Traditional Soda-based recipes

I've been researching a little; how was developers, before developers was sold?

Back in the day people would buy glass plates or contact papers to the same size as their large negatives and make pictures. Since there was no photographers around in sparsely populated areas, people was supposed to do their own, and mix their own. Luckily since photography was invented and since people used a lot of what is now considered strange chemicals to do house chores, it was easy to find the basic chemicals. And there where druggists, or apotecharies who sold medicine, who quickly filled the need and supplied those special chemicals needed for film and paper development.

But where did they get the necessary recipes?  Dead simple, it was meticulously printed on every box for the glass plates or the photo paper.  In connection with a project for the local history chapter I've been scanning some old glass plate negatives. Some of those plates where still in their old boxes, and on the boxes was printed developer recipes.

Those I will share here.

The developers was soda based, because that was a common household chemical I believe, and used Metol, Hydroquinone or staining developers like Pyrogallol.  These was the early, stalwarth stuff they got by with, and frankly they didn't need extremely advanced stuff either, given the negative size they worked with.

Looking at the negatives and the scans I can see that when the old guys guessed exposure right, this worked very well for them, they got good developed negatives with good contrast and long tone scale with ample details in the shadows.

Since this was back in the pre-panchromatic days, this was done by tray development, and hence constant agitation, probably in a matter of minutes only.  These guys lived by the old adage "expose for the shadows, and develop for the highlights, and did so by inspecting each and every plate during development. This is probably why so few are hopelessly under-developed.

Fisrst a recipe on an old glass negative box :

Imperial Dry plate Company, Ltd of London

Here is offered two recipes and advice of how to use them for both under and over-exposure.

The Pyro-Soda developer is stated to be used for correct and full exposures, I think that translates to box ISO and plus one stop today.

The Standard developer i stated suitable to general snapshots and under-exposures, I think that translates to box speed and minus one stop today.

Or simply stated the Standard developer here is the more active, while the Pyro-Soda developer could possibly be a softer working, more fine grained recipe.

Measures is given in English and French measures which would be british and metric measures today and are equivalent.

Recipe,    Imperial Pyro-Soda

Dissolve chemicals in the order given

 

Stock solution

Potassium metabisulphite  10  gram

Pyrogallic Acid                  83  gram

Potassium bromide            13  gram

Water to    1000 ml

     

From this stock solution one mixes

Part 1

Stock Solution                            150 ml

Water (boiled or distilled)    to   1000 ml 

Part 2

Sodium Sulphite                         100 gram

Sodium carbonate                       100 gram

Water (boiled or distilled)  to    1000 ml

In use  mix one part 1 with one part 2. For underexposure increase part 2, for overexposure increase part 1.

Metric measures translates to these british measures :

Stock solution

Potassium metabisulphite 50 grain

Pyrogallic Acid 1 oz

Potassium bromide 60 grain

Water to 22 oz

From this stock solution one mixes

Part 1

Stock Solution 3 oz

Water (boiled or distilled) to 20 oz

Part 2

Sodium Sulphite 2 oz

Sodium carbonate 2 oz
Water (boiled or distilled) to 20 oz

In use mix one part 1 with one part 2. For underexposure increase part 2, for overexposure increase part 1.

***************************

Personally I think this could be translated to caffenol, if one replaces the Pyrogallic acid with Instant Coffe and tries that, but at this point this is pure speculation.

____________________________________________________

Recipe  Imperial Standard
Dissolve chemicals in the order given


Part 1
Metol                                      5 gram
Potassium Metabisulphite       14 gram
Pyrogallic Acid                        6 gram
Potassium bromide                  2 gram
Water (boiled or distilled) to   1000 ml
              
Part 2
Sodium Carbonate                  200 gram
Water (boiled or distilled) to   1000 ml
In use mix one part 1 with one part 2


Metric measures translates to these british measures :

Part 1

Metol                                  45 grain
Potassium Metabisulphite   120 grain
Pyrogallic Acid                    55 grain
Potassium bromide              20 grain
Water (boiled or distilled) to  20 oz

Part 2
Sodium Carbonate                    4 oz
Water (boiled or distilled) to     20 oz

In use mix one part 1 with one part 2


***********************

Personally I think this could be translated to caffenol, if one replaces the Pyrogallic acid with Instant Coffe  and replaces Metol with ascorbic acid, and tries that, but at this point this is pure speculation.



