Organoleptic properties of Harvey's 777 type developers

Pixophrenic · May 10, 2018

Alan Johnson said:
Mees & James, 3rd ed p371 notes the temperature coefficient T is the ratio of the rate of development at a particular temperature to the rate at a temperature 10 degrees lower on the Centigrade scale.
It is particularly high for developers containing ppd. Among other things, T for a soft emulsion is substantially higher than that for a hard emulsion. Maybe Harveys contains an ingredient to harden the emulsion.

So you are not opposed to the idea that this ingredient could be both a hardener and a developing agent. Or such that it becomes a hardener during the development reaction. It has been assumed without reason that Harvey's developer uses one or more of the better known developing compounds, while it was overlooked that he made hundreds of tests, in his own words, to come up with an original compound. "The formula for the Harvey developer will not be disclosed. Great skill is required to manufacture it. The reducing agent is original and not obtainable in the market anywhere." Sounds like there was a capable friend who could synthesize it. Or was it all a smokescreen?

Alan Johnson · May 10, 2018

It's not my intention to guess the ingredients but from Clerc and Jacobson "Monochrome Developing Practice"1971 [apart from sodium sulfate]
"The addition of hardening agents to the developer may be made...inorganic hardening agents such as chrome alum cannot be used because they only harden gelatine in acid solutions...
Formaldehyde cannot be used because it causes fogging of the emulsion...
The most suitable compounds are organic compounds such as dialdehydes or diketones (eg diacetyl, glutaraldehyde or acetonyl acetone). "
Thus the existence of an original compound that both develops and hardens is unlikely to be true, although a hardening agent may be used.
Also the use of some addition product of two developing agents or one of dozens of developing agents listed in Mees and James cannot be ruled out as an original reducing agent.

Lachlan Young · May 10, 2018

Alan Johnson said:
"The most suitable compounds are organic compounds such as dialdehydes or diketones (eg diacetyl, glutaraldehyde or acetonyl acetone)."

They also can have quite, uh, 'distinctive' smells.

I will laugh & laugh & laugh if it turns out that 777 is essentially a Microdol-esque developer with an incorporated hardener & (possibly) an anti-swelling agent. It would certainly explain the decline of 777 in favour of various other fine grain developers once film hardening improved... It should also be noted that of the list of famous photographers linked upthread, by the 1960's Penn was apparently using Ethol UFG in a replenished system, and by the 1990's Avedon's film was being run in replenished D-76, which pretty strongly suggests that it wasn't necessarily aesthetics that drove the use of 777.

Pixophrenic · May 10, 2018

Alan, isn't tanning actually differential hardening? So, one way is to look for relatives of di/tri hydroxybenzene, just not so easily oxidized.

Alan Johnson · May 10, 2018

Some examples are in post 11:
https://www.photrio.com/forum/threads/what-was-is-meritol.22133/
IDK if these have good stability but with ppd they should have fine grain.
If they tan as well, marks for trying.

Pixophrenic · May 10, 2018

Alan Johnson said:
Some examples are in post 11:
https://www.photrio.com/forum/threads/what-was-is-meritol.22133/
IDK if these have good stability but with ppd they should have fine grain.
If they tan as well, marks for trying.

On the one hand, you may be right. Something was definitely going on in my Edwal 12 when it was sitting for a week. Negatives have a weak stain, but no obvious tan. On the other hand, adducts/admixes of catechol with PPD probably may tan in high sulfite as there is, but will they be exceptionally stable? In the meantrime I have found that there is a funny looking compound called methenamine, used in silver staining in histology, which releases formaldehyde and ammonia during slow decomposition. Harvey <could> know about silver staining. A little formaldehyde with sulfite equals sodium hydroxide, and a little ammonia dissolves grain, soo...we still need a developing agent.

removed account4 · May 10, 2018

pdeeh said:
I expect I shall regret jumping into this thread, but I'm feeling reckless today; and I can always mute it if it goes even further sideways

You need to try harder, john; also a magic incantation is required (which I have vowed not to reveal).

I tried this years ago when I was first fussing about with Caffenol.

Ascorbic acid powder and Caustic soda in solution will develop film, and very quickly too. Unfortunately it's such a high contrast developer that you almost don't get any midtones at all. Washing soda instead of Caustic slows it down (lower pH) somewhat, but it's still rather unsatisfactory.

Adding coffee slows it down a bit more and by superadditivity (it is assumed) makes it into a useful developer.

