Modified D-76.

[Keith Tapscott.]

Keith Tapscott. submitted a new resource:

(there was a url link here which no longer exists) - Modified D-76.

I wanted to try a custom formulation of the ever popular D-76/ID-11 formula for myself that differs slightly from the bog-standard formula.
The formula is as follows:
Sodium Hexametaphosphate or Sodium Tripolyphosphate (Optional) 1-2g/litre.
Metol/Elon = 2g
Sodium Sulphite (anhydrous) = 85g
Hydroquinone = 5g
Sodium Metabisulphite = 3.5g
Sodium Metaborate = 4g
water to make 1 litre of stock solution.

The balance of Metol and Hydroquinone is the same as the classic D-76/ID-11 and...

(there was a url link here which no longer exists)

 

[Tom Hoskinson]

Keith, if you haven't yet done so, take a look at:

D-76 Type Film Developers, by Ryuji Suzuki

Konica SD-20

Fujifilm FD-122

Suzuki DS-8

http://silvergrain.org/Photo-Tech/d-76.html

 

[Keith Tapscott.]

Keith, if you haven't yet done so, take a look at:

D-76 Type Film Developers, by Ryuji Suzuki

Konica SD-20

Fujifilm FD-122

Suzuki DS-8

http://silvergrain.org/Photo-Tech/d-76.html

I looked at the information written by Ryuji a long time ago Tom.
It`s an interesting article.
Cheers.

 

[Ryuji]

Combining metaborate and metabisulfite will make same results as using borax and sulfite if you adjust the agents' quantities and the resulting pH. So, it's just a matter of convenience to choose which agents to use.

I've also looked at the description of FX-7 and compared it to FX-4. I see much more significant change in the bromide content and that's more significant than the difference between borax and metaborate. I haven't made up the solution to compare the pH, but I bet FX-7 has higher pH as well. I'm not sure what the point of FX-7 is.

 

[Keith Tapscott.]

Combining metaborate and metabisulfite will make same results as using borax and sulfite if you adjust the agents' quantities and the resulting pH. So, it's just a matter of convenience to choose which agents to use.

I've also looked at the description of FX-7 and compared it to FX-4. I see much more significant change in the bromide content and that's more significant than the difference between borax and metaborate. I haven't made up the solution to compare the pH, but I bet FX-7 has higher pH as well. I'm not sure what the point of FX-7 is.

I didn`t pay much attention to the differences between FX-4 and FX-7, now that you`ve pointed it out, there is a difference in the weight of sulphite and potassium bromide.:confused:
The main thing that caught my eye as I said in my original post, was the comment that the old Ilford films performed better in developers with a Metaborate system. I also used the same balance of Sodium Sulphite, Sodium Metabisulphite and Sodium Metaborate as that used in the Xtol formula on page 49 after reading the comment on page 50 that the Xtol developer was highly buffered. It seemed logical that the MQ developer that I mixed would also be well buffered too.
Have I wasted my time with this formula? I`ve had good results with it so far, so it would be disapointing if my efforts were in vain.
Cheers.

 

[Ryuji]

I'm not sure if you wasted your time or not. It was at least for your learning experience, although I could tell you just the same thing if we got to talk before

If your formula makes any different result from standard D-76, it must be due to difference in pH and different sulfite concentration.

Firstly, I don't see any reason why Crawley said metaborate worked better than borax. He might have just meant higher pH. If the pH is adjusted to the same point by NaOH, both borax and metaborate make chemically identical solution. Don't believe the word "highly buffered" etc. alone, as they are relative terms.

 

[Keith Tapscott.]

I'm not sure if you wasted your time or not. It was at least for your learning experience, although I could tell you just the same thing if we got to talk before

If your formula makes any different result from standard D-76, it must be due to difference in pH and different sulfite concentration.

Firstly, I don't see any reason why Crawley said metaborate worked better than borax. He might have just meant higher pH. If the pH is adjusted to the same point by NaOH, both borax and metaborate make chemically identical solution. Don't believe the word "highly buffered" etc. alone, as they are relative terms.

So if the pH of what I made is the same as the standard formula, then no actual advantage and perhaps an unnecessary addition/change of two components?
Still, it was part of the fun and as you say, part of the learning process, so no harm done because of a personal experiment.
Thanks for the constructive comments.

 

[Keith Tapscott.]

The Boric Anhydride Myth.

Since posting this recipe, I have done some research into the MSDS that I have for the commercially sold `Kodak` D-76 and I have also discussed the MSDS with a photo-chemist. The MSDS is as follows:

Weight % - Component - ( CAS Registry Number).
Concentrate:
85-90 Sodium Sulphite (007757-83-7)
1-5 Hydroquinone (000123-31-9)
1-5 Sodium Tetraborate (001330-43-4)
1-5 Bis (4-hydroxy-N-methylanilinium) sulphate (000055-55-0)
< 1 Boric Anhydride (001303-86-2)
< 1 Pentasodium (carboxylatomethyl) iminobis (ethylenenitrilo) tetraacetate
(000140-01-2)

Weight of concentrate = approximately 110 grams/litre.

