On the Acidification of Paper for Traditional Cyanotype

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fgorga

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Looking at the “literature” on cyanotype, there are reports of acid affecting the outcome at two points in the process. One of these points is the pre-treatment of paper to remove the calcium carbonate “buffer” present in many papers not specifically made for alt process printing. The second place that acid enters into the ‘equation’ is during development of the print. It is reported that using vinegar gives better mid-tone contrast compared to water.

My normal practice in making cyanotypes using the traditional sensitizer is to use papers as they come out of the package (i.e. no pre-treatment before coating) and to develop cyanotypes using 25% (v/v) vinegar as developer.

I have been quite satisfied with prints made this way, but given the repeated mention of acid pre-treatment I decided to experiment in order to see the effect for myself. In addition, I had never done a direct comparison between using vinegar and water as developer so I added this to my experiment.

Paper was acidified by soaking it in dilute hydrochloric acid for three or four minutes, washing the paper in water for about 5 min and air drying it. I used concentrated hydrochloric acid (HCl) (i.e. “muriatic acid” sourced from the hardware store; the label reads “20 degrees Baum/31.45%”) and diluted it 1:10 with water (i.e. 100 mL in 1L total volume). Remember to always add acid to water and not the other way around! The resulting solution is about 1 molar.

The first paper I treated was Stonehenge Warm. Evidently this paper is heavily buffered. I could see numerous bubbles emanating from the paper upon placing it in the acid and putting my ear close to the tray I could hear it fizzing! I also treated two other papers: Hahnemuhle Biblio and Fabriano Artistico (hot press). Both of these papers reacted similarly to the acid however the reaction was not as vigorous as with the Stonehenge Warm.

After the acid treated papers were dry, I coated these sheets, as well as some untreated paper, with the traditional cyanotype sensitizer.

For my first experiment, I exposed four sheets of the Stonehenge Warm paper (two untreated and two acid treated) under the same negative for eight minutes. One pair of sheets was developed in 25% (v/v) vinegar and the other in plain water.

The results shown in Figure 1 (compare the two images in the left column) clearly show, as others have reported, the improvement in mid-tone contrast using vinegar as developer. Additionally, these results clearly show that pre-treating the paper with acid increases its sensitivity to UV light after coating.

The latter result is not entirely unexpected as I have noticed in the past that unbuffered papers made for alternative processes (such as Arches Platine and Hahnemuhle Platinum Rag) generally require less exposure to make an acceptable print than do other papers.

Figure 1
effect-of-acid.jpg

In order to better ascertain the effect of acid pre-treatment on print quality, I made a second set of exposures in which, aiming for a similar Dmax on pre-treated and untreated paper, I used shorter exposure times for the pre-treated paper than that used for the untreated paper. I used two different papers for this experiment Fabriano Artistico (hot press) and Hahnemuhle Biblio. Again, the same negative was used for all exposures.

The results are shown in Figure 2. Prints made on untreated paper (left column) show somewhat higher contrast than those on paper pre-treated with acid (right column).

Figure 2
effect-of-acid-matched-exposures.jpg

My conclusion from these tests is that I will continue my usual practice of coating “straight out of the package” paper with traditional cyanotype sensitizer and developing images with 25% (v/v) vinegar.

Looking at the overall quality of these prints, at least in my hands, the added complication of pre-treating paper with acid is not warranted. However, the minimal cost (both financial and temporal) of using vinegar in place of water for development is reasonable.

I hope that this information is useful to someone other than myself!

Regards,

--- Frank Gorga (www.gorga.org/blog)
 

glbeas

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Thank you! Ive noted too that a dribble of vinegar in the developing tray gives much better results for my van dykes, reducing the amount the print lightens in that first step quite a bit.
 

J 3

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I wonder if the acidifing the paper recomendation is a carry over from salt and platinum printing which are more sensitive to this kind of thing. Interesting experiment.
 

nmp

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Missed this thread....usually this kind of topics are on Alternative Processes sub-forum. Not sure what the difference is between the two. Then there is the Hand-coated Wet Prints, seemingly with similar topics. Kind of confusing.

Anyhow, I think the main problem that I saw with pre-acidification was that it increased the propensity for "dark" reaction, thereby causing blue staining in the highlights/unexposed areas. If I can discern correctly from your attachments, the pre-acidified prints show the first step is not paper-white (or close) even with water-development which tends to give cleaner whites than acid-development.

In my experiments, what I did was compare unexposed coated/dried papers - one with pre-acidifiaction and the other without by developing them at several time intervals. The former had much greater blue staining than the latter, starting at time zero - the difference exacerbated with acid-development.

As far as I know, pre-acidication is mandatory for the Ware's new cyanotype (no first hand experience.) For the classic cyanotype, if you like whitest whites or lowest Dmin without sacrificing Dmax, which I do - not pre-acidifying is the way to go, in agreement with the above conclusion.

:Niranjan.
 