Saying 'ascorbic acid does most of the work in Caffenol' is a bit like saying 'in D76, metol does most of the work, so we can disregard the hydroquinone'

PE has been heard to say something to the effect that experimental results always trump theory. And faced with your experience versus someone else's unevidenced theory, I'm inclined to your side of the bargain ...

well maybe i didn't know the magic incantation
maybe next time i'll say " bim skala bim ! "
i've never used caustic soda so i can't travel there, just washing+baking soda
and stuff like, well you know, soda pop
im sure coffee is doing something in there, but who knows what and who knows why or how
to me its a great riddle and ill leave it at that !
i wish i could remember which photroite or appugger it was who just brewed a pot of coffee
and stuck his film in there, nothing else ... and it worked fine for him.

photography is such a great parlor trick...

Pixophrenic · May 11, 2018

Alan Johnson said:
Some examples are in post 11:
https://www.photrio.com/forum/threads/what-was-is-meritol.22133/
IDK if these have good stability but with ppd they should have fine grain.
If they tan as well, marks for trying.

I am not sure anyone was watching, but two days ago a pack of Harvey's Panthermic went on sale on German Ebay. It was detected through "image search" and the seller kindly took pictures of not only the outside but also of the included instruction. It calls for dissolving part A at 60 degrees Celsius, and part B at 23 degrees, and then adding A to B. This is not how you would prepare a sulfite-rich metol developer. It fits, though, with the suggestion that Harvey's developing agent is kind of original, something that does not readily dissolve in water but does not oxidize as easily as metol or PPD without sulfite, The clue to what that original developing agent could be lies in who the chemist friends of Mr. Harvey were.

Alan Johnson · May 11, 2018

At the end of the following, Don Cardwell mentions that a liters worth of 777 weighs about 155 grams and a liters worth of Germains weighs about 91 grams.
It seems possible that the difference is made up of sodium sulfate included to suppress emulsion swelling and giving the developer its panthermic name tag.
Having to heat part A to 60 degrees may represent an attempt to dissolve glycin.
http://stores.photoformulary.com/content/01-5085 Remembering 777.pdf

Lachlan Young · May 11, 2018

Alan Johnson said:
At the end of the following, Don Cardwell mentions that a liters worth of 777 weighs about 155 grams and a liters worth of Germains weighs about 91 grams.
It seems possible that the difference is made up of sodium sulfate included to suppress emulsion swelling and giving the developer its panthermic name tag.
Having to heat part A to 60 degrees may represent an attempt to dissolve glycin.
http://stores.photoformulary.com/content/01-5085 Remembering 777.pdf

Given that it's almost always described as a 'borderline suspension', something in it is right at the edge of saturation at the pH of the solution. Glycin is a substituted P-Aminophenol, & it's entirely possible that the developing agent is a different substitution again, or has similarities in its production to the methylation of P-Aminophenol that leads to Metol. In other words, it might be 'unique', but is it functionally that different from P-Aminophenol or Metol? It would have been well within the abilities of Henn & KRL to analyse this & I suspect that their sticking to Metol was driven by a lack of benefits from this 'novel' substance. For all we know, it may have been an organic chemist working in an entirely different sector (who Harvey came in contact with via his photography work) who made a suggestion that he followed up. Medicine & herbicides are both areas where the necessary reagents would have been known & used. It might also explain the absence of the product from the market if the synthesis/ substitution had to be redesigned/ the process altered to comply with safety legislation (some seriously nasty chemicals could potentially be involved).

Pixophrenic · May 11, 2018

Lachlan Young said:
Given that it's almost always described as a 'borderline suspension', something in it is right at the edge of saturation at the pH of the solution. Glycin is a substituted P-Aminophenol, & it's entirely possible that the developing agent is a different substitution again, or has similarities in its production to the methylation of P-Aminophenol that leads to Metol. In other words, it might be 'unique', but is it functionally that different from P-Aminophenol or Metol? It would have been well within the abilities of Henn & KRL to analyse this & I suspect that their sticking to Metol was driven by a lack of benefits from this 'novel' substance. For all we know, it may have been an organic chemist working in an entirely different sector (who Harvey came in contact with via his photography work) who made a suggestion that he followed up. Medicine & herbicides are both areas where the necessary reagents would have been known & used. It might also explain the absence of the product from the market if the synthesis/ substitution had to be redesigned/ the process altered to comply with safety legislation (some seriously nasty chemicals could potentially be involved).

I agree, Another obvious area would be hair and fur coloring. The latter may explain how Bluegrass found a substitute in modern time.

Pixophrenic · May 13, 2018

Pixophrenic said:
I agree, Another obvious area would be hair and fur coloring. The latter may explain how Bluegrass found a substitute in modern time.

