On the Toning of Cyanotypes

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fgorga

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I recently started up making cyanotypes again after a hiatus of about twelve years.

Although I enjoy the Prussian blue of the native cyanotype, I also enjoy the variety of tones made available by further treating a cyanotype to alter its tone.

However, one of the things I was dissatisfied with in the past was the irreproducibility in the toning of cyanotypes. Thus, I have spent some time over the past few weeks working out a more stable procedure for toning cyanotypes.

To a chemist (I am a retired chemistry professor), the toning of cyanotypes involves the sequential exposure of the native print to solutions of two types of compounds, a polyphenol (typically tannic acid, gallic acid or pyrogallic acid) and an alkali (typically sodium carbonate or ammonium hydroxide). I have also started using sodium bicarbonate as the alkali as well. I am unaware of a prior report of use of bicarbonate in the toning of cyanotypes.

My procedure is simple and general in that one can pick and choose from the various components and obtain a variety of different tones using the same set of steps.

Here is the procedure:

I usually use print the have been “aged” a day or two to become fully oxidized and in this case, I soak the prints in water for a minimum of two minutes before starting.

1) Soak the print face down in a 2% (w/v) solution of polyphenol for 5 minutes with occasional rocking. The tone of the print will not change significantly at this stage.

2) Dip the print in a tray of water very briefly (10-15 seconds)

3) Place the print face down in an alkali solution (details below) and immediately turn the print face up. Rock the tray constantly and as soon as the desired tone is achieved transfer the print to a tray of water. The total time of exposure to alkali is 30-60 seconds; it should be just long enough to cause the change in tone. Longer times will result in more bleaching.

Sodium carbonate (washing soda) and sodium bicarbonate (baking soda) are used at 7.5% (w/v). The ammonium hydroxide solution is 5% (v/v) household ammonia in water.

4) Wash the print thoroughly before drying.

This procedure results in a mild bleaching of the print so I usually start with prints that are a bit on the dark side of acceptable.

There is also a bit of staining of the highlights with a resulting small loss of contrast. Pyrogallic acid seems to be the worse in this regard. Also, some papers stain more readily than others.

The results of some combinations of the various compounds are shown below:

Figure 1
Effect-of-Polyphenol.jpg

Figure 2
Effect-of-Base.jpg
 

Vaughn

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Excellent! I have only played with it...tannic acid and ammonia was the combo I used years ago...experimenting going back and forth for different effects. Might return to it someday and this will be of some help!

I think I beached first in ammonia and brought back the image in the tannic acid, or I had to return to the ammonia again after the tannic acid. Very unscientific, I'm afraid!
 

ChristopherCoy

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Very nice! Thanks for the well written explanation too!
 

awty

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Very nice work. My methodology usually involves boiling up a fist full of tea bags, cool down with water and pour over the print and let sit over night. I admire your dedication.
 

nmp

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Thanks Professor for the succinct presentation of this systematic study on cyanotype toning - just in time as I was getting ready to embark on it myself soon.

I will probably will have more questions later as I get involved in this first-hand, but one comes to mind immediately. Most what I have read the process always starts with the alkaline bleach, which is then followed by the polyphenol treatment. What made you to go the other way around?

:Niranjan.
 

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Very interesting. Need to read in detail when better able to concentrate!
 
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fgorga

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Excellent! I have only played with it...tannic acid and ammonia was the combo I used years ago...experimenting going back and forth for different effects. Might return to it someday and this will be of some help!

I think I beached first in ammonia and brought back the image in the tannic acid, or I had to return to the ammonia again after the tannic acid. Very unscientific, I'm afraid!

Thanks!

Bleaching with ammonia or carbonate first is probably the most commonly seen procedure, It was my thought that this was/is the root cause of the poor reproduciblity .

At the concentrations of alkali used bleaching is quite rapid and once the image has faded how does one know how long to continue the bleaching.
 
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fgorga

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Thanks Professor for the succinct presentation of this systematic study on cyanotype toning - just in time as I was getting ready to embark on it myself soon.

I will probably will have more questions later as I get involved in this first-hand, but one comes to mind immediately. Most what I have read the process always starts with the alkaline bleach, which is then followed by the polyphenol treatment. What made you to go the other way around?

:Niranjan.

No need for the formality of "Professor"... "Frank" works just fine!

Hopefully you will find this procedure to you liking. Of course, I will attempt to answer any questions you have .

