significant level a bromo-Choride paper becomes warm-toned anyway.
Ian

??? what level is that?

Do you mean still below the half way point, so it is technically (according to your terminology) still a bromo-Chloride paper?

or after it passes that half way mark and it becomes a chlorobromide paper?


Oh well, I will send you that questionable list to you shortly.


I do have one major request for anyone reading this: I am looking for trustworty documentation of which papers contained Cadmium...

For which paper do you have evidence that it contained Cadmium?

Cold or Warm, feel free to PM/skype me if you have a package with a lable on it: "Cd Free!" or "No Longer Contains Cadmium" etc., or have official company ads or publications or whatever... I would like to know about them.

Thanks,

Ray

 

[Photo Engineer]

Ray, Ian;

The correct nomenclature uses the following order:

Ag/Cl/Br/I in order of solubility of the respective salts, in decreasing order. The correct usage also includes the halide percentages such as Ag/Cl/Br/I, 1:98:1. I think that is obvious as is Ag/Cl/Br, 50:50.

BTW, the 50:50 that I last used was pretty crappy.

PE

 

[Ray Rogers]

Disengaging Stealth Mode...

The correct nomenclature uses the following order:

Ag/Cl/Br/I in order of solubility of the respective salts, in decreasing order. The correct usage also includes the halide percentages such as Ag/Cl/Br/I, 1:98:1. I think that is obvious as is Ag/Cl/Br, 50:50.
PE

Hi Ron.

Your input on this and Cd use has been appreciated.

Yes, I am aware that that is a rather common method used more often these days.

However, I have to inquire as to the source of your conviction... was there an internal memo that circulated directing employees to use that convention and if so, from who and dating from when?

Hopefully "externals" like myself might be pardoned for not knowing what goes on behind closed curtains, but Mees did state that the correct convention placed the major halide last.

Did he change his mind?

(To be fair, the article was written I think, by two Frenchman and a Fruit [Sorry. That would have been Dr. (I presume) C. R. Berry.], but it was OK'ed (if not added!) by Dr. Mees)

So I am just wondering how tightly the use of terms was controlled...
Did you have a "Kodak Manual of Style" for use in preparing reports and publications? Or was it more of a "free for all"?

Ray

 

[Ian Grant]

I think you are wrong about the placement of Gevaluxe in the chlorobromide category!

Quite probably, it was not Gevaert's main warm-tone paper, they were Gevartoand Prestona, the bromide paper was Orthobrom. Gevaluxe is in fact a bromide paper on a heavily tinted cream base, but it is it's unique look that distinguishes it from other papers. The tinted base gives it the warm look.

I do have one major request for anyone reading this: I am looking for trustworty documentation of which papers contained Cadmium...

The evidence of the various papers use of Cadmium is more difficult as no company publishes their emulsion formulae. But Agfa published press releases when the launched the Cadmium free version of Record Rapid stating they had removed it, and similar information would probably have been available from other companies.

It's relatively easy to find when various companies ceased using Cadmium in certain warm-toned papers:

Agfa - 1989/90 removed Cadmium from Record Rapid
Kentmere - 1999 removed Cadmium from the Kentona range
Kodak - approx 1999 removed Cadmium from it's B&W papers & discontinued Ektalure (which contained cadmium)
Forte - late 90's / early 2000's -Removed Cadmium from Polywarmtone
Foma - 2008 reported to still be using Cadmium in Fomatone MG

The people with the most information, other than the manufacturers themselves, are people like Martin Reed (Silverprint), and Tim Ridman & Wolfgang Moersch. There are plenty of examples of Lith prints published in various books & on the internet showing prints made with the older papers using cadmium and the newer cadmium free version.

I have samples of Bromesko that look neutral to me, and warm looking kodabromide etc., and I would much rather prefer to measure tone or hue more objectivly before I really could be confidant in anything here; perhaps I am a bit mono-chromaticaly color-blind? I don't know!