In reply to myself, I would like to add that this is probably going to be my last addition to this thread. Upon re-reading the aforementined Unblinkingeye article, I found all the clues I needed. There is no proof that it contains p-phenylenediamine and especially glycin. It is just an opinion. It was Fred de Van, who "posted the fact that 777 contains p-phenylenediamine". How did he know? Ted Kaufman was "sure" that it contained glycin from a host of indirect organoleptic clues, with which Don Cardwell disagreed, but was cut short before he could elaborate. The most of clues, however, came when looking into the link at the end, which downloads the apparently original instruction for the developer. Let's not dwell too much on the fact how many times this instruction contradicts the article. The key point is that the inventor intended this developer to be used with replenishment. And constant agitation. Which fact points to the suggestion that it may have contained some sort of PPD derivative, which needs to be dissolved in near boiling water! As also follows from the instruction, initially the developer was sold in several packages, including very small ones, for occasional use during travel, which came without a replenisher. It is clear that without replenishment, the developer quickly goes bust, and barely 3 films (120?) can be processed in half a liter without serious loss of quality. So, if the replenisher is not available, this developer quickly loses its attraction.
Second point worthy of mention is that it is explained in great detail that the developer exhibits a tanning action, which hardens the emulsion, but only temporarily, so a hardening stop and a hardening fixer formulas are included and highly recommended as companions in the processing. Overall the meticulous instructions and extensive time/temp tables show how much work went into just one commercial product. I am thoroughly impressed and humbled, and herewith, I would like to finish reporting about my investigations.

Monday317 · Mar 10, 2019

jnantz said:
OR

you could always offer to BUY the formula from them.
and then post what the formula actually is
(instead of hopeful rumors, and hearsay formulae )

Not to bogart the thread, but assuming one won a significant pile of shekels in a Lottery, I wonder what the price of the 777 formula would be, and if that would include all the variants of the stuff from Day One, 1930-whatever..?

Pixophrenic · Mar 11, 2019

Monday317 said:
Not to bogart the thread, but assuming one won a significant pile of shekels in a Lottery, I wonder what the price of the 777 formula would be, and if that would include all the variants of the stuff from Day One, 1930-whatever..?

I think a more interesting question would be: are you truly interested in owning the original(s) or you would be happy with a formula that gives results that are hard to tell from those obtained with the original? Especially that today some of the components of the original, such as those conferring temporary emulsion hardening, would be superfluous.

Monday317 · Mar 11, 2019

Well I’d simply publish everything, and let the eggheads decide what they like.

Besides, it’s probably just Germain’s anyway...

Pixophrenic · Mar 11, 2019

Monday317 said:
Well I’d simply publish everything, and let the eggheads decide what they like.

Besides, it’s probably just Germain’s anyway...

No it is not. There is no glycin in 777. But if you take glycin away from Germain's you may be getting closer.

Lachlan Young · Mar 11, 2019

Having subsequently found Henn & Crabtree's 1945 Pop Photo articles on D-25 & Microdol (September & October 1945, on Google Books), it becomes increasingly clear that they'd very, very extensively & systematically analysed the other ultra fine grain developer formulae & eventually arrived at Microdol as offering better results & with much less of the nasty side effects the PPD developers had. Compared to the rather extemporaneous fine grain formulae of the 1930's, it's clear their approach was much more firmly scientific & analytical in methodology - ruthlessly minimising ingredients to only those that had the desired effects.

Worth noting that they also disclose that adding a small amount of benzotriazole to Microdol made even finer grain on the films of the time.

Monday317 · Mar 11, 2019

Pixophrenic said:
No it is not. There is no glycin in 777. But if you take glycin away from Germain's you may be getting closer.

Do you have a bona fide formula for Harvey’s no one else has seen..? No one really can say for certain what’s in the stuff, much less what’s not in it, except the folks @ BPI.

I have seen a few other published Harvey formulae that contain some peculiar stuff. “Cloric reduction of ammonia” or something like that was one or two of the types of things I read. I suppose it has Utopian Salts of Unobtanium as well.

If nothing else, maybe a batch of D23 is the best option after all?

Rudeofus · Mar 12, 2019

Are there reasons to believe, that 777 is a particular fine grain formula? Pixophrenic listed its unique selling proposition in post 14 in this thread, and ultra fine grain wasn't one of them. If one declares 777 pure magic, then certainly none will find a proper substitute for it. Reality may be different. Speaking for myself here, temperature independent processing and long term tank life alone is not enough of an argument to buy into a developer.

Lachlan Young · Mar 12, 2019

Rudeofus said:
Are there reasons to believe, that 777 is a particular fine grain formula? Pixophrenic listed its unique selling proposition in post 14 in this thread, and ultra fine grain wasn't one of them. If one declares 777 pure magic, then certainly none will find a proper substitute for it. Reality may be different. Speaking for myself here, temperature independent processing and long term tank life alone is not enough of an argument to buy into a developer.

