Fujicolor Eterna 250D and Dignan-2bath-developer

I have been using Dignan developer for C-41 films now for quite a long time and gained some experience using it. Results depend much more on the second bath composition and duration. The first bath may be kept as it was proposed by Dignan but I had to change the second bath several times in order to achieve better results. Durations of both baths have also to be adapted.

Let me remind you about the original recipe of the first bath:

500 ml water
9 g Sodium Sulphite

1 g Sodium Bisulphite

11 g CD4

Water to make 1 liter

pH should be less than 6.5
Time duration: 3 min. at room temperature

One may use Sodium Metabisulphite instead of Bisulphite, in a 1:1 basis. 3 min. duration is very short and may lead to poor results, specially if the bath is not fresh any more. I use always 15 min. and this first bath will keep for some 2-3 months, developing about 40 films. Because I prepare only 500 ml each time, I use it for about 20 films. In a closed amber bottle and if not still used it will keep longer than 3 months. I thought that this first bath could live for ever but no, it will loose its «strength» and you need to increase its duration. So, 15 minutes will work 20 times with minimum changes in results. When the image density starts to decrease, even with a long 2.nd bath, it is time to make a fresh 1.st bath.

Now, let me talk about the 2.nd bath. Remember that the original recipe was:

500 ml water
53 g Potassium Carbonate
0.5 g Potassium Bromide
Water to make 1 liter.

optional: Benzotriazole (Kodak anti fog #2) 2 milligrams
pH: 11.8
Time duration: 6 minutes at room temperature


I am now quite sure that the second bath must be adapted to the particular film we are using. But in general the original recipe is to concentrated and some films will 'overdevelop' in the sense that the dyes may be so dense that the color will tend to loose saturation.

Most of the modern films worked well with following recipe, where Potassium Carbonate is reduced to less than the half and the time prolonged to 15 minutes, frequent agitation for even development:

500 ml water
25 g Potassium Carbonate
0.6 g Potassium Bromide
Water to make 1 liter.

Example:

Fujicolor Superia 100 with reduced soda version

I purchased, at ebay, 400 ft of an old 35mm movie colour film (Fujicolor Eterna 250D) and I intend to use it for taking photographs. Movie films have an anti-static layer on the back, which need to be removed and this may happen before or after normal development. But with Dignan 2-bath you don't need to care about it, it will be removed naturally in a more prolonged second bath that will be then discarded.

Following my reduced soda recipe, I developed a first batch using 15 min. first bath and 30 min. second bath, frequent agitation. See result below:

Fujicolor Eterna 250D with reduced version

The colors were very dense and looked fast B&W in film. I had to use auto color correction of scanner and increase saturation in order to get colours.

I was hesitating between «Is it so with movie films? Do they need to be darker because the projection light is very strong?» and «Is it possible to get better results diluting even more the second bath?». And because I have nothing to loose, I diluted the 2.nd bath even more:

500 ml water
20 g Potassium Carbonate
0.5 g Potassium Bromide
Water to make 1 liter.

And yes, I have got a better result, almost like it came out, setting the scanner to full automatic.

Fujicolor Eterna 250D with extra-reduced soda

I liked the result, the red could be a little more saturated but it is much better than the above one.

Is Caffenol a fine grain developer?

 I got two packs of 30.5 m TMax-400 film expired in 1998. From the beginning I saw that this film was very grainy and I had to search for a fine grain developer. After some bad experiences, I decided to make a batch of a Diafine clone and it worked more or less well, giving still grain but acceptable.

Expired TMax-400 developed with a Diafine Clone

But I always had the impression that films developed with Caffenol using only coffee and not too much soda had very small grain. So, I tried it with the above mentioned expired film. I was positively surprised. In fact, I got much less grain, as shown bellow:

Expired TMax-400 developed with Caffenol

The Caffenol I am using now has following recipe:

20 g/l soluble cheap coffee
10 g/l Potassium Carbonate
4 g/l Table Salt

Usage: 90 minutes at 20ºC, almost stand development. Agitation each 5 minutes or so.

My last developed film with this developer was a 120 TMax-400 but not expired, exposed with a Weltaflex 6x6.

