Ammonium Chloride

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Do any chemists out there anything about Ammonium Chloride? I have been experimenting with it as an additive(10% solution) to paper developer. I'm getting interesting results and would like to know more about it but the texts that I've consulted have only told about it's use in salt and albumen prints. I've also read about the potential danger in combining it with a base, but my working developer is very dilute with the only alkalis being Sodium Carbonate and Sodium Sulphite. I also know that combining a nitrate with Ammonium Chloride is extremely dangerous, but does that include silver nitrate in a paper's emulsion? Am I correct in assuming that this Ammonium Chloride is a restrainer (as my experiments would indicate?) Is the print color's shift towards red a result of a lower pH? Any advice would be greatly appreciated.

-- Steve Wiley (wiley@accesshub.net), October 17, 2001

Answers

MSDS is at http://www.jtbaker.com/msds/a5724.htm. Sounds as though you have already read it. It says it is incompatible with concentrated acids, strong bases, silver salts, etc. Hopefully Pete Andrews will respond to this post. What interesting results are you getting?

-- Ed Buffaloe (edb@unblinkingeye.com), October 17, 2001.

Ed, you may find this useful. I had read about chlorides being used as restrainers in film devs. I was hired to do some experiments and solarizations for a photographer, so after reading about duotone solarizations on your site, I decided to try replacing the additional bromide in the second dev. with Ammonium Chloride. The effects I achived are pretty spectacular. I've used as much as 15 grams/L and got best results using Bergger CB Style(!). I am getting metallic pink highlights with olive green shadows. These colors are not subtle. Nelson Gold Toner gave a cobalt blue tone rather than the usual warm tones. My concern, as you may have gathered from my origial post, is about the possible dangers in using it. Obviously it stinks, so I keep the tray covered and wear a respirator. I'm also careful to flush copious amounts of water down the drain once I've poured it out as I don't want it sitting in the drain trap.

-- Steve Wiley (wiley@accesshub.net), October 17, 2001.

I forgot to add- I did check the MSDS as well as the Merck manual and an old copy of the Focal Encyclopedia, as well as the Darkroom Cookbook (always found that the Pharmocopia there leaves a lot to be desired). Merck manual and MSDS mentioned the solvency of Ammonium Chloride as well as it's incompatibility with silver salts. Does this account for the metallic look? i.e. is the high solvency actually replating the image?

-- Steve Wiley (wiley@accesshub.net), October 17, 2001.

Ok from my freshman chemistry (wayyyyy long time ago) if you combine ammonium chloride and silver nitrate you will get ammonium nitrate and silver chloride precipitate, not a good think unless you are trying to make fertilizer and/or a bomb...lol. as a salt ammonium chloride should have similar restraining properties as potassium bromide. Other than that I don't see any other advantage of using this chemical in a developer. It is also used in fixers but now a days the most commonly used rapid fixer is ammonium thiocyanate. Anyways, if you like the results good for you but I dont see any advantages on adding this to your developer unless you are getting too much fog with your current developer.

-- Jorge Gasteazoro (jorgegm@worldnet.att.net), October 17, 2001.

Fascinating! Does it smell of ammonia? Or chlorine? Have you tried toning in selenium or Polytoner? How would you classify that Bergger paper--is it a cold toned paper? What other papers have you tried? My best results since the demise of Brovira have been with Luminos and Galerie. When you tone with the Nelson Gold Toner, do the highlights or the shadows turn cobalt blue? Or is it everything? Have you tried a thiocyanate-based gold toner, or one with thiourea? I wonder what would happen if you used some other chloride, like table salt?

-- Ed Buffaloe (edb@unblinkingeye.com), October 17, 2001.


Two things, Ed: Ammonium chloride smells like ammonia....it is wise to use a respirator when working with it. Steve: you are correct, since you are in a way "making" nitric acid the pH is lower and probably the cause of your red shift, but on the other hand it could also be the ammonia...As a curious note I once left Agfa portiga in the selenium toner for too long and the image turned into a coppery red/brown, I also see the same effect with Oriental Seagull FB, selenium toning turns the image warmer, but I have not left it long enough to see if it turns the same coppery brown as the Agfa. That's all for me...

-- Jorge Gasteazoro (jorgegm@worldnet.att.net), October 18, 2001.