Pretty much every reference to 777 in the 40's & 50's refers to it as a 'fine grain developer' & groups it in with others that would be described as PPD based (or similar) very fine-grained developers.

Rudeofus · Mar 12, 2019

Lachlan Young said:
Pretty much every reference to 777 in the 40's & 50's refers to it as a 'fine grain developer' & groups it in with others that would be described as PPD based (or similar) very fine-grained developers.

I have yet to find a developer which is sold commercially and which is not described as "fine grain developer" in its documentation and data sheet. The statement "fine grain developer" is about as meaningful as "modern look" or "made from high quality components" or "your call is important to us, please hold while ...".

If 777 was as super fine grained as some people here make it sound, then please someone submit pictures with evidence of this. Adding PPD to a random developer does not make it super fine grained. These ancient PPD super fine grain developers were also known to lose 2-3 stops of usable EI, as far as I know 777 does not do this.

Lachlan Young · Mar 12, 2019

Rudeofus said:
I have yet to find a developer which is sold commercially and which is not described as "fine grain developer" in its documentation and data sheet. The statement "fine grain developer" is about as meaningful as "modern look" or "made from high quality components" or "your call is important to us, please hold while ...".

If 777 was as super fine grained as some people here make it sound, then please someone submit pictures with evidence of this. Adding PPD to a random developer does not make it super fine grained. These ancient PPD super fine grain developers were also known to lose 2-3 stops of usable EI, as far as I know 777 does not do this.

The specific words used in various descriptions of 777 at the time were "for very fine grain" in the contemporaneous context of categorisation of "medium grain", "fine grain" and "very fine grain", with D-76 & DK-50 characterised as "medium grain", and Edwal 12 & Microdol as "fine grain". The extent to which those claims hold up to modern analytical methods is obviously open to question.

Also found the official description of the colour of oxidised 777 as being a "deep wine-red color", so it's pretty clearly got PPD or a derivative in it. It's also the reason I have no great desire to try the stuff. In comparison, Henn & Crabtree's work provides more interesting (and much less toxic) routes & will still work well with today's materials.

Monday317 · Mar 12, 2019

Rudeofus said:
Are there reasons to believe, that 777 is a particular fine grain formula? Pixophrenic listed its unique selling proposition in post 14 in this thread, and ultra fine grain wasn't one of them. If one declares 777 pure magic, then certainly none will find a proper substitute for it. Reality may be different. Speaking for myself here, temperature independent processing and long term tank life alone is not enough of an argument to buy into a developer.

The legends of 777 include, but are not based on reports of ultra fine grain, but more over glowing highlights, superb shadow detail, and linear midtones. The last three of the four attributes get my attention, as most developers can’t manage all four. D-23 in some variants comes close, as does D-76.

Monday317 · Mar 12, 2019

Rudeofus said:
I have yet to find a developer which is sold commercially and which is not described as "fine grain developer" in its documentation and data sheet. The statement "fine grain developer" is about as meaningful as "modern look" or "made from high quality components" or "your call is important to us, please hold while ...".

If 777 was as super fine grained as some people here make it sound, then please someone submit pictures with evidence of this. Adding PPD to a random developer does not make it super fine grained. These ancient PPD super fine grain developers were also known to lose 2-3 stops of usable EI, as far as I know 777 does not do this.

Jay DeFehr came up with a PPD-based formula called “Halcyon” some time back. He thought it was the bee’s knees, though it didn’t break him of his pyro addiction. I’ve played with it, but my ancient scanner died, and they don’t make the vacuum tubes for it these days... Anyway, his formula is pretty modern if you want to play with PPD. It gives super-fine grain, at least box speed, if not a little faster, and is fairly exposure-tolerant. I believe he posted it on our APUG predecessor, and other forums as well.

Murray Kelly · Mar 13, 2019

Monday317 said:
Jay DeFehr came up with a PPD-based formula called “Halcyon” some time back. He thought it was the bee’s knees, though it didn’t break him of his pyro addiction. I’ve played with it, but my ancient scanner died, and they don’t make the vacuum tubes for it these days... Anyway, his formula is pretty modern if you want to play with PPD. It gives super-fine grain, at least box speed, if not a little faster, and is fairly exposure-tolerant. I believe he posted it on our APUG predecessor, and other forums as well.

Here is the link to Jay's article.
https://www.photo.net/discuss/threads/superfine-grain-film-developer.434467/
In that thread is mention made of quercetin as a developer. It is hard to dissolve and the red colour I seem to remember is one of its characteristics. Another contender for 777?
Also I have a collection of vacuum tubes - maybe I have the one you need?

Organoleptic properties of Harvey's 777 type developers

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