TMax-400 developed with Caffenol

C-41 without CD4?

A reader and friend of this blog, Matveev Vladimir from Russian Federation, is in contact with me since some time, maybe months now. And he is also trying to develop C-41 films without CD4. In fact, CD4 is only a modern stuff, if we read about the history of color photography, other substances came first.

Perahps this is the case of PPD, paraphenylenediamine, that has been used before CD4, besides CD4 is a derivative of paraphenylenediamine.

OK, nevertheless, old technics are sometimes forgotten and someday nobody knows how it was first. For instance, one of the first fixers in silver photography was common salt but nobody believes it today.

Returning to the theme, this friend from Russia, Matveev Vladimir, wrote me and shared his experiment of developing a C-41 film without CD4, but using PPD instead. And it worked very well indeed.

The first picture is the direct scan of the negative developed w/o CD4 and the second is the same picture automatically adjusted by the scanner. To be sure of this, I downloaded the first pic and made auto adjustments with a software and I've got the same result. 

 

This is, for me, an importante step in the search for an alternative C-41 developer using a common product and not a commercial one. This common product may be a product containing PPD, such as hair dye for instance. I have been trying it without success, but now I have a proof that PPD does develop color in C-41 films and I will be trying again, in order to find an alternative C-41 developer from scratch.

I am back to Dignan's 2-bath C41

I could use a 500ml batch of the multipurpose developer I suggested in the latest posts a couple of times, maybe 6 times in the period of one month or so. It is now exhausted and colors got a little less vivid. I decided to use the last prepared baths A and B of Dignan's (slightly modified by me) that stayed all the last month at shelf, after have been used a couple of times. They worked splendid, what means that this method is much cheaper than the one bath solution. My main and only problem now is to find the best agitation process because I already understood that C-41 needs a constant and gentle agitation during the bath B in order to avoid uneven development. The best would be a motorized agitation but certainly not that cheap. I have to see if I find some time to produce a homemade agitator.

And her are some pictures made with my Agfa Clack, one of the best simple cameras I ever found.

Theory and praxis

Below you may see 2 photos, one in color and another in B&W. The first photo was exposed in a Clack camera, using Fuji Superia 100 expired 1998. The second was exposed in a Pentax MZ-60 using TMax-400 expired 2000.

In common they have the expired date but they have more in common: they were developed simoultaneously in the same tank with the same developer. Both were developed for 30 minutes, then rinsed and fixed. After this the B&W was taken off from the tank and putted to wash and the color film underwent a blix process to remove remaining silver and finally washed together with its 'black brother'. And then both were hanged to dry.

I made some changes to the recipe I gave in the last post and, like expected, it worked well, I might have to reduce developing time from 30 to 20 minutes because both looked a bit overdeveloped.

Recipe:

3 g Potassium Metabisulfite
20 g soluble coffee
6 g CD4
30 g Potassium Carbonate
1.3 g Potassium Bromide
Water to make one liter

Use at 20ºC, agitation first 30s then 10s each minute for 20 minutes

A multipurpose developer

I've been long looking for a film developer that could be used both for color and black and white films. I have not yet the final formula but it will not take too long anymore to establish it.

If you are following this blog since its beginning, you will remember that I started developing color films with a very simple homemade soup which included only CD4, coffee and sodium carbonate. I succeeded but having to adjust colors and it was a one-shot thing you had to prepare each time, so not practical.

Then I started using Dignan's 2-bath developer (at room temperature) and I made several changes and experiments with the second bath in order to achieve better results. This was quite a long enterprise.

In a recent discussion with a net good fellow we came to the conclusion that color films may be developed in a one-bath developer at any lower temperature than the recommended by brands, if we only adjust the times. At 20ºC it takes about 20 minutes and the results are very good.

If you read this recent article of mine, you will understand how I discovered that coffee can replace an important agent used in C-41 developers called HAS (Hydroxylamine Sulfate). And having in account the several variants of the formulas of a C-41 developer, I composed following recipe:

3 g Potassium Metabisulfite
1,2 g Potassium Bromide
5 g CD4
10 g Coffee
25 g Potassium Carbonate
Water to make 1 liter

 This recipe has a lower amount of Carbonate for pH reasons and takes slightly more time, about 30 minutes to develop a C-41 film at 20ºC.