Firstly, there's no Silver Nitrate in photographic paper, only Silver Bromide and Chloride, so I think there's very little danger of your developer blowing up in your face.
I seem to remember something about Ammonium Chloride being recommended for giving warm to red tones as a pre-bath to the developer. Whether it reacts with the emulsion directly, or whether it's simply 'carried over' into the developer, I don't know.
I tried it once, a long time ago, and it gave me rusty red/orange results that I didn't much like.
I've got an idea that it's the free ammonia that causes the reddening, but I really haven't looked into it. Sorry.

-- Pete Andrews (p.l.andrews@bham.ac.uk), October 18, 2001.

Pete, thanks for refreshing my memory. Maybe you could answer another question I have. Can Ammonium Chloride replace Potassium Bromide in a rehalogenating bleach in order to end up with a chloride paper, as opposed to a pure bromide paper? I came across some toner formulas that work best with chloride papers, but using Azo isn't an option. Ed, to answer your question, Bergger CB Style is a chlorobromide emulsion on an Ivory base with a nice semi-gloss surface. I really like it. It tones like a champ. A straight print in the Ammonium Chloride enriched dev (we'll call it AC-120) sort of resembles a lith print with a shift towards coppery- red. I was surprised it solarized. It seems to work best with shorter second- exposures. I would be curious to hear your thoughts on it as I have very limited experience with the Sabattier process. I usually end up bleaching back the highlights with double-strength Farmer's and this seems to have some effect on the color. In general, I get better results solarizing VC papers when using a blue bulb for the second exposure, my rational being that high contrast is governed by the blue end of the spectrum. Not sure if this theory holds water, but it seems to work. I tried just about every paper I had on hand which included: Forte Polywarmtone (good), Forte Polygrade (not so good, but interesting), Oriental Grade 4-- new and original (interesting), Bergger Variable NB ( not so good), Bergger Art grade 4 (good), Ilford MGF (O.K)and Agfa Insignia grade 4 (O.K.). CB Style was the best for my purposes. As far as toning, I tried Polytoner 1:50 (peachy, almost flesh color), Ilford IT-2 (more sepia than Polytoner), Selenium 1:30 (performed as expected) and 1:9 (nice split-tone when used with Ansco 120 an Forte Polywarmtone; copper tone with CB Style and AC-120). Most striking results with Nelson Gold Toner- blue highlights, olive shadows. Haven't tried other gold toners yet; maybe today. Does anybody Know an archival green toner formula that doesn't require Nitric acid or Vanadium? Thanks for all the responses.

-- Steve Wiley (wiley@accesshub.net), October 18, 2001.

Good for youse guys. I grouse when the Dektol is slow disolving, while y'all is out there on the cutting edge with raw chemicals. My hat's off to you. Bill

-- Bill Mitchell (bmitch@home.com), October 18, 2001.

My experience has been that print solarization works best with pure bromide papers, except that they are quite rare (possibly nonexistent) these days. My best results have been with Ilfobrom Galerie grades 3 and 4, Luminos Classic cool tone, grades 3 and 4, and Bromofort Grade 3 or 4. I have read that the particles of silver in chloride papers are much smaller than those of bromide papers, and because they are smaller they reflect or refract light differently, giving the warm tone. When you reduce a print, it often tones to a warmer color, and I have assumed this was because the silver particles were reduced in size. Similarly, when you use a restrainer like potassium bromide the print gets warmer and will tone to a more brown or reddish-brown color. Again, I assume that the restrainer somehow reduces the size of the silver grains in the emulsion.

So, using a second developer with a large amount of potassium bromide in it essentially makes the paper respond more like a chloride paper-- the areas affected by the second developer will tone to a brownish or reddish color in selenium. I think the same thing is happening with your ammonium chloride additive. I wonder what sodium chloride (table salt) would do? I should think it wouldn't smell so bad.

I think your Bergger CB Art paper is a chloride or chloro-bromide emulsion, and I would expect it to require a very brief solarization exposure. My experience is that the harder the paper, and the more bromide in the emulsion, the longer and brighter the solarization exposure needs to be. And vice versa. Most chloride papers don't solarize well at all--I never had any luck with Portriga or Insignia, though the Luminos Classic Warm worked. I could also never get Oriental Seagull or Ilford Multigrade to solarize satisfactorily.

-- Ed Buffaloe (edb@unblinkingeye.com), October 18, 2001.



Pete there is Silver Nitrate in salted paper, albumen sensitized paper, etc. Since I don't know what kind of process he is using I answered as if it was present. OTH you are correct regular production papers are sensitized with silver salts of chlorine and bromine but as we say here in America, never assume, cause you make and ass out of you and me.....

-- Jorge Gasteazoro (jorgegm@worldnet.att.net), October 18, 2001.

Steve: I don't see why you can't turn the silver image into a Chloride, as opposed to a Bromide, but surely common salt would be the obvious thing to use? This avoids any potential health problem from Ammonium chloride as well.

WRT ammonium nitrate being formed: I think this is really a non-issue. Ammonium Nitrate is commonly used as an agricultural fertiliser, with complete safety from any danger of explosion. True, it can be used as a high explosive, but for that purpose the water content has to be reduced to a very low level by heating it, and then kept there by mixing with parafin or some other water repellent coating. It also has to be detonated with a fulminate capable of producing a supersonic shock wave. Normal ignition does not cause it to explode. (source: The anarchist's cookbook!)
So, given that any ammonium nitrate generated from a photographic process is going to be in an aqueous solution, in tiny quantities, and not likely to have a detonator set off near it; I think the likelihood of it presenting an explosion hazard is diminishingly small to non-existent.
BTW, you should now eat this post to prevent the above information falling into the wrong hands.

-- Pete Andrews (p.l.andrews@bham.ac.uk), October 19, 2001.


I decided to try the Ammoniun Chloride because of an old formula for chloride papers that I found, and now I've got a pound of the stuff so I best use it. I intend to try Sodium Chloride soon, though. I made a mistake in the above post regarding toning results (didn't have my notes in front of me). A deep copper tone was achieved with the CB Style/ AC 120 combo that was bleached then redeveloped in a thiourea/ sodium hydroxide dev. Really beautiful. Used a thicyanate based gold toner. Lovely, yet predictable. Great results with Viradon 1:50 then rinsed for 5 minutes in 120 degree water. Rich, beautiful orange. As I said before, I'm doing these prints for a photographer who has a book coming out, this month I think, about bullfighters. I printed the book and was slated to print the exhibition. Unfortunately, he started experimenting with Iris prints and decided he prefered the arty, watercolor paper look of the Iris print to the 30x40 test prints I had done for him. Now, he's decided that he wants some of the exhibition prints to be solarized, his rational being that the exhibit should be different than the book so people will come back a second time, as opposed to just looking at the book. Whatever. He intends to scan the solarized prints and have Iris prints made. So, I'm starting to get a little annoyed thinking about how people are going to go into this exhibit, see Iris prints and think some guy behind a Mac performed these manipulations. I should probably just be happy with the paycheck, but I did work quite hard on these. Any thoughts? Incidently, if my posts seem horribly stream-of-consciousness, it's probably cuz' I just quit smoking.

-- Steve Wiley (wiley@accesshub.net), October 19, 2001.

I just have one question Steve, how good are the photographs? It seems to me this photographer is relying more on the gimmicks than on the strenght of his photgraphs. Now don't take me wrong I don't mind toning etc, I love the way Kenna tones his prints, but it seems to me this guy is trying evrything under the sun, is it to improve the prints? I also don't understand his logic about the exhibit being different than the book, heck when I bought my first Caponigro print, it was because I had seen it in his book and then when I saw it real life it was the same just so much better...I hope this makes sense.. ok, I guess I should stop rambling and let you go, but maybe you can tell us how goos the photographs are.

-- Jorge Gasteazoro (jorgegm@worldnet.att.net), October 19, 2001.

I completely agree with your thinking. Although I am fascinated by the whole alchemelogical process of printing, toning, etc. I agree that it can be crutch or a gimmick and certainly can't salvage a bad image. Fortunately, this guy's work is good. Really good, in fact. He's got a great eye for light and composition, and he has respect for the craft and history of photography. I've seen the proofs for the book and they are amazing, four-color repros that would stand up next to Camera Work and Penn's Moments Preserved. Obviously, I'm proud to be involved in this project and probably shouldn't be griping. Hard work should be rewarded with more than a paycheck, though. The techniques I'm using do befit the subject matter, though. The tones are rich and earthy and the solarizations subtle. He selected images that are very graphic and that work nicely with the manipulations. They're quite mystical, actually. Think of F. Holland Day, Wm. Mortensen or maybe Curtis if you need some reference points. The show is in February. I'll keep you posted.

-- Steve Wiley (wiley@accesshub.net), October 19, 2001.


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