The first papers I used seriously were Bromesko and a small amount of Kodak Bromide paper, the few Bromesko prints I have left are all mildly warm toned, the Bromide paper neutral, I was using D163 at the time.

Ian

 

[Ray Rogers]

Thanks Ian -

Your time line is useful, but I wonder if there is an explanation of the 30 year discrepancy between your Kodak dates and those Ron gives... ?

Ray

 

[Ray Rogers]

Ian,

Was that "Tim Ridman" a typo?

Ray

 

[Photo Engineer]

There was a Kodak booklet on "Elements of Style" regarding internal reports as far as content and matters of language usage, not this subject though. There were two conventions used for describing halide content of emulsions. The one you describe was out of vogue in the early 20th century, but there was no written convention AFAIK on this matter. It was merely adopted by workers in the field, and was by no means universal. Many workers never described the emulsion in any detail and others went into great detail. The convention of the majority was as I described.

In the 80s, computer programs followed this convention as well, as defined by CELS (Committee for Emulsion Lab Standardization) and KEDS (Kodak Emulsion Design Software). So, automated printout and screen layout followed what I describe here by agreement of the emulsion making community at EK.

As for Cadmium removal in Kodak products. Our program started in the mid 60s and the Cd and Hg were removed from color papers introduced in 1969. B&W products had the Cd removed on a similar schedule and all came out of one lab which had several teams of emulsion makers and product engineers working on redesign. I don't know their time tables, but I doubt if the use of Cd lasted much beyond the mid 70s in any product. The effort was massive. Kodak introduced many new products to fix this problem and gain ISO and US EPA approval. I cannot see them using Cd up to the 90s, especially in view of the fact that all B&W product development virtually ceased as a separate division in about 1988 and also due to the massive amount of Cd used in an emulsion (compared to other chemicals) to get the desired effect.

The Kodak patents on this issued in the mid 70s IIRC.

I will concede that a tiny runner that had filled a special niche and could not be redesigned might have been kept on for the sake of customers, but that might elicit howls of disapproval from those Kodak haters here on APUG.

PE

 

[Ian Grant]

Yes I just spotted it, should be Tim Rudman

Ektalure certainly contained Cadmium, this was the reason it was discontinued, whether other Kodak B&W papers still did in 1999 we can't be certain but a number were reformulated at that time.

Ian

 

[Photo Engineer]

Ian;

Kodak was converting from Cl/Br and Cl/Br/I to Cl and Cl/I emulsions at about that time. The Iodide in several products was put on via epitaxy IIRC. That was done to achieve better contrast control and better keeping. It was done in the Supra line of color papers at the same time. The work was done in concert with another team working on getting the sulfur finish work right on pure chloride emulsions.

The main goal was the RA process for color, and the spill to B&W resulted in some new papers. There was no formal B&W R&D division in KRL, but the Paper Division and Photographic Technology did some development work on this crossover.

PE

 

[msdemanche]

Wow, gentlemen I had no idea I would start such a discussion. As just the simple printer I know that I could get warm tones out of Kodak papers up until about 86 or so. At that time I could still get the Protiga, but after 90 all was lost. I will certainly test the Bergger mentioned about 15 replys ago and see if it is simular. I never quite knew the full chemical formula of my papers back 30 years ago, and had not yet moved into a university setting where I quickly began to see the need for chemical understandings. Cd is not something I would want to play with these days and would hope that the substitutions are ones that can approximate, and I use that word carefully.
Wonderful and informative discussion, thanks so much.
Michel

 

[Photo Engineer]

Michel;

If you paint, Cadmium Yellow is of course made from a Cadmium salt. So it is present in a lot of common items including paints. We never seem to get rid of it. It can be used as a dopant in some electronic equipment, but AFAIK it is far less common there.