I made a 500ml batch of the recipe above and it developed several C-41 films in a time interval of about 2 months but now I think it is becoming weak and I will have to prepare another. Neverthless, I exposed the day before yesterday a B&W film and, after estimation of the developing time with a stripe of the same film, I gave it a try developing for 90 minutes. And it did develop the film satisfactory.

It would be much better if the development times for color and B&W were the same, but B&W is taking about the double of time. So, the next step is to prepare a new soup with twice the amount of coffee and adjusting Carbonate to get the same pH as the previous recipe, about 11.

If I succeed to have a developer that develops both color and B&W in the same time, I can imagine that it will be possible to load a developing tank with color and B&W films and develop them together. But, attention, B&W can't be bleached, only fixed. So, the procedure would be following:

1. Developer - X minutes
2. Rinse or stop bath
3. Rapid Fixer - 3-5 minutes
4. Open the tank, take the B&W film out and put it in water to wash for 30 minutes
5. Blix the C-41 film to remove remaining silver and filter layers - 15 minutes
6. Wash C-41 for 15 minutes
7. Hang both films to dry

Long expired TMax400 developed in Caffenol-color

One roll, eight pictures

When using a 6x9 camera, like Agfa Clack, we have to be spared for not repent having spent one shot with nothing interesting. This is totally different when shooting with a digital camera. Recently I erased a card of a digital camera and I realized that in «quality» mode I still had about 1000 pictures to shoot. With so many shots it becomes difficult to choose afterwards what to keep and what is rubbish. And this is the only reason that maybe will limit our shooting digital addiction.

If I know that I have only a few shots, automatically I make a selection of what is worth and what is not much. And this will perhaps play an important role in the results. Of course you may not agree with me, I hope!

Good news for caffenolics?

When I started this blog, I intended to find a C-41 developer using common household products like coffee, lemon juice, aspirin or whatsoever.

Of course I was open to several failures before something interesting appeared by chance or by searching. And, at that time, I knew very little about processes and my experiments were more or less dictated by trial-and-error.

But one of the first C-41 alternative developers I tried was this one:

1 tsp sodium carbonate, aka washing soda
4 tsp soluble coffee
10 ml of a 5% solution of CD4, CAS number 25646-77-9
water to make 500 ml

Yes, it worked like regular developer at about 40ºC but 30 minutes time. This is because maybe I used very little CD4, about 1g/l  instead  of the standard 5g/l. Never mind, but I remember the results were not so bad and this stayed in my memory until now.

Then I discovered the room temperature process Dignan 2-bath developer that was promising but it has been a long way until I found a way to improve it in order to get better colors, grain and sharpness. My latest improvement lead to:

Bath A

500 ml water
9 g Sodium Sulfite
1 g Potassium Metabisulfite
11 g CD4
Water to make 1 liter

Bath B

500 ml water
25 g Potassium Carbonate
0,6g Potassium Bromide
Water to make 1 liter.

10 minutes bath A and 15 minutes bath B stirring frequently but gently and it will produce stunning colors and acceptable grain.

But, recently I was discussing C-41 with Reinhold G. and he showed me that one-bath developers also develop at room temperature, it's only a question of more time, I do not need to complicate it with a 2-bath developer. So, I started making one-bath at room temperature. Searching for recipes at the internet I found these:

One special stuff used in C-41 developers is HAS (hydroxilamine sulfate) and it is said to be a stabilizer for the developer. Well, investigating about the paper of HAS in the developer, the most complete answer I found was this one at APUG. It is acidic, a weak B&W developer and a preservative.

Considering that COFFEE is acidic too and a weak B&W developer, adding a preservative like metabisulfte to the formula, could make HAS unnecessary. I would prefer that CD4 could also be replaced with something else but by now, I found no substitute.

Resuming, I prepared following developer:

3 g Potassium Metabisulfite
1,2 g Potassium Bromide
5 g CD4
10 g Coffee
25 g Potassium Carbonate
Water to make 1 liter

 I tried this formula with coffee and without and the formula without is very flat, low saturation, low contrast, unsharp. With coffee I had much better results. Besides, much less post treatment, just accepting automatic adjustments of scanner/software. Without coffee I had to adjust saturation and contrast until a certain point. To get more was almost impossible.