If one chooses to try this, make a note that the standard recipe when translated to Caffeine, stores better than the pyro-soda recipe, because the ascorbic acid in part 1 protects the instant coffe from oxydation. But also note that instant coffe as always is the weak link in all the Caffeine recipes, coffe is no chemical, it is a wildly variating mixtore of substances that we have no control over, that contains degradable foodstuffs and those will quickly go sour as all coffe drinkers know.

However this trip back a century in time or so is a valuable insight into how they did things back in the days, soda based developer is nothing new, on the contrary they once was the base and foundation that photography was built upon. These developers also was what guys like Patric Gainer was looking at, no doubt, when the alternative developers first surfaced some 20 years ago.

In closing a quick look at the fixer mentioned here :

Acid Fixer solution :

Sodium Hyposulphite            500 gram

Potassium metabisulphite         60 gram
Water (boiled or distilled)  to 2500 ml

Metric measures translates to these british measures :


Sodium Hyposulphite     1 lb
Potassium metabisulphite  2 oz
Water (boiled or distilled)  50 oz,

Since a soda based developer combined with an acid fixer can give rise to spots in the emulsion, at least the soda from the developer needs to be watered out by 3 changes of plain water as a stop bath, instead of a traditional stop bath.

Note a plain, non-acidic fixer can be made simply by not adding metrabisulphite, this might be preferred



More will follow

Phenidone-C Developers - I've Learned A Few Things

I've been tweaking my phenidone/c developers recently and learned a few interesting things so I thought I would share.  Here are some quick points:

1. The amount of phenidone is directly proportional to developer activity.  Using PCB (19g borax + 6g ascorbic acid + 0.15g phenidone + water to 1L) as an example, reducing the phenidone from 0.15g/L to 0.1g/L makes a huge difference in developer activity.
2. The more phendone/c you have, the lower pH you need for active development.  I discovered that with enough phenidone/c you can have very active development at a pH of 7.2.  On the other extreme, you can use ridiculously small quantities of phenidone/c (e.g. PCM uses 0.8g/L ascorbic acid +  0.02g/L phenidone) but increase pH for similar activity.  This means you can adjust the activity of phenidone/c developers either by varying the pH or the amount of ingredients.
3. More vit-c doesn't make much difference in activity but does extend shelf life.  For example, using ascorbic acid at 4g/L vs 8g/L shows no discernable difference in activity but makes a re-usable developer last longer.
4. pH does not affect grain very much.  Grain from developers at pH 8.4 and 9.6 look very similar.  This is based on observations with a scanner and RC prints.
5. Stand development doesn't work the way we think.  Testing showed no significant difference between full stand development (60s initial continuous only) vs minimal agitation (60s initial continuous, 10s every 5 mins) except for time when using a very dilute developer (PCM).  Agitation more frequent than 5 mins showed more highlight development and increased contrast.
6. You really don't need much potassium bromide.  Even without potassium bromide, fog is minimal (most won't notice it), but adding 0.04g/L clears it up with no effect on developer activity.

If you like to concoct developers as I do I hope you find this useful.

MM

TCB - Trouble In Paradise

I've been playing with p-aminophenol developers again.  I found that parodinal + ascorbate + borax (RCB) makes for a fine grain full speed developer.  I also found that substituting ascorbate for sulfite in parodinal works too (TCB).  However, doing side-by-side tests as a one-shot developer, I find that I need twice as much ascrobate-parodinal as I do sulfite-parodinal to get the same level of activity.  This bugs me a bit as ascorbate-parodinal is half as efficient as sulfite-parodinal which means I'm wasting a fair amount of  ingredients.

Activity levels aside, the visible difference between the two is the formation of long needle-like crystals in the sulfite version and not in the ascorbate one.  I don't know what the crystals are but if they are p-aminophenol that means that sulfite-parodinal is super-saturated while ascorbate-parodinal is not which would explain the difference in activity levels.  Could it be that the conversion of acetaminophen to p-aminophenol needs sulfite to complete?

I have nothing against sulfite and it's something I stock anyway as I use it in my fix.  I'm just curious about the chemical process here so I can better understand what is going on.  I am not a chemist in any way so I'm hoping to learn from others with more knowledge about this.

