Phenidone vs. dimezone?

[Ian Grant]

There's only been two editions of the Film Developing Cookbook, that must be a mistake carried over from the First into the Second edition. It's the Darkroom Cookbook that's now in it's 4th Edition, it's not listed in the 2nd or 3rd editions.

I had it published in a EFKE datasheet some years ago as FR2 and also it's been in many copies of the BJP Almanac and then Annual. It's definitely supposed to be 2 gms, as Mark says it would be quite significantly different with just 1gm of Metol.

Ian

 

[Rudeofus]

I did indeed mix up the number of editions from dark room cookbook and film developing cookbook. Either way, the latest edition states 1 or 2 g/l Metol, and anyone can ask Bill or Steve about the origin of the 1 g/l number.

Typing errors in formula books were quite common back then, so there's a good chance, that 2 g/l was the authentic number, but 1 g/l also made it into literature and saw wide use. At 1 g/l it would certainly be different from 2 g/l, but not necessarily better or worse.

 

[Ian Grant]

I did indeed mix up the number of editions from dark room cookbook and film developing cookbook. Either way, the latest edition states 1 or 2 g/l Metol, and anyone can ask Bill or Steve about the origin of the 1 g/l number.

Typing errors in formula books were quite common back then, so there's a good chance, that 2 g/l was the authentic number, but 1 g/l also made it into literature and saw wide use. At 1 g/l it would certainly be different from 2 g/l, but not necessarily better or worse.

I've only seen the Adox Borax MQ developer in the BJPA and on EFKE data and I think there website. The source for the FDC would have been a BJP Annual as all the data on Crawley's FX developers in the FDC also come from there and haven't been published apart from one or two in other books. Have to admit I never noticed that mistake in the FDC, I'd assume it was Typo

Of course EKE didn't have the rights to the Adox brand name so listed the developer as FR2.

At some stage I must get around to listing the developers in the transition from Wellington and Wards MQ Buffered Borax developer and D76/ID-11. Wellington worked for George Eastman as a manager at Kodak Ltd, left set up on his own with I think his Brother in Law Ward, and finally the company was taken over by Ilford. There's a logical step progression between them though at Kodak with side shoots as they increase the Sulphite, altering the MQ ratio all taking place when Kodak were doing more pure research than really concentrating on developers etc. DK50 & DK60 were on the way . . . . . . .

I should add Wellington left Eastman Kodak In 1894, 4 years before Kodak Ltd was formed as a separate company and many years before Mees joined in 1913 from Wratten and Wainwright to establish Kodak Research.

Ian

 

[Alan Johnson]

I did indeed mix up the number of editions from dark room cookbook and film developing cookbook. Either way, the latest edition states 1 or 2 g/l Metol, and anyone can ask Bill or Steve about the origin of the 1 g/l numb.

1g/L metol is a direct quote from Crawley BJP 1960 p 684, IDK where he got it from but it seems to be wrong.

 

[Ian Grant]

1g/L metol is a direct quote from Crawley BJP 1960 p 684, IDK where he got it from but it seems to be wrong.

You are right, I missed that because it's in paragraph text not a table, which is probably why Crawley missed it as well. But a typo.

Crawley re-wrote the set of articles as one for the 1961 BJP Almanac but left out Adox Borax MQ this was around the time Luminos the UK Adox distributor closed and moved to the US. In 1961/2 we lost a lot of UK photographic companies, or they drastically scaled down.

What it does show you need to check primary sources, something you have to do for a University Thesis.

Ian

 

[albada]

@Rudeofus - Now that we know the formula for it, I'm still wondering: In what ways is Adox MQ Borax better than Xtol?

 

[Rudeofus]

@Rudeofus - Now that we know the formula for it, I'm still wondering: In what ways is Adox MQ Borax better than Xtol?

I have never used or recommended Adox Borax MQ, Ian already pointed this out. Ian has also cleared up his stance on Adox Borax MQ vs. XTol, so I guess the thread can return to Phenidone vs. Dimezone-S.

 

[albada]

I have never used or recommended Adox Borax MQ....

In posting no. 17, you wrote: "Adox MQ Borax is the best developer of all times and beats XTol like a drum in every aspect." Did you have the names reversed, so you actually meant that Xtol is superior?