Without coffee

With coffee

FotoSketcher

Film Photography, B&W or color, have reached a very high quality. Lens, shutters, films, chemicals, papers, scanners, all parts of the process are pushed to the highest levels. But still we miss old looking pictures, watercolors and pictures on canvas.

Digital was supposed to replace all those ancient imperfect reproductions of reality. But, surprisingly, every image software offers the possibility of distorting the perfect pictures in a number of ways. And here are some examples that I produced using the free software FotoSketcher.

Vintage look

Watercolor look w/ frame

Watercolor with texture

Mixed fixer, Potassium & Sodium Thiosulfates

Recipe:

100 g Potassium Metabisulfite
36 g Sodium Hydroxide
29 g Sulfur

Preparation:

First dissolve separately the Metabisulfite and Hydroxide, each in about 500 ml water. Then pour the Hydroxide solution on the Metabisulfite. In this step you are preparing a mix of Potassium and Sodium Sulfites, according to:

K₂S₂O₅ + 2 NaOH = K₂SO₃ + Na₂SO₃ + H₂O

Bring this 1 liter solution to the fire and when it starts boiling lower the flame and add the 29 g of Sulfur. Let it boil slowly and stir. At a certain point the Sulfur sinks to the bottom. Wait some more minutes and then switch off the fire. Let it cool and filter the solution with coffee filter. Not all Sulfur reacts, but you will end with Potassium and Sodium Thiosulfate and the remaining unreacted Sulfites.

If all Sulfites had reacted the overall reaction would be:

K₂S₂O₅ + 2 NaOH + 2 S = K₂S₂O₃ + Na₂S₂O₃ + H₂O

Usage:

Use the solution you got, about 700-800 ml, undiluted. It takes 5 minutes to fix the normal grain films and 15 minutes the T grain films.

Agfa Clack is gold!

While most of the 6x9 cameras use a 105 mm lens, Agfa Clack uses a meniscus single lens of 72 mm. This makes it a wide angle camera. And I am quite surprised about its quality. Just a few sunset captures...

Improvements

First of all, let me tell you how I prepare my salt fixer solution:
I use 300 g salt per liter of water. But, for one single bath, I don't need to prepare one liter, 500 ml is enough.

1. Weight 150 g of kitchen salt, yes, the grainy one. it's cheaper than table salt.
2. Put the salt in a heat resistent beaker and add hot water until you reach 550 ml.
3. Stir for several minutes, 10-20, until most of the salt is dissolved
4. Filter the solution with coffee filter and you will have about 500 ml of a concentrated salt solution. Filtering is important to avoid impurities but also to filter very small salt grains that will induce recrystalization of salt that may harm the film to be fixed.

This salt solution may be used as fixer but takes some 24 hours to fix at room temperature for common films and 48 hours or more for T grain films like TMax.

I challenged myself to find some additive that could make salt a better fixer, working faster. 

The first additive I discovered by trial and error was Potassium Bromide. Small amounts like 3 g/l will prevent recrystallization of salt and speed up the solution to some hours less.

Next stuff that went under my tests was Sodium Hypochlorite, common household bleach, less than a 5% solution of Sodium Hypochlorite. I knew, because already tried that a small amount of this bleach in water would eat the silver completely. But I thought that, maybe in a very small concentration, it could help salt to fix better.

Tests with stripes of film showed me that the idea was not silly, the film was cleared faster when I added some ml/l to the salt solution. At 5ml/l of bleach I could clear a stripe of TMax in 1 hour. So, maybe in 2 hours it fixs completely.

First result:

5ml/liter, fixed in 2 hours

I didn't count on this side effect, some white (in positive) spots that were produced by some deposits of some unknown material. On the other hand, the silver started to be dissolved too and the spots may be of silver 'condensate'. The film base was completely clear, with a yellow/brown stain that came out by washing for more than half an hour.

In my last experiment I reduced the amount of bleach to only 2 ml/liter and the fixing time to 4 hours. Waiting for the film to wash and dry. I will post in some hours... Be patient. I don't know how it will scan but looks better.