Vaughn

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HCl is known to be a little rough on papers -- and sign of paper damage?

Other acids might work better...citric or oxalic for example -- I have used them with platinum printing.
 
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fgorga

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Thank you! Ive noted too that a dribble of vinegar in the developing tray gives much better results for my van dykes, reducing the amount the print lightens in that first step quite a bit.

Good to know. I've added a note to my vandyke notebook to try this if I ever get back to them.
 
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fgorga

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Missed this thread....usually this kind of topics are on Alternative Processes sub-forum. Not sure what the difference is between the two. Then there is the Hand-coated Wet Prints, seemingly with similar topics. Kind of confusing.

Anyhow, I think the main problem that I saw with pre-acidification was that it increased the propensity for "dark" reaction, thereby causing blue staining in the highlights/unexposed areas. If I can discern correctly from your attachments, the pre-acidified prints show the first step is not paper-white (or close) even with water-development which tends to give cleaner whites than acid-development.

In my experiments, what I did was compare unexposed coated/dried papers - one with pre-acidifiaction and the other without by developing them at several time intervals. The former had much greater blue staining than the latter, starting at time zero - the difference exacerbated with acid-development.

As far as I know, pre-acidication is mandatory for the Ware's new cyanotype (no first hand experience.) For the classic cyanotype, if you like whitest whites or lowest Dmin without sacrificing Dmax, which I do - not pre-acidifying is the way to go, in agreement with the above conclusion.

:Niranjan.

I agree the multiple forums are confusing. I guess that I posted here after realizing that the alternative processes sub-forum is in the analog only section. I use digital negatives exclusively these days.

Thanks for the rest of the information, it is useful. Especially the observations regarding Dmin

I was motivated to do this experiment because I had noticed that unbuffered papers (platine and Crane's, specifically) seemed to require much less light for the same exposure compared to other papers.
 
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fgorga

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HCl is known to be a little rough on papers -- and sign of paper damage?

Other acids might work better...citric or oxalic for example -- I have used them with platinum printing.

Hmmm... this suggests another experiment.

HCl is strong (mineral) acid. Citric and oxalic acids are weak organic acids. Thus at similar molar concentrations the pH of HCl will be much lower than that of the organic acids. Thus HCl might work without being 'rough on papers' if used at a lower concentration. Time to break out the pH meter!

I'll put it on my to do list, but don't hold your breath for the results... these days, I'd rather make art!!
 

Andrew O'Neill

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When I was acidifying papers, I used Sulfamic acid at 10%. That was with papers that really needed it like Rising Stonehenge, and an unknown paper from a Japanese dollar store (that was absolutely gorgeous after acidification). Now that I've been using Hahnemuhle Platinum Rag, no need to acidify.
 

nmp

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I agree the multiple forums are confusing. I guess that I posted here after realizing that the alternative processes sub-forum is in the analog only section. I use digital negatives exclusively these days.

Thanks for the rest of the information, it is useful. Especially the observations regarding Dmin

I was motivated to do this experiment because I had noticed that unbuffered papers (platine and Crane's, specifically) seemed to require much less light for the same exposure compared to other papers.

I thought as long as you are not actively discussing the digital negative part of the process, you are OK to put it in the alt forum. This topic is about basic aspect of the alternative process so no need to come to the hybrid section.

Regarding the buffer, there is a dependence of the reduction of FAC on the pH. For example, Ware's Simple cyanotype (which essentially involves in-situ formation of FAC) uses varying amounts of ammonia in the sensitizer to fine tune the contrast - higher the ammonia content and the pH, greater the contrast. Perhaps the alkaline buffer is playing such a role. Of course, there might be other things going on - it never is simple when it come to interaction between paper and alternative chemistries.

:Niranjan.
 
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I acidify all papers with sulfamic acid. And develop in Citric Acid. I get no bleed out with deep tones as well as high speed. The only paper I've tried that was odd was Strathmore Bristol IIRC. It solarized a little. I arrived at this by making a few hundred prints over a short time which was aided by exposure times as little as 90 seconds with an LED light I built. After doing all the experiments I did, I'm pretty convinced pre-acidifying and a citric acid bath are about as good as you can get. I also do two other things but I'll save those for if I ever write about it myself....
 

nmp

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I acidify all papers with sulfamic acid. And develop in Citric Acid. I get no bleed out with deep tones as well as high speed. The only paper I've tried that was odd was Strathmore Bristol IIRC. It solarized a little. I arrived at this by making a few hundred prints over a short time which was aided by exposure times as little as 90 seconds with an LED light I built. After doing all the experiments I did, I'm pretty convinced pre-acidifying and a citric acid bath are about as good as you can get. I also do two other things but I'll save those for if I ever write about it myself....

Hi, Patrick:

Do you use the classic formula or Ware's New formula?

And if you did a side-by-side comparison (like Frank's above) with all else kept equal, what exactly was the problem with paper as received that was solved with acidification? Just curious.

:Niranjan.
 
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