Ammonia / tri-ammonium citrate for Simple Cyanotype

[Andrew O'Neill]

{Moderator edit: this thread was split off of the Ferroblend process thread: https://www.photrio.com/forum/threads/a-blended-ferrocyanide-print-process.212808 where these posts started as a follow-up on the possibility to use Simple Cyanotype, but the question is relevant in general, so it deserves its own thread}

Question for @Raghu Kuvempunagar or @koraks:
The Simple Cyanotype calls for 10% ammonia. I only have the Kroger brand, which is 1-3%. Can I still use it? What adjustments if any, would I have to make to it? Thanks!

 

[Andrew O'Neill]

I just checked online sources for the higher grade ammonia hydroxide, and there is no way that I will pay what they are asking!

 

[koraks]

I've never used Simple Cyanotype, so I'd have to check the documentation to see if you can substitute the 10% ammonia with 10x the volume of 1% ammonia. That would be the obvious solution.

 

[Andrew O'Neill]

@koraks thanks! That would be the obvious solution, but only if the ammonia I have is 1%. It could be, but I'm not 100%.

 

[koraks]

I quickly checked the formula and you cannot substitute a larger volume of 1% ammonia - or even 2% for that matter. You'd end up with a sensitizer that's at best something like 3 times less concentrated than it should be. Maybe it would still work e.g. if you double coat the paper, but it's going to be suboptimal.

The local supply situation of chemistry is notoriously variable between countries, so IDK what the situation is in Canada. But I'd be surprised if there's no way to get hold of e.g. 10% ammonia at a reasonable price. It's such a common chemical building block; there are thousands of tons of the stuff in Canada, so there's bound to be a way to get hold of a tiny amount of it. There may be regulations in effect on higher concentrations of the stuff, but I'd expect that 10% should be accessible also for private individuals. But that's just a guess.

I just checked and I can buy 25% ammonia here with ease at a cost of around €4/liter and this seems to be available to private consumers just the same. It's sold as a cleaning product. It's also commonly used as a de-greasing agent in painting.

PS: ammonia sold here in supermarkets etc. for household purposes is around 5%v/v. That should work. Maybe something similar is available where you live as well.

 

[Andrew O'Neill]

Too expensive here. I'll put Simple Cyanotype on the shelf for now. Oh well...

 

[Raghu Kuvempunagar]

I'll put Simple Cyanotype on the shelf for now. Oh well...

If Triammonium Citrate is available to you, it can be used in Simple Cyanotype in place of Ammonia as per @Mike Ware's recommendation:

Simple Cyanotype

Critical tests of cyanotype by John Isner, leading exponent of the Piezo Digital Negative system, have inspired me to devise a sensitizer that is much more reliable than the ‘Classic’ cyanotype and more photochemically precise than my ‘New’ version of 1995. To distinguish it from the other two...

www.photrio.com

 

[Andrew O'Neill]

@Raghu Kuvempunagar thanks for that! I don't have any on hand, but I'll see if Jacques at Argentix does. Cheers!

 

[Andrew O'Neill]

@Raghu Kuvempunagar I am unable to source Triammonium Citrate through Argentix... I did find it at a chemical supplier here in Canada, but they want an arm and a leg. Is there anything else that could replace Triammonium Citrate?

 

[Andrew O'Neill]

The closest maybe would be ammonium citrate, Dibasic? What do you think?

 

[nmp]

The closest maybe would be ammonium citrate, Dibasic? What do you think?

You can make your own with ammonium carbonate (NH4)2CO3 and citric acid. The former is easily (and cheaply) available as Baker's ammonia.

:Niranjan.

 

[Andrew O'Neill]

You can make your own with ammonium carbonate (NH4)2CO3 and citric acid. The former is easily (and cheaply) available as Baker's ammonia.

:Niranjan.

Thanks! So, Baker's Ammonia can be used in place of Triammonium Citrate?

 

[nmp]

Thanks! So, Baker's Ammonia can be used in place of Triammonium Citrate?

You still need a source for citrate to make ferric ammonium citrate. Mike's formula uses triammonium citrate so what you do is make it in situ with baker's ammonia and citric acid and then add the ferric nitrate.

You can use this to calculate the amounts (I used 15g ammonium citrate as product which is what Mike's formula requires and the others are calculated automatically):

https://www.webqc.org/balanced-equation-C6H8O7+(NH4)2CO3=(NH4)3C6H5O7+CO2+H2O

Mike requires 40 cc of water to start, the reaction produces 1.67g so you start with 40-1.67= 38.33 cc (or gm) of dist water, dissolve 11.85g of citric acid. Then add 8.9g of Baker's ammonia. Use a large beaker and add very slowly as the reaction will produce CO2 fizz (like Alka Seltzer.) Once the addition is done, you have now 15g triammonium cirate in 40 cc of water. Then add 12g ferric nitrate as stipulated to make Mike's cyanotype part A.

:Niranjan.

 

[Andrew O'Neill]

You still need a source for citrate to make ferric ammonium citrate. Mike's formula uses triammonium citrate so what you do is make it in situ with baker's ammonia and citric acid and then add the ferric nitrate.

You can use this to calculate the amounts (I used 15g ammonium citrate as product which is what Mike's formula requires and the others are calculated automatically):

https://www.webqc.org/balanced-equation-C6H8O7+(NH4)2CO3=(NH4)3C6H5O7+CO2+H2O

Mike requires 40 cc of water to start, the reaction produces 1.67g so you start with 40-1.67= 38.33 cc (or gm) of dist water, dissolve 11.85g of citric acid. Then add 8.9g of Baker's ammonia. Use a large beaker and add very slowly as the reaction will produce CO2 fizz (like Alka Seltzer.) Once the addition is done, you have now 15g triammonium cirate in 40 cc of water. Then add 12g ferric nitrate as stipulated to make Mike's cyanotype part A.

:Niranjan.

Wow! Thank you for that!

 

[nmp]

Wow! Thank you for that!

You are welcome. Let us know how that turns out.

 

[Andrew O'Neill]

@nmp and after adding the 12g of ferric nitrate, I also add the 12g of potassium ferricyanide, correct?

 

[Andrew O'Neill]

You are welcome. Let us know how that turns out.

Will do, must waiting for Baker's Ammonia to arrive in a few days...

 

[nmp]

@nmp and after adding the 12g of ferric nitrate, I also add the 12g of potassium ferricyanide, correct?

Yes, if you want to make a One part sensitizer. For a 2 part which should have longer shelf life, Mike suggests make ferricyanide separately with 10g in 50cc of water. For one part, add 10g ferricyanide to the previous solution and add water to 100cc.

Also, let me make a correction/addendum to the earlier formula. It seems Baker's ammonia while they call it ammonium carbonate might actually be ammonium bicarb - NH4HCO3. In that case the balance is:

C6H8O7 + NH4HCO3 = (NH4)3C6H5O7 + CO2 + H2O. - Balanced chemical equation, limiting reagent and stoichiometry

Balance Chemical Equation - Online Balancer

www.webqc.org

Now 15g triammonium citrate requires 14.6g amm. bicarb and (40 - 3.3 = 36.7g or cc water) with 11.85g citric acid.

:Niranjan.

 

[Raghu Kuvempunagar]

FWIW I have previously prepared Simple Cyanotype sensitiser Part A without using Ammonia directly. The idea is to use Ammonium Chloride and Sodium Hydroxide to in situ generate Ammonia in solution. So, after making a solution of Citric Acid and Ferric Nitrate as per Mike Ware's instructions, dissolve calculated amount of Ammonium Chloride in it. And then add calcluated amount of Sodium Hydroxide solution little by little and stirring well after each addition. When Ammonium Chloride reacts with Sodium Hydroxide, Ammonia is generated which reacts with Ferric Citrate to form Ferric Ammonium Citrate. However, the sensitiser thus prepared contains Sodium Chloride in it as a biproduct of the reaction that supplies Ammonia.

 

[PGum]

Its hard to say if some of the surplus sodium will complex. Ferric X citrate, where X may be sodium, potassium, lithium, ammonium can all form soluble green complexes - even calcium. Key to simple cyanotype, at least as described by Mike Ware is the crystal structure of this form of FAC In the “Simple cyanotype” Another cation may interfere, then again it may not, so the outcome may be different.

 

[Raghu Kuvempunagar]

Its hard to say if some of the surplus sodium will complex. Ferric X citrate, where X may be sodium, potassium, lithium, ammonium can all form soluble green complexes - even calcium. Key to simple cyanotype, at least as described by Mike Ware is the crystal structure of this form of FAC In the “Simple cyanotype” Another cation may interfere, then again it may not, so the outcome may be different.

The possibility that you described exists no doubt and the resulting sensitiser might not be Simple. But it works well for me in FerroBlend process. I had made a small volume of the sensitiser many months ago using the procedure outlined in my earlier post. I made a print this morning with the same sensitiser and I will post the pic after the print dries.

 

[PGum]

Raghu, that is informative!
In a post some time ago, I mentioned that the insitu AN formed might have more to do with the effects on image than whether its monomeric or polymeric based on some observations without the insitu AN. Still we can’t rule out that yours isn’t monomeric or a mix of a mono and poly FAC!

 

[Andrew O'Neill]

I mixed up some Simple Cyanotype, two solution (I already had a batch of 10% Ferricyanide mixed up). One thing to note... TriAmmonium Citrate has a very strong ammonia odour... Work in a well ventilated area (I had my fan sucking air out, as well as wearing a respirator). It does fizz a bit when mixed in water, containing the Citric Acid, but nothing like baking soda and vinegar! The Ferric Nitrate went in nicely, and made the solution a familiar green colour. The following day, I made a small test print. Yes, Simple Cyanotype is a bit faster than traditional recipe, but no where near 3 to 4 times faster...at least for me. SC (so I don't have to keep typing out Simple Cyanotye) does indeed have a longer tonal scale. My Cyanotype negs were not suitable. Adjustments in the profile and curve had to be made. At the end of the day, I got a decent image. Now I'll need to see if it works better than traditional Cyanotype, for Ferroblend...

 

[PGum]

Yes, Simple Cyanotype is a bit faster than traditional recipe, but no where near 3 to 4 times faster...at least for me

This speed discrepancy has been noted by others. Curious about your exposure unit wavelength?

 

[Andrew O'Neill]

This speed discrepancy has been noted by others. Curious about your exposure unit wavelength?

I've been using Barrina TF5 UV LED Blacklight Bar, picked up on Amazon. They are rated at 395-400nm. Everything is bloody fast with them! My Kallitypes are one minute!