From the book "Modern Photographic Processing" by Grant Haist, Volume 1:

Borate Alkali's: "Borax,Na2B4O7.10H2O, is the common name for sodium tetraborate, an alkaline compound used in the preparation of low-contrast, fine-grain developers. Borax may be written (NaBO2)2.B2O3, which shows the boric anhydride that limits the alkalinity possible from borax.
Borax acts as a buffer; that is, it maintains a reservoir of alkali but delivers only small quantities of hydroxyl ions at any one time. The alkalinity is maintained relatively unchanged until all of the borax has been neutralised."

It has been mentioned in some threads, that the Eastman Kodak D-76 packaged developer may be closer to D-76d, however, this doesn`t seem to be the case according to the description of borax in Haist`s book and it is probably very close, if not identical to the ORIGINAL formula as published over many, many decades. I wonder if anyone has conducted any test to compare the pH of the commercial EK product with the scratch mixed developer when stored over several weeks or months?

 

[Keith Tapscott.]

Having experimented with several D-76 derivatives including D-76d and D-76H, I have decided that I can not improve on the `ORIGINAL` formula.
I now make up 500ml of stock of the `standard` formula at a time as I need it and use it within 24-48 hours of mixing for optimum consistency.
I find that I prefer the results when the developer is diluted 1+1.

 

[martellsv]

observation about qualities

You beat the tonal range, and probably the conservation more than 6 moths in a full bottle, is quite different from the original... 100 grs of sulfite is like a lorry, hard to move, the developing speed is lower compared when you work stock... haven`t you beat d-76 ? i think you have done something different (other cuestion is 1+1 dilution)... with greater possibilities. I am not according at all with the opinion of R. Suzuky based in my own expirience, i am not chemist but i like, concerning to kodalk qualities, the tonal scale and the preservation when you change the alcali e.g. Carbonates or borax, most of the times, is clearly better, it`s easy to take a photo of apple and see the differences, e.g Dk-50 1+1 or 1+2... and T grain film (Curiously this is a new and modern film/emulsion and kodalk work excelent). You have found another way in the D-76 world.

 

[Gerald C Koch]

I don't know what is meant by "The Boric Anhydride Myth." Kodak owns many patent for single powder mixes. They are therefore able to supply D-76 in a single bag whereas Ilford must use two for ID-11. One of the reasons it can do this is the use of boric anhydride rather than boric acid. To insure stability all the ingredients in the bag must be anhydrous to prevent undesired reactions.

 

[Gerald C Koch]

The successful modification of an existing formula or the creation of a new developer requires an extensive knowledge of chemistry and in particular developing agents. There are all sorts of pitfalls to catch the unknowledgeable. It is not like a Chinese restaurant menu, choosing a developing agent for column A, and alkali for column B, etc. For example, the pH of any modification to D-76 cannot become too low. The activity of developing agents is pH dependent. In the case of D-76 hydroquinone loses all its activity at a pH of 5.5.

 

[Keith Tapscott.]

I don't know what is meant by "The Boric Anhydride Myth." Kodak owns many patent for single powder mixes. They are therefore able to supply D-76 in a single bag whereas Ilford must use two for ID-11. One of the reasons it can do this is the use of boric anhydride rather than boric acid. To insure stability all the ingredients in the bag must be anhydrous to prevent undesired reactions.

It was a long time since I made that post Gerald and I would like to think I have learned a little something since then.
Back then, I contacted a chemist who regularly wrote articles about photographic processes and mentioned the boric anhydride given by Kodak for their MSDS for D-76.
He replied saying that Kodak put borax in bags, rather than boric anhydride and that borax actually releases boric acid when it goes into solution. He might not have been aware about the patents for single-powder developers at the time we corresponded back then. To be honest, the original D-76 (ID-11) formula is hard to beat.

 

[Gerald C Koch]

It was a long time since I made that post Gerald and I would like to think I have learned a little something since then.

Hi Keith. My post was a very general one directed to the entire APUG readership. It was intended to prevent a lot of frustration among this audience. It is a point that I have made several times before.

Concerning the work by Ryuji Suzuki mentioned in the thread, he did extensive reading related to his work in developers.

Kodak also uses boric anhydride in such developers as D-72 (Dektol). Its use in them is to coat the granules of alkali such as sodium carbonate to prevent them from reacting with the developing agents.

 

[Keith Tapscott.]

Hi Keith. My post was a very general one directed to the entire APUG readership. It was intended to prevent a lot of frustration among this audience. It is a point that I have made several times before.

Concerning the work by Ryuji Suzuki mentioned in the thread, he did extensive reading related to his work in developers.

Kodak also uses boric anhydride in such developers as D-72 (Dektol). Its use in them is to coat the granules of alkali such as sodium carbonate to prevent them from reacting with the developing agents.