Anyway, in posting no. 4, michael_r mentioned that Dimezone might have lower fog than Phenidone. I have seen this clearly in developers dissolved in propylene glycol. With some (but not all) films, such a developer produces more fog than if Dimezone were used instead. But if you remove the PG and dissolve directly in water, I saw no difference.
Mark Overton

 

[Rudeofus]

In posting no. 17, you wrote: "Adox MQ Borax is the best developer of all times and beats XTol like a drum in every aspect." Did you have the names reversed, so you actually meant that Xtol is superior?

Ian Grant typically speaks very highly of Adox Borax MQ, and I frequently got the impression, that he advertised it as the best developer ever made. I paraphrased him here, maybe a bit more pointed than it should have been, and achieved irritation and strong response from Ian and a confused Mark. I do not consider any of this a great accomplishment on my side and wish, that my posting would finally disappear in the foggy past of this forum.

On a personal level: I have used D-76 once, and I have used neither Adox Borax MQ nor XTol. From the few things I have learned in all those years, I highly doubt, that there is much image difference between D-76 and Adox Borax MQ. Over the years every B&W film has been optimized for D-76 due to its massive market dominance, any differences between Adox Borax MQ and D-76 would rather tilt in D-76's favor after so many decades of extra knowledge in and technology for emulsion making. I would expect XTol to offer better speed, grain and sharpness than both D-76 and Adox Borax MQ.

 

[Ian Grant]

I, for one, have quite a few APUG posts I would like to erase from history.

Indeed XTOL was essentially the first (and last) developer to improve - albeit slightly - on the “triad” properties of D-76 with the films we have at our disposal.

Edit: If I recall, Ian prefers Pyrocat.

I do indeed prefer Pyrocat HD these days. I'd still be using Xtol for any commercial work but that went digital many years ago.

Before I started using Pyrocat I was using Rodinal for most of my personal work and replenished Xtol for commercial work and my preferred films were APX100/APX25 and Tmax400. I'd disagree with Rudeofus that all films are or were optimised for D76/ID-11, the recommended developer for APX100 and APX25 was Rodinal and the combination produces exceptionally fine grain, and Tmax100 is excellent with it as well.

Tmax films weren't as good in D76/ID-11 compared to Xtol, so one can't say they were optimised for D76. Ron Mowrey (PE) did state a few times that Kodak's house developer for film testing was Ascorbic based for some time before Xtol was released, and when Kodak released Tmax films there was also an announcement that two new developers better suited to them would be available in a few moths - they were Tmax developer and Xtol.

One could ask why Xtol wasn't available earlier if Kodak had worked on Ascorbic based developers for some years. I think because of Patent issues, there's a US Patent for Ascorbic based developers granted to a Swedish company in the 1960s.

I switched fom Rodinal to Pyrocat HD just before moving abroad and found I preferred it, it wasn't practical to use Xtol replenished, I had no darkroom and very little storage space. I found I could mix Pyrocat HD Part A double strength to cut weight when flying and source the Potassium Carbonate locally. I also found that unlike Rodinal Pyrocat HD works well with with faster films particularly HP5.

In the end it's the results that matter and I'm getting the same print quality 35mm to LF from Pyrocat HD as I did with Rodinal & Xtol, somewhere in the mix I had to switch to Ilford and Foma films as Tmax or any Kodak B&W film was near impossible to find abroad.

Ian

 

[Ian Grant]

Ian Grant typically speaks very highly of Adox Borax MQ, and I frequently got the impression, that he advertised it as the best developer ever made. I paraphrased him here, maybe a bit more pointed than it should have been, and achieved irritation and strong response from Ian and a confused Mark. I do not consider any of this a great accomplishment on my side and wish, that my posting would finally disappear in the foggy past of this forum.

On a personal level: I have used D-76 once, and I have used neither Adox Borax MQ nor XTol. From the few things I have learned in all those years, I highly doubt, that there is much image difference between D-76 and Adox Borax MQ. Over the years every B&W film has been optimized for D-76 due to its massive market dominance, any differences between Adox Borax MQ and D-76 would rather tilt in D-76's favor after so many decades of extra knowledge in and technology for emulsion making. I would expect XTol to offer better speed, grain and sharpness than both D-76 and Adox Borax MQ.