... waiting!

A little more time because refixing for more 2 hours was needed. Some typical vertical marks showed bad fixing in 4 hours. But for normal films could be more than sufficient, perhaps 2 or 3 hours would be enough.

... and waiting!

Here is the result, after 6 hours fixing of TMax400, expired 1991. The next I will experiment with Ilford FP4 or similar. I think that even after 6 hours TMax is not completely fixed. But I was affraid that the image could be eaten like the one before. This time no artifacts like stars in the sky and I will see how long I may fix to have a total fix. The film base was still slightly cloudy. The stripe will return to the fixer for some hours more. Maybe 10-12 hours in total which represents 4 times less than with salt alone. 
.

Fixer used:

150 g salt
Hot Water to make 500 ml
2 g Potassium Bromide
1 ml of 5% solution of Sodium Hypochlorite

Still about using salt as fixer for films

Although salt has been used in the past to fix daguerreotypes, it became then a myth among photography hobbyists. People who tried it, didn't know were to start when preparing a salt bath that possibly could fix the films used today.

I like testing if myths are true or false. So, and because at the time I was experimenting with daguerreotypes too and reading how it worked, I decided to try whether salt was able to fix modern films.

I was using at the time Fomapan and Shangai GP3, the cheapest on the markt.

Intuitively, and after I tried a randomly dissolved salt solution, some grams per liter (don't know anymore), and this didn't work in a reasonable time span, I decided to make the more concentrated solution I could and wait the longest time I could consider reasonable, the whole night. If we develop films at night, this is a time that will not affect our patience because we are sleeping.

So, after some time shaking a PET bottle full with salt and water, I putted a stripe of virgin film in a bowl and poured the salt water on it and went to sleep.

Next day, the stripe of film was completely transparent, what showed me that salt as fixer is not a myth, but it does make the job.

Further investigation showed me that if the salt solution is enough concentrated and warm it will take less time to work. For films like Fomapan, Shangai GP3, Ilford FP4 or HP5, it is possible to completely fix with salt in 3 hours, using 300 g/l of salt and temperature above 30ºC.

All my tests and results were made publicly, at Flickr. This all happened 3 years ago, in 2012. Since then, nobody spoke about, as far as I know. Recently, at the forum of Filmasters.com there was a discussion about it were salt as fixer was not a myth anymore, meanwhile my results were spread, thanks to Reinhold and trough his fine blog Caffenol. 

Some days ago, someone wanted to see pictures I made and fixed with salt. But because these pictures were at Flickr, where I closed my account, but I found this information at ipernity were I have an account now: http://www.ipernity.com/search/photo?w=303455&q=salt&view=2

Fixed with salt

Well, but the introduction took too long and what I wanted to bring you today are some more information on how to better use salt as fixer and this is particularly interesting for countries were travelling with chemical stuff is very illegal and old fashion photographers will have troubles with the law.

When preparing salt fixer, be aware to dissolve as much salt you can. 300 g/l, if you succeed, will do the job. Use warm water and try to get it all dissolved.

The next, pass the solution through a coffee filter. This step is important, as I found recently. Not only to retain some impurities of the salt but to prevent that small and invisible undissolved salt stay in the solution. These salt particles are, I think, responsible for the rapid formation of salt crystals that may affect your emulsion during fixing. They may produce holes in the emulsion. A filtered solution will not produce crystals for more than 24 hours, the time you may need to fix the film.

Another improvement is adding to the salt fixer some grams of Potassium Bromide which is a veterinary medicine easy to get. 5g/liter are enough. Potassium Bromide will speed up the fixer and it will also delay the crystallization of the salt as I observed now.

24 hours fixing

48 hours fixing

Testing with drops of pure Rodinal 

Legend:

Kodak TMax-400 stripes «fixed» with salt.

On the left side I used only salt, in the middle salt+potassium bromide and on the right salt+potassium metabisulfite.

I didn't use temperature in this experiment.

Results:

The bowl with just salt already started crystallizing. The others not. The stripe on right acquired a brownish stain and is not better fixed than with just salt, but metabisulfite also prevented crystallization. Maybe other salts will also do it.