The use of it in compounding single-powders is making sense now Gerald.
I think (but not sure) that developers such as Acufine, Ethol UFG film developers and the LPD paper developer are also sold as single-powders.

The feedback from this thread has been very helpful to me and hopefully others who have read it. It is also nice to know that someone has tried the formula I posted.

Back then when I started this thread, I was having some fun with raw constituents for making my own developers. Today, I would just mix the original D-76 (ID-11) formula and either D-72 (Dektol type) or ID-20 for developing B&W papers.

 

[Keith Tapscott.]

Another thing I am thinking over, would the coating of the actual developing agents be more likely rather than the alkaline components?

 

[Keith Tapscott.]

You beat the tonal range, and probably the conservation more than 6 moths in a full bottle, is quite different from the original... 100 grs of sulfite is like a lorry, hard to move, the developing speed is lower compared when you work stock... haven`t you beat d-76 ? i think you have done something different (other cuestion is 1+1 dilution)... with greater possibilities. I am not according at all with the opinion of R. Suzuky based in my own expirience, i am not chemist but i like, concerning to kodalk qualities, the tonal scale and the preservation when you change the alcali e.g. Carbonates or borax, most of the times, is clearly better, it`s easy to take a photo of apple and see the differences, e.g Dk-50 1+1 or 1+2... and T grain film (Curiously this is a new and modern film/emulsion and kodalk work excelent). You have found another way in the D-76 world.

You are the only person I am aware of who has tried my formula. I am glad you liked it.

As for Ryuji, I miss seeing his posts on APUG, as I have always found him helpful.

 

[Gerald C Koch]

Acufine is supplied in a small can sealed under nitrogen. Probably the best way to package developers. However when Baumann first began sales the cans exploded on the store shelves. The developer had be reformulated.

 

[Keith Tapscott.]

martellsv has reported a pH of 8.15 for my formula. I believe that standard D-76 (ID-11) is around pH 8.5-8.6.

In theory, the modified formula should provide slightly finer-grain and better resolution, but I do not know how to test properly to confirm it.
If the speed yield matches standard D-76, then it is worth mixing from scratch.

martvellsv also mentions a significantly longer shelf life than the 6 months that Kodak quote, although I suspect that Kodak have erred on the safe side for shelf life of stock solution.
Anyway, thanks to everyone who has commented to this thread.

 

[Gerald C Koch]

martvellsv also mentions a significantly longer shelf life than the 6 months that Kodak quote, although I suspect that Kodak have erred on the safe side for shelf life of stock solution.
Anyway, thanks to everyone who has commented to this thread.

Kodak was always rather conservative in their estimaes. Of course they also had to consider the worst storage conditions too.

 

[martellsv]

If I am correct, standard D-76 is around pH 8.5-8.6, so the modified D-76 developer at pH 8.15 should in theory provide slightly finer-grain and higher resolution. If the film speed yield matches standard D-76, that along with a longer shelf life makes it a worthwhile formula. I am not sure how to conduct such stringent test though.

IMHO (i messured the two versions comercial and homemade) D-76 kodak comercial version has boric anhidride less than 1 gr. convert to borix acid less than 1.78 gr. if you put less than 5 gr. of Borax decahydrate, you'll get Ph of 8.8-8.9, never obtain 8.5 but if i mix de D-76D i get be bear 8.5 and there is a important difference in the developement time. Thinking about moles if i don't remember bad my calculation was just the double 0.0125/0.025 (buffer pair Boric with Borax) curiously it could be a 1:2 ratio and i get Ph of 8.8-8.9 ... with 1:1 ratio i get ph 8.5.

(i haven`t done any scientific calculations but i hope this looking the print) If Developers like Adox MQ give full Speed, you can compare with it or with other standar look at other threads on apug... My neg shows an excelent shadow detail, i wait more than D-76 stock of gradation, sharp, and high resolution... i begin to do the long life test this is one... i was working on a personal proyect closed to your modified developer i am about 87 grs. sulfite and with Kodalk, sodium metabisulphite , its accelerating and working with sulfite and with long life properties...

i am not chemist but reading about sinergism it appears that occurs something similar like with mq, pq ... in the sense that there is a collaboration between two agents and the result is better than one alone, my phmeter shows a cleardrop in the Ph of the solution because sodium metabisulphite, despite Keith's developer shows at least the same activity when develope a film if no more.

Looking to R. Suzuky comment (i read similar words in the focal encyclopedia of photography 1994) Alkalis does more than Ph because there is a curve of energy, and a ditribution of this energy (this energy could be constant or not, and could has peaks and fluctuations despite tha total amount of this alkalis could be adjunsted to get the same PH), e.g Naoh begin very strong several minutes later slows ... and not everyone has the same effect in the shelf life properties etc... ceratin Lith developers e.g. begin slowly and increases the activity formaldehyde plus SO3NA2----Naoh bit a bit, only this has a great effect at least in contrast, reading some patents and chemist i sometimes think "have you ever made a print?"

 

[Keith Tapscott.]

Did you measure the pH of the formula of this thread?