Thanks Rudeofus, I used ID-11 (D76) for many years both commercially and for my personal work almost always replenished, in fact I think I only used it at 1+2 for a friend at his request and he supplied the developer. I tried Adox Borax MQ first in the early 1980's again replenished and found that Crawley's comments about better sharpness and slower contrast rise were mirrored in my results there was also a slight increase in films speed. The difference were most noticeable with 35mm film, two friends both commercial/advertising photographers also tried it and agreed so for a period of time I made up the developer for their deep tanks. Of course the downside was it wasn't commercially available so unless you made up your own solutions which was rare.

Now back to Phenidone, at the time I worked as an emulsion/photo chemist but also photographed rock bands for a recording studio/record company. I used Microphen/ID-68 which in some ways is a PQ version of Adox Borax MQ, the Sodium Sulphite level is dropped in this case to 85g/l compared to the 100g/litre of ID-11/D76 and also Ilfords PQ photofinishing developer Autophen - a PQ version of ID-11. I only used Microphen/ID068 for push processing, I didn't like the grain and tonality for normal use.

Over the previous years I had tried various Crawley/Paterson developers Acutol, Aculux, FX-18, most of which were PQ developers and with FP4 weren't as good as ID-11/D76.

Ian

 

[MattKing]

wish, that my posting would finally disappear in the foggy past of this forum.

You could always ask a moderator to insert [sarcasm alert on] and [sarcasm alert off] flags

 

[Ian Grant]

You could always ask a moderator to insert [sarcasm alert on] and [sarcasm alert off] flags

It isn't worth worrying about

Ian

 

[albada]

I only used Microphen/ID068 for push processing, I didn't like the grain and tonality for normal use.

Ian, what PQ developer is best in your opinion? I thought ID-68 was nearly the best possible using PQ, so I'm surprised you disliked its grain. Actually, I'm wondering how the best PQ compares to the best PC, primarily in terms of grain, but also for sharpness.
Mark Overton

 

[Rudeofus]

Now back to Phenidone, at the time I worked as an emulsion/photo chemist but also photographed rock bands for a recording studio/record company. I used Microphen/ID-68 which in some ways is a PQ version of Adox Borax MQ, the Sodium Sulphite level is dropped in this case to 85g/l compared to the 100g/litre of ID-11/D76 and also Ilfords PQ photofinishing developer Autophen - a PQ version of ID-11. I only used Microphen/ID068 for push processing, I didn't like the grain and tonality for normal use.

One striking feature of Phenidone and its derivatives is the 1/2 stop extra emulsion speed it gives with normal development. Obviously its inventors tried to bank on this trait and sacrifices grain and sharpness to get maybe even a full stop of extra speed, c.f. Microphen, FX-11, ... Evidently it took decades until XTol was released, which ignored the "gives an extra 2/3 speed" obsession and stuck a better balance between speed, grain and sharpness.

 

[Ian Grant]

Ian, what PQ developer is best in your opinion? I thought ID-68 was nearly the best possible using PQ, so I'm surprised you disliked its grain. Actually, I'm wondering how the best PQ compares to the best PC, primarily in terms of grain, but also for sharpness.
Mark Overton

Some people use Autophen and rate it highly, ironically they think they are mixing Microphen because the Photolab Index assumed the Axford-Kendall PQ Fine Grain Developer "Autophen" formula was that for Microphen, this error continued in various US books and I think into the Darkroom Cookbook 2nd edition.

I would think Autophen is slightly better than ID-68/Microphen, Ilford research realised the PQ version of ID-11/D76 gave a slight speed increase over the MQ developer and took this a step further by cutting the Sulphite for ID-68/Microphen, they also dropped the Phenidone from 0.2g/l to 0.13 g/l so requiring an increase in development times.

In Kendall's 1940 Phenidone Patent there's an Example of a PQ version of ID-11/D76 just substituting the 2/l Metol with 0.2g/l Phenidone, but with no changes in buffering, By 1954 which is around the time of Phenidone's commercial introduction by Ilford. In the next few years there's some slight tweaking of the buffering until the final published Autophen formula and its introduction in 1957.

As you can see from the above image Autophen was not sold in "Amateur" sized packaging, and was available in Powder as well as Liquid form.