PE

 

[Ray Rogers]

There were two conventions used for describing halide content of emulsions. The one you describe was out of vogue in the early 20th century, but there was no written convention AFAIK on this matter. It was merely adopted by workers in the field, and was by no means universal... In the 80s, computer programs followed this convention as well... So, automated printout and screen layout followed what I describe here by agreement of the emulsion making community at EK.
PE

But that did not deter the proponents of the earlier convention that I credited to Mees.

"early 20th century" is what? Up to 1937 or thereabouts?

The description I was referring to was actually in James, 1966, and that brings me up to at least mid 20th century I would think

But then again, looking at recent patents reveals both conventions are still in use at Kodak:

Assignee: Eastman Kodak Company (Rochester, NY, US)
Application No.: 12/022,543
Filing Date: January 30, 2008

The silver halide emulsions may be comprised of any halide distribution. Thus, they may be comprised of
silver chloride, silver bromide,

silver bromochloride,
silver chlorobromide,
silver iodochloride,
silver iodobromide,

silverbromoiodochloride,
silver chloroiodobromide,
silver iodobromochloride, and
silver iodochlorobromide emulsions.

I think it clear that here, the major halide is placed last.
Since this system is still being used this year, for patents, by Kodak, I think it not too much of a streach to characterize it as a contempoary, 21st century convention.

However, the other system is also still in use:
see eg.:
US Patent 7422835 - Imaging element having improved durability
US Patent Issued on September 9, 2008

"silver halide crystals or mixtures thereof and can comprise, for example,
silver chloride,
silver bromide,
silver bromoiodide,
silver chlorobromide,
silver chloroiodide,
silver chloro-bromoiodide"

I think it clear that here, the order of the halides follows their solubility, from greatest to least, left to right.

So this also appears to be a contempoary, 21st century convention.

When actual molar ratios are given, it doesnt really matter, but when that information is absent, I much prefer the earlier, Mees/James convention, as it provides additional, useful information.

Ray

(afterthought: Are the any advantages to using the convention that follows solubility?)

 

[Ray Rogers]

Michel;

If you paint, Cadmium Yellow is of course made from a Cadmium salt. So it is present in a lot of common items including paints. We never seem to get rid of it.
PE

And if you use a traditional darkroom, the cadmium in your old paper probably felt right at home... under the cadmium light of your traditional (incandescent) safelight bulb!

Ray

 

[Photo Engineer]

MMmm, not sure about Cadmium light Ray. If you refer to yellow darkroom lamps of the last century or earlier, they were generally Sodium, not Cadmium.

As for usage in generic terms in patents, you notice that the exact percentage is missing? They were being vague while being specific at the same time. I know that this may seem confusing, but it "allows for slop" in a patent. Also, adding a given percentage of halide to a crystal does not assure that is what the crystal is. For example, if I mix a 50:50 Cl/Br solution and add silver nitrate to it, I don't get a 50:50 Cl/Br emulsion.

So, what you state is a quibble done for the sake of defining the range of a patents specification without being specific. Thus Ag/Br/Cl and Ag/Cl/Br can cover any range whatsoever in the patent without giving an exact figure.

PE

 

[Kirk Keyes]

Can't you guys post this stuff in the emulsion making forum so that peoples interested in it can find this discussion.

Also, nice to see that "conventions" that all the major photo chemistry books use? Mees, James, Carroll, Kowalski, and I think Tani all use the last halide listed as the major component of a mixed halide emulsion (i.e. bromide is major component in an iodobromide emulsion).

If someone has their Haist handy, maybe they can look there and we can let Haist have the last word!

 

[Ray Rogers]

MMmm, not sure about Cadmium light Ray. If you refer to yellow darkroom lamps of the last century or earlier, they were generally Sodium, not Cadmium.

As for usage in generic terms in patents, you notice that the exact percentage is missing? They were being vague while being specific at the same time. I know that this may seem confusing, but it "allows for slop" in a patent.Thus Ag/Br/Cl and Ag/Cl/Br can cover any range whatsoever in the patent without giving an exact figure.