MM

Phenidone-C Divided Developer - Strangeness

I've been toying with the idea of a Phenidone-C divided developer akin to divided D-76 or Diafine.  Based on my experience with Phenidone-C so far, I propose the following formula:


Part A
Ascorbic Acid - 80g
Sodium Bicarbonate - 60g
Water - 750mL (make sure all is dissolved and effervescence stops)
Phenidone - 1g
Water to make 1L

Part B
Sodium Hydroxide - 1.45g
Borax - 6.92g
Water to make 1L

Agitate for 5 mins in part A then 5 mins in part B.

I did a quick test with the recipe scaled down to 100mL and use film clips to get an indication of activity.  What I expected to happen and what actually happened really surprised me.  I expected there to be no visible evidence of development in part A while the ascorbate + phenidone soaked into the emulsion and expected all the development to be visible when in part B.  To my surprise, after about 1 min in part A I noticed a slight darkening of the film and after two mins it was nearly black.  I thought I was going nuts here as everything I read and experienced showed that you need a higher pH to get decent activity out of Phenidone-C.  The time in part A is within range of a normal 8-10 min developer.  I thought I may have contaminated part A and increased the pH so I checked it with a calibrated meter and it showed 7.2 ... about what I expected being near neutral.  Now this is confusing ... ascorbate developing at a pH of 7.2?  I still don't believe it but I ran the same test 3 times with the same result.  I have no idea what's going on here and cannot explain it.  On the plus side I'm thinking with the really low pH this very concentrated phenidone-c-bicarbonate mix could be an extremely fine grained re-usable developer.

On one hand this really complicates my idea for a two part phenidone-c developer but on the other hand I may have stumbled across a new unexpected developer.

Next step is to actually process film instead of test clips to see real world results.  I propose two initial tests, one with just part A for 8 mins and one with part A for 2 mins and part B for 6 mins.

Adox CHS-50 and Caffenol

Some experiments with Caffenol and Adox CHS-50 Art film; a range of development times. The images were all taken on the same day on 35mm, using an Olympus OM-10 in its default auto-exposure, manual focus mode. A cheerfully sunny day, so some high-contrast images at times.

A single batch of developer to the recipe below - nothing exciting, it's just the standard CCM at 1+1 concentration - was made and the film segments developed at approximately three-quarter-hour intervals; that means that the developer for the 16 minute strip had been hanging around open to the air for perhaps two or three hours. That may or may not be significant.

Ingredients:

A point to note is that my sodium carbonate is in the decahydrate form; that means that it needs 2.8 times as much - by weight - as the anhydrous form. If you have the anhydrous form, you will need to use proportionally less than in this recipe; you should also note that it will raise, not cool, the water in which it is dissolved.

The vitamin C is a pure powder from a health-food shop; the coffee is the cheapest 'strong instant' from my local supermarket. The same supermarket provides the soda, from the washing department. My tap water here in the UK is rather hard.

Recipe:
Water at 25C - 800ml
Sodium Carbonate Decahydrate - 54g
Vitamin C - 8g
Coffee - 20g
Water at 20C to make up to 1000ml

Mix in order, allowing the fizzing to subside before adding the coffee. The temperature will be close after the soda has cooled the original water.
Prewash 2 minutes in water, wash after development 2 minutes in water, and fixed in Ilford Hypam 1+4 for 4 minutes.

Images are all scanned with no gain, black, or gamma adjustments to permit comparison of contrast range. These levels have been set for the positive images.

10 minutes:
The images appear slightly underdeveloped in the shadows, but produce acceptable scans.
Contrast range 22-224, gamma 0.8














12 minutes:
The image appears properly exposed - there is good shadow detail under the roof, for example.
Contrast range as for the 10 minute development, but gamma set to 1.0.







14 minutes:
Contrast range has decreased to 35-235; gamma at 0.8.
A high-resolution scan at 4800dpi shows resolution as good as the lens and no visible grain.














16 minutes:
Contrast reduced further: 45-235, gamma at 0.8 again. Still producing an acceptable picture, but the fine detail appears to be soft; this could be a focus issue but I doubt it.






Conclusions:
For box-speed Adox CHS-50 35mm (and probably 120 roll) a development time in Caffenol 1+1 (20C) of 12 minutes is probably the best. Acceptable pictures will be produced at anything from 10 to 16 minutes, but increasing the time decreases the available contrast and may cause some softening of detail. I don't have a mechanism to explain this.
It's curious that the decreasing contrast is not due to increasing fog; there is none visible at any development time. Rather, the minimum black level, after inversion, appears to rise slightly. I can't explain this, either...
This does not apply to CHS-50 sheet film, which has a different response and upon which I am still experimenting.

KafeaFine

Michael just offered a suggestion on Flickr:

".........I think metaborate (a.k.a. Kodalk)



borax.com/pdfs/dist/DataSheet.Borates.SodiumMetaborate8Mo...


is a more suitable non-carbonate alkali ( than borax) as it has much lower molar mass, much higher solubility, can hit a higher pH, and still have relatively good buffering characteristics. 1g metaborate = 0.692g borax + 0.145g sodium hydroxide if you're interested.


On a slight tangent, I did have an experiment in mind that is somewhat related to this but I have not had time to try so I'll share it here. My goal was to create a longer lasting two part Caffenol-C developer. I was thinking of mixing coffee + vit-c in a very concentrated solution (as little water as possible) with enough hydroxide to make it neutral (this is part A). Part B would be a suitable alkali solution (borax, metaborate, carbonate) with potassium bromide if necessary. My thinking for part A is that the solution might last longer due to the high concentration of ingredients, the vit-c being in sodium ascorbate form, and the pH being neutral. Part B would not have to work so hard as part A is already neutral.

Another possible permutation is to mix part A with alcohol (methanol, isopropyl, etc.) instead of water to minimize oxidation but I have absolutely no idea if coffee + vit-c is soluble in alcohol. "


Lets give this a spin!  I will ponder a bit upon this, hopefully Michael will be back with more inputs, and even more welcome, others might offer comments too, I think this is a good idea, and a possible alternative to now out-of-production Daiafine.  A two part developer with an extremely long shelf life, little if any time and temperature dependency is nice.


Comment from Michael :
"Haha ... I didn't expect to find this here ... cool.

Anyway, I'm pretty sure we cannot get this to work as a conventional two-part developer such as Diafine or divided D-76 because we need so much coffee for active development. I think it may work by using x volume of part A + y volume of part B + z volume of water, most likely suitable only for one-shot use.

I think that a Phenidone/Vit-C developer would make a better candidate for a true two-part developer like Diafine as so little developing ingredients are required.
The problem here is oxygen ... it's the oxidation of developing agents that makes them weak. I have a fair amount of experience dealing with this problem as Phenidone has this same issue and a few approaches have been used to address this.

Alcohol (methanol) has been used as it generally has little water, hence little O2. Ethylene Glycol, Propylene Glycol, and Glycerin have also been used as they have no water and no O2.
The potential problem with alcohol or glycol is solubility of the developing agents. Experimentation is required to determine how much coffee can be dissolved in various solvents.

Another idea that came out after alcohol/glycol was to use water but have excess preservative, vit-c in this case. The theory being that the excess ascorbate preserves what's there and it seems to work. These principles have been used and proven, the excess ascorbate one is used in PCB, and the glycol one is used in PCM.

If I were to attempt a Phenidone/C two-part developer I would make part A with an Ascorbic Acid to Phenidone ratio of 80:1 and enough sodium bicarbonate to neutralize the solution.
This could work out roughly as 80g ascorbic acid, 40g sodium bicarbonate, and 1g phenidone in 1L water.
Part B would be a 1% sodium metaborate solution.
The pH will be high enough to get some good development and the buffering should make the chemical reaction last as long as is required to exhaust the Phenidone/C from part A. I would do 3-4 mins agitation in part A and 5-10 mins agitation in part B.

I have absolutely no idea if any of this would actually work but I think it could.

Thank you Michael, I have to put my thinking cap on, will be back with questions.....

Cafenol ingredients.

We get questions all the time of what is the right ingredients to be looking out for and to buy in different parts of the world.

This is important, because the wrong ingredient will leave us with a non-working or malfunctioning developer.

I ask you to submit pictures of the ingredients you use, and state what country, and where you found what you use.

I will set up an extra page, like the recipes page, where a log of ingredients sorted country by country will be kept.

Anyone can send me a short not and appropiate pictures on e-mail.  Thank you beforehand.


email :

erik.prestmon@hotmail.com

erikp

My final word on Iodized salt as a restrainer

Once again Reinhold has come forward with an excellent post in his blog :

http://caffenol.blogspot.com/2011/07/salt-in-soup.html#comment-form

he clearly demonstrates what one can expect, using ordinary non-iodiozed salt, iodized and comparing that to KBr, all done with the same type of film, and I think he has deliberately chosen a type of film that REALLY will give you fogging, judged on an example of a test with no anti-foggant added that he published some time ago.

His conclusion is simple : non-iodized salt will work, but one has to add more than what is accepted for iodized salt, and one run the risk of another type of fog. dichroic fogging.

Iodized salt will work, and better the higher concentration og KI in the salt.

He also demonstrates clearly that nothing compares to straight KBr, if you can find it, by all means go for that, all kinds of iodized kitchen salt seem to leave a certain fog level, and worse in the cases one really needs an anti-foggant.

Reinhold demonstrates this with pictures of the film, scanned side by side and shown as negatives, very enlighthening, and solid work as always by reinhold, he was and remains the master!

I have come to the conclusion, based on this and other examples from other blogs and net-sources that I need not concern myself any more with this. Reinhold has yet again saved me and other interested workers a lot of hard work and his recommendations are absolutes sound and solid.

I recommend Reinhold's blog BTW, visit it often and read all of it, it is well worth the time, he has put a lot of effort into his work.

IKEA to the rescue!

Anyone that has a hard time finding volumetric measures now has an excellent source : the swedish furniture & storeys supplier meglamorate IKEA!

In their warehouse I recently discovered a set of excellent volumetric measures, 1 ml, 5 ml, 15 ml and large, translated to US measures these are 1 pinch, 1 teaspoon (1 tsp), 1 tablespoon (1 tblsp) and 1 coffee-measure.

It is very convenient to use volumetric measures, once one has calibrated & adapted one's workhabits to them.  As soon as one gets used to working with coffenol and mixing developer on the fly it is very easy and rewarding to leave the weights behing and enter the float-zone and rely on volumetric measures.'

I routineously use these measures, but at the same time issue a warning : whenever one of the components are changed, then re-calibrate the measure for said component. How this is done in a scientific manner is thoroughly described already in this blog, just have a quick look at the the instalment "What IS a teaspoon...." .

The IKEA-set of measures are so cheap, in the best IKEA tradition, that any worker can buy more than one set. Buy FOUR : one for the missus, to keep the calm in the house and 3 for the Master of the House, that way one can mark the measures with for instance nail polish and reserve one for Soda, one for Ascorbic acid and one for Coffe, saves time on cleaning for those concerned about that.

Also the teaspoon measures are fine for 1 tank - 1 film usage, while the tablespoon measures are fine for 1 litre mix use, they just needs to be calibrated for the purpose.

Myself I have calibrated my components thusly :

Water to fill 11 US fluid ounces (start with 8 oz and top up as soon as all components are in.
Soda  (anhydrous, decahydrate needs 2.7 times as much)  3 teaspoons
Ascorbic acid powder (pure powder marked E300 in Europe) 2 teaspoons
Instant Coffe (blackest, cheapest you can find, "office coffee)  7 teaspoons.


Now I strongly urge anyone to meticoluosly calbrate their own measures to their own chemicals.

But I note in passing : Coffenol is a very forgiving mix, many workers report success from wildly variating recipes, one can get away by slightly altering development times for instance.
Therefore, chances are you can use my recommendations here as is, and get a mixture quite similar to the mixture known as Reinhold's Caffenol CC-M. If you add ca 0.5 gram KBr (Potassium bromide to this mix, the result equals Reinhold's CC-M mixture.

Start times are 15 - 16 minutes for most film types, with a little longer for C41 and longer still for Fuji C41 films and 400 ISO films.  Feel free to experiment, it is fun!

STÄM set of 4 measures

Glanced from the IKEA catalog these comes in several colors,

I only found these green colored ones

From the label here one can clance all data,

it should be possible to order this by phone or the Net from Ikea

order number 801.523.58  several colors.

The catalog names these measures as :

1 spicemeasure, 1 teaspoon, 1 tablespoon (spiseskje in scandinavian) and 1 desiliter (1/10 liter)

These are marked 1ml, 5 ml, 15 ml and 1 dl respectively.

Update on mixing a litre :

Since 11 US fluid oz is close to 1/3 of a litre and since the difference between 1 teaspoon and 1 tabklespoon is also 1:3 it is *real easy to use volumetric measures for a litre mix also.
Just use the tablespoon measure and measure out 3 tblsp, 2 tblsp and 7 tblasp from each ingredient as outlined above and top up the water to 1 litre and you should be close enough to be able to home in on perfect results!

Best of luck and please do share examples of your work, either by sending them to me or sharing them on Flickr!