Back in the mid to late 1980's I did some extensive testing and actually found that Ilford PQ Universal gave very fine grain and excellent sharpness with FP4, but then it was one of the recommended developers for Ilford Ortho film which we'd used for work. I didn't use the usual recommended dilution of 1+19 instead tested it at 1+29 and 1+39. There was logic to this, May & Baker (now Champion) Suprol a similar PQ developer came with a very comprehensive photo-copied data booklet. They gave comprehensive details for it's use in Photo-finishing machines, and also for reversal processing of cine films, there was also a section on it's use dilute as a Fine grain developer at these dilutions.

While he results with PQ Universal were excellent in terms fine grain and sharpness, but compared to ID-11there was a slight speed drop maybe half a stop, but it was very "Clean" working. By clean working really we mean less base fog, although this is more to do with dissolved colloidal silver at higher Sulphite levels which is why the 70-85g/l is more optimal than 100g/l

Of course there are the more recently formulated PQ liquid developers HC-110, Ilfotec HC/LC29, DD-X, Ilfosol 3, I found HC-110 and Ilfotec dropped film speed the others were released later.

Back to your question, I'd expect Autophen to be slightly better than ID-11/D76 sat between them and ID-68/Microphen. In terms of overall balance of speed, fine grain, and sharpness they aren't as good as Xtol or Rodinal. The caveat with Rodinal is its better with some films than others while Xtol is excellent with all, in comparison to PC which I assume you mean Pyrocat HD in terms of fine grain, sharpness and tonal range there's no noticeable difference in practical terms.

If I wanted to increase sharpness I'd try Pyrocat-M. The ratio of Phenidone to Pyrocetchin in HD is 2:50 but Pyrocat-M isn't a straight Metol Pyrocatechin equivalent as the ratio is 2.5:50 an 1/8th the quantity (assuming Phenidone is 10x more active than Metol). Sandy King has said Pyrocat-M is sharper but then it's getting closer to Hans Windisch's Pyrocatechin Surface developer.

Ian

 

[Ian Grant]

One striking feature of Phenidone and its derivatives is the 1/2 stop extra emulsion speed it gives with normal development. Obviously its inventors tried to bank on this trait and sacrifices grain and sharpness to get maybe even a full stop of extra speed, c.f. Microphen, FX-11, ... Evidently it took decades until XTol was released, which ignored the "gives an extra 2/3 speed" obsession and stuck a better balance between speed, grain and sharpness.

Yes Ilford themselves stated ID-68 was an entirely new formula rather than the tweaking they did to produce Autophen. Of course it's come from observations with formulating Autophen and exploiting both the slight speed increase of Phenidone and a speed increase by dropping the Sulphite. DD-X is supposed to be similar to a liquid form of Microphen.

In terms of fine grain traditional emulsions are more dependant on developer choice, with T grain and similar films it's more inherent in the emulsion. Hence why Rodinal is better with smoe films than others.

Ian

 

[Rudeofus]

In terms of fine grain traditional emulsions are more dependant on developer choice, with T grain and similar films it's more inherent in the emulsion.

All color film is T grain, yet Kodak still calls for the much more expensive HQMS in E-6 FD. Evidently there are significant differences to be achieved even in T grain films.

 

[Rudeofus]

While he results with PQ Universal were excellent in terms fine grain and sharpness, but compared to ID-11there was a slight speed drop maybe half a stop, but it was very "Clean" working. By clean working really we mean less base fog, although this is more to do with dissolved colloidal silver at higher Sulphite levels which is why the 70-85g/l is more optimal than 100g/l

If you want to reach smallest possible grain, you have to keep most image detail somewhere around a density of 0.3. 0.3 is the density with the lowest granularity, since you have an even balance between silver and no silver, and if you deviate too far from this optimum, spatial resolution goes down the drain. These "beautiful fat negatives" with important image matter happening between D=1 and D=3 are bound to be grainy.

If you want to keep all significant image detail between D=0.1 and D=0.8, you have to avoid fog at all cost, and avoiding fog at all cost (which you called "clean working") suppresses the toe region and quickly leads to speed loss.

 

[Ian Grant]

If you want to reach smallest possible grain, you have to keep most image detail somewhere around a density of 0.3. 0.3 is the density with the lowest granularity, since you have an even balance between silver and no silver, and if you deviate too far from this optimum, spatial resolution goes down the drain. These "beautiful fat negatives" with important image matter happening between D=1 and D=3 are bound to be grainy.