Regarding for the question of order... As I said in my reply to Vaughn, I suspect that the bleaching step is the cause of variability in the typical procedure. There were a few hints in the "literature" which made me suspect that the order was unimportant... so I just decided to do the experiment and see what happened.

This is one of the advantages of bringing a scientific bent to photography (or art in general). I made a career of doing experiments.... at least when I wasn't teaching or writing grants or papers! Thus, as a friend recently commented, I have no fear of experimentation!!! ;-)
 

nmp

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No need for the formality of "Professor"... "Frank" works just fine!

Hopefully you will find this procedure to you liking. Of course, I will attempt to answer any questions you have .

Regarding for the question of order... As I said in my reply to Vaughn, I suspect that the bleaching step is the cause of variability in the typical procedure. There were a few hints in the "literature" which made me suspect that the order was unimportant... so I just decided to do the experiment and see what happened.

This is one of the advantages of bringing a scientific bent to photography (or art in general). I made a career of doing experiments.... at least when I wasn't teaching or writing grants or papers! Thus, as a friend recently commented, I have no fear of experimentation!!! ;-)

Thanks, Frank for the explanation. I can empathize with an experimentalist - I was one myself at one time, though in an industrial setting not an academic one. I have to be careful though in dealing with alternative processes, at times (more often than not) the experimental/scientific self gets better of the creative me....in the end there is nothing to show.

I am going to order up some of these acids....where did you source your tannic acid? There seems to many different ones, I am not sure what the differences are.


:Niranjan.
 

Andrew O'Neill

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Thanks, Frank for the explanation. I can empathize with an experimentalist - I was one myself at one time, though in an industrial setting not an academic one. I have to be careful though in dealing with alternative processes, at times (more often than not) the experimental/scientific self gets better of the creative me....in the end there is nothing to show.

I am going to order up some of these acids....where did you source your tannic acid? There seems to many different ones, I am not sure what the differences are.


:Niranjan.

I get my tannic acid from a DIY wine shop just down the road from me...
 
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fgorga

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I am going to order up some of these acids....where did you source your tannic acid? There seems to many different ones, I am not sure what the differences are.


:Niranjan.

Niranjan,

I have been using lab grade tannic acid left over from my days of having access to a chemical stock room. However, i am running low and just ordered a new supply from Bostick & Sullivan. I sourced gallic and pyrogallic acid from Bostick & Sullivan as well.

I am pretty sure that if you bought these materials from any of the usual alt process suppliers that they will be fine, as would reagent grade material form a standard chemical supply house.
 
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fgorga

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I get my tannic acid from a DIY wine shop just down the road from me...

In my limited experience the "tannic acid" sold for wine making is NOT suitable for the process I describe.

I put tannic acid in quotes in the previous sentence because as far as I can tell the material sold for wine making is more properly called tannins. It is a complex mixture of compounds one of which is tannic acid is one component.

Lured by the low price of wine tannins, I purchased some and did one or two experiments using it.

Wine tannins do indeed tone cyanotype, but the result is much more akin to toning with tea or coffee that it is to the result which I describe. In my hands, even at very low concentrations, there was heavy staining of the highlights in addition to a change in the tone of the pigment. The resulting toned print was very low in contrast and very unappealing to my eye.
 

Vaughn

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I used some tannic acid I had in the cupboard (of the photo stockroom I was in charge of). You can get it at Bostick and Sullivan at about $45 a pound. From Photographers Formulary it is about 3x the price -- $125/lb.

Artcraft has it for $40/lb.
 

nmp

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Apparently wine tannin is also more easily soluble in water unlike tannic acid which tends to form muddy suspension or so I have heard. I might go visit the local wine/beer making shop (wonder if they stayed open as essential service) and see if they have "tannic acid" as well. They usually sell in smaller quantities, which is nice for preliminary tests.

Otherwise, Artcraft seems to be a better bet for me, it's closer and I have some other stuff to buy anyhow.

Thanks all for suggestions.

:Niranjan.
 
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fgorga

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Apparently wine tannin is also more easily soluble in water unlike tannic acid which tends to form muddy suspension or so I have heard.

In my limited experience, it is the other way around. The tannic acid I have makes a nice clear yellow/tan solution. The wine tannins made a murky brown liquid (solution or suspension, I did not investigate)... think really, really strong muddy coffee!

Tannic acid from Artchem should be just fine in my estimation.
 

nmp

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In my limited experience, it is the other way around. The tannic acid I have makes a nice clear yellow/tan solution. The wine tannins made a murky brown liquid (solution or suspension, I did not investigate)... think really, really strong muddy coffee!

Tannic acid from Artchem should be just fine in my estimation.

Oh, well. You can't believe everything on the internet....:smile:
 
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I am looking to tone my first cyanotypes shortly and my plan was to use these "mixed tannins" intended for toning wood and leather, and allegedly 75% tannic acid content: https://www.amazon.com/dp/B008A9MFHY

Though perhaps based on the commentary above, this product may not be suitable. I'll give it a go and report back if I get acceptable results!
 

Andrew O'Neill

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In my limited experience the "tannic acid" sold for wine making is NOT suitable for the process I describe.

I put tannic acid in quotes in the previous sentence because as far as I can tell the material sold for wine making is more properly called tannins. It is a complex mixture of compounds one of which is tannic acid is one component.

Lured by the low price of wine tannins, I purchased some and did one or two experiments using it.

Wine tannins do indeed tone cyanotype, but the result is much more akin to toning with tea or coffee that it is to the result which I describe. In my hands, even at very low concentrations, there was heavy staining of the highlights in addition to a change in the tone of the pigment. The resulting toned print was very low in contrast and very unappealing to my eye.

I use it all the time and it works. No, it is not the same as toning with tea or coffee. I bleach out the image first with washing soda, then bring it back with tannic acid... from the wine store. It works.
Here is a 14x17 print I made on Hahnemuhle PR last summer:

FraserCanyonTrestles.jpg
 
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fgorga

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I am looking to tone my first cyanotypes shortly and my plan was to use these "mixed tannins" intended for toning wood and leather, and allegedly 75% tannic acid content: https://www.amazon.com/dp/B008A9MFHY

Though perhaps based on the commentary above, this product may not be suitable. I'll give it a go and report back if I get acceptable results!

It's worth a try. Please do let us know how it works.

I can't seem to find the stuff I used that did not work well.

I ordered mine from Amazon, but my order history is messed up so I can not find the exact item. The package says it is for wine making.
 
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fgorga

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I use it all the time and it works. No, it is not the same as toning with tea or coffee. I bleach out the image first with washing soda, then bring it back with tannic acid... from the wine store. It works.
Here is a 14x17 print I made on Hahnemuhle PR last summer:

View attachment 246294

That print is very nice.

I think it's pretty clear that there are lots of different crude mixtures available.Some will work and some won't.
 

nmp

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In my limited experience, it is the other way around. The tannic acid I have makes a nice clear yellow/tan solution. The wine tannins made a murky brown liquid (solution or suspension, I did not investigate)... think really, really strong muddy coffee!

Tannic acid from Artchem should be just fine in my estimation.

I think the tannic acid you used being that it was pure lab grade perhaps does give a nice clear solution. May not be so for the commercial variety. Like being shown by this guy:



(his paper came out real nice and white, hmm...)

:Niranjan.
 
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Máx Arnold

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Thank you, professor. This post is very useful for those researching on toning cyanotypes.
It also makes me wander: If for toning a cyanotype you have to expose the blue compound prussian blue to to a polyphenol and a base, what's a polyphenol then?
Normally we'll use tannins from tea or coffee. You mention tannic acid which is industrially produced from grape seeds, as well as gallic acid and pyrogallic acid.

Now, a quick search on google took me here: https://www.healthline.com/nutrition/polyphenols#benefits
Now, regardless of the "health benefits" it gives some examples of things containing this or that kind of polyphenol.

I'm surely going to experiment toning cyanotypes with extracts of "weird" things like pepper... We'll see what happens.
I really wanna try out curcumin.-
 
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fgorga

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I'm surely going to experiment toning cyanotypes with extracts of "weird" things like pepper... We'll see what happens.
I really wanna try out curcumin.-

Max,

Experimentation is good!

Just be aware, that , in general, polyphenols are present in natrual materials at fairly low concentrations.

Also, be aware of the difference between true toning where one actually changes the chemical nature of the pigment and more general staining where one add a second colored material to an image. The latter can occur if there are colored compounds in whatever mixture you use.

Of course, if you get an interesting visual effect, the mechanism really doesn't matter.

Let us know your results at some point.
 
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