It is clear that the stripe in the middle, with Potassium Bromide, is better fixed than the others, after 48 hours. But not completely fixed yet!!! If so, no stain would appear after droping Rodinal pure on it.

Note:

Kodak TMax and similar films (T grain), multicoated films, are more difficult to fix. Even using regular Rapid Fixer, you would better let it for 30 minutes instead of just 2 minutes. Once I had some drag marks with Rapid Fixer and refixing for 30 minutes solved the problem. The fixer was not that new.

I might try to improve the results. making it possible to fix completely TMax films with salt.

I think I have it now...

Since I found Dignan's 2.bath C-41 developing method I am using it but always trying to improve it in order to get better results. Well, my last but maybe not the ultimate and superb adjustment to the method lead to the following recipe for the 2 baths:

Bath A:

1 g/l Potassium Metabisulfite
9 g/l Sodium Sulfite
11 g/l CD4

Bath B:

25 g/l Potassium Carbonate
0,6 g/l Potassium Bromide

Bath A should be kept  in a dark bottle with little air volume. If it gets pink it is oxidized and will work very slow, it should be discarded then. But if kept in a dark bottle with little air volume it will last for months. This first bath is to be used as first and because of this it will decrease with time, some 10 ml each time. If you need 500 ml of it to fill the tank for 120 films, you should prepare 1000 ml and use it until you reach your minimum. And if the bath is still good (no color), prepare more 500 ml and mix with the remaining and so on.

Bath B is, IMMO, the key for good results. Trial and error showed me that 53 g/l of Carbonate is too much and will give green negatives, magenta positives, and you have to tweak a lot in software. A slight increase in Potassium Bromide from 0,5 to 0,6 g/l and a reduction of Carbonate to the half, from 53 to 25 g/l, gave me the best results. Even so, too much or too less agitation may produce spots and drag marks. Frequent and soft agitation is needed. I am using now 5 gentle rotations with the axe of the tank inclined each minute, after the first 30 seconds of constant agitation.

Generally I develop my C-41 films as follows:

Bath A - 10 minutes or more at room temperature
Bath B - 10 minutes or more at room temperature
Wash - I wash for several minutes, maybe 10 minutes too
Fix - I fix for 5 minutes with rapid fixer, the same I use for B&W
Bleach - until the base is clear and double the time.
Rinse 3 times
Refix for other 5 minutes
Wash very well for 30 minutes
Hang to dry

Normally I use Blix instead of the 3 steps bleach, rinse and refix.

After the first Fix you may open the tank and follow the process at light. This is the reason why I fix first, Exhausted Blix or not properly aerated may produce surge marks and it is annoying to rebleach and refix and wash and wait for drying.

Do not hesitate to ask me for more details. I do not use Stabilizer because modern film s already have it in emulsion. A drop of dish washer in the last washing water will help to avoid water spots.

Some pictures using the last improvements:

 

Recovering cameras

I don't know which of these activities I like better, photographing, tinkering, processing, experimenting new recipes, viewing others pictures, etc., all about photography.

The camera above was almost unrecoverable. Very damaged by exposure to sun, many parts cracked, like lens holder and back and a broken film rewind button. It was an acquisition of my youngest daughter at a flee market at the place where she was studying arts, The piece must be exposed at sun for many time because it started falling apart a short time after she bought it. She gave me the camera and said, «have fun recovering it».

I started dismantling the camera 2 years ago but only in the last days I finally had time to finish the work. The back is now covered with an opaque material, the lens holder was replaced with PVC 50mm tube black painted and with an adapter 43-52 mm allows me to use filters. The single lens is the original but the aperture is now fixed and the focus too. Pictures are sharp in the centre but out of focus at the edges, the left side more than the right side. Last tree pictures were made with this piece.

The pictures were made with B&W film, TMax 400 long expired, developed with the Parodinal 645. The film came up with a brown stain at the bottom (inverse of the positive), I think it was the fixer saying goodbye. Neverthless I scanned the film as color and... I liked what I got!

Hi! Just more pictures...

This time I used my Parodinal 645 with an expired 400 ISO film, Kodak TMax 400. It would normally have huge grain and fog. Yes, 'honest' grain but no terrible fog and nice range of greys...