PE

Oh don't take it too literally... I did not mean that the light was cadmium light in the same sense as a sodium light is sodium... I meant that the little yellow safelight bulbs... the kind that have two power levels, not that that is a requirment here, but that such bulbs contained cadmium and that that cadmium product was also removed from the market.

As for deception in pantentry, I know nothing.

I do not think that the Kodak Patent Division or whatever they are called, were behind this issue but, I guess you are right... it is partly their responsibity since they allow both conventions to leave their office.

And for Kirk,
Sorry for giving you the slip there. (77 Sunset Strip?)
Oh yea I could have mentiond those and lots more, but my point was that there is more than one system in current use, and as Ron pointed to the possibility of... industry may not always be totally straight in their own use of these terms.

Ray

 

[Photo Engineer]

Kirk;

Grant was not in the emulsion business. He was more of a theoretical guy and monobath guy. Different line of work. We crossed paths when he needed specialized product type work done in an experimental way out way. So, we came up with thermal dye bleach and things like that. He had the thermal and I knew how to make dye bleach. A melding of talents so to speak.

All of his emulsion expertise came second hand from experts in the field just as mine did at that time. We used to "buy" emulsions back then from the Emulsion Division.

I might add that this was not intended to be an emulsion related thread by any means.

PE

 

[Martin Aislabie]

I found an old box (30+yrs) of Agfa Portriga (?) a couple of weeks ago.

Printing with it was a wonderful but rather sad experience.

Yes, of course the base fog was a bit high but the tones it produced, particularly in the mid tones to highlights were wonderful.

It makes me realise how much we have lost with the cadmium free papers

I am not condoning the use of Cadmium, the stuff was dreadfully harmful to both us and the environment at large, but we definitely lost something when it was removed.

Martin

 

[Photo Engineer]

Martin;

The sad thing is that in your box of paper, you have such a minute amount of Cd, it is virtually undetectable in a single sheet. It would take thousands of sheets to produce enough Cd effluent to cause any significant problem. Most of the problem was in the manufacture, and EK had gotten a handle on their effluent, but who can convince an environmentalist once they have their teeth into a problem. Remember, Cd is bad but not as bad as some metals.

Today, there is far more lead in your home in the form of electronic appliances, and far more Arsenic than there was Cd those many years ago. Where are the complaints about them? You cannot replace (at this time) lead solder or Arsenic dopants, but you could replace Cd as the "tone" was considered by many to be a luxury feature that could be dispensed with.

BTW, to those reading this, did you know that the Tabacco and Cannabis plants preferentially absorb some metals and concentrates them in the leaves and buds? Cadmium is one of them! So, those who smoke are likely getting their daily dose and more of Cd and other heavy metals directly into the lungs.

PE

 

[PHOTOTONE]

Martin;


Today, there is far more lead in your home in the form of electronic appliances, You cannot replace (at this time) lead solder

PE

I think you are incorrect on this. New manufacture of electronic products does require the use of "lead-free" solder. It is available.

 

[Roger Pellegrini]

I would like some old 777.

 

[Photo Engineer]

Yes, that is correct to some extent. Do they use lead free solder in China?

OTOH, Lead doping is used in TV screens of several types, and is still used in paints in many parts of the world. Red Lead is famous world round AAMOF.

So, if your product is made in North Americal or Europe or to their standards it is probably lead free. If it is not, the coin is in the air. Your call. Oh, but then how many products are made to "our" standards. Remember that Kodak quit all production of film products in China and stopped all technology transfer.

Mining for heavy metals often has other toxic metal byproducts, lead being one of them.

PE

 

[Photo Engineer]

I would like some old 777.

?????

PE

 

[AgX]

7 grams of this, 7 grams of that, 7 grams of...


I guess Roger is hinting at

"Harold Harvey’s Panthermic “777” Developer"


http://unblinkingeye.com/Articles/Harvey/harvey.html

 

[Photo Engineer]

Yes, but I don't want to repeat what others have done. I want to study that work, find the faults and do them one better! That is my strategy.

Thanks for the reference.

PE