If you want to keep all significant image detail between D=0.1 and D=0.8, you have to avoid fog at all cost, and avoiding fog at all cost (which you called "clean working") suppresses the toe region and quickly leads to speed loss.

Kodak themselves have used the term "clean working" to describe Xtol, "KODAK PROFESSIONAL XTOL Developer is very clean-working, and will rarely need replacement in a properly replenished and maintained process. " But this is what Ilford say about the almost Infinite life of replenished Autophen decades earlier and borne of of very extensive testing.

By clean working Kodak mean insignificant build up of sludge usually caused by Colloidal silver, some of this colloidal silver remains in the emulsion as well and is measured as base fog.

Now this raises something interesting about the use of Phenidoone or Dimezone instead of Metol as well as the optimal Sulphite level. So we know that ID-ii/D76 is not a clean working developer and sludge builds up, we would decant the developer from our ID-11 deep tank every few weeks to remove the sludge, we'd make a fresh batch every 9 months or so. I used Xtol replenished for about 20 years keeping 2.5 litres of working solution replenished with what was left from a 5 litre pack there would be slight sludging over time but in comparison nothing like you get with ID-11/D76.

So the question is why is the problem less significant with Phenidone or Dimezone compared to Metol. Of course there's the Metol/Bromide build up issue with ID-11/D76 but why foes Autophen keep going indefinitely with little build up when essentially it's a PQ version of the developer same Sulphite level etc and only a slight difference in buffering.

Ian

 

[Rudeofus]

I have no real data on Phenidone, but would suspect, that it sticks to silver much tighter than Metol. This may well prevent silver sulfite complexes from escaping the emulsion.

 

[Ian Grant]

I have no real data on Phenidone, but would suspect, that it sticks to silver much tighter than Metol. This may well prevent silver sulfite complexes from escaping the emulsion.

I suspect it has something to do with the effects of Bromide both globaly in the developer as a whole as it builds up in a replenished developer, and then locally in the emulsion. The huge difference between Phenidones as a group and so Phenidone-A and Dimezone-S is they aren't affected by Bromide like Metol and can tolerate substantially higher levels more like a factor of 10x.

It's why I never use Metol in a regular print developer, the only exception being ID-3/D165 (Selectol Soft) with Graded papers which I rarely use. Oddly a PQ version of an MQ formula gives warmer tones so finer grain (in the paper) unless you add Benzotriazole. So that raises a question of whether Autophen gives any difference in grain to D76/ID-11.

Ian

 

[Raghu Kuvempunagar]

I have no real data on Phenidone, but would suspect, that it sticks to silver much tighter than Metol. This may well prevent silver sulfite complexes from escaping the emulsion.

What happens to these silver sulfite complexes that remain in the emulsion? Are they removed by the fixer?

 

[albada]

Yes Ilford themselves stated ID-68 was an entirely new formula rather than the tweaking they did to produce Autophen. Of course it's come from observations with formulating Autophen and exploiting both the slight speed increase of Phenidone and a speed increase by dropping the Sulphite. DD-X is supposed to be similar to a liquid form of Microphen.

Do you think Xtol's grain is better than the best PQ developer? I'm assuming the PQ developer reaches box-speed and has decent sharpness.
If Xtol is less grainy than the best PQ (and no worse in some other respect), then PC is better than PQ.
Mark Overton

 

[Ian Grant]

Mark, It's over 30 years since I did a lot of comparative developer tests. Xtol was a new generation developer better fine grain than any PQ or MQ developer I'd used, My own experiences agree with Kodak's developer comparison chart with regards to Xtol, D76 and HC110.

Could there be PQ developer that match Xtol, possibly, maybe something like Ilford DD-X. Cost would a factor in my developer choice more because it's uneconomic a developer like DD-X at 1+4 dilution is not economic for the way I process, 6 sheets of 5x4 in 1 litre of developer in my Jobo 2000 inversion tanks. £16 to process 30 sheets of 5x4 compared to £10 to process 600 sheets in Pyrocat HD, Xtol replenished works out at £14 for 267 sheets (approx).

It's the first time I have looked at it this way but I'd choose Xtol rather than DD-X because it's so much more economic, buying re-packaged Pyrocat HD would be about the same as Xtol, Economies of scale make mixing Pyrocat HD myself very cheap as I buy my chemistry in bulk, 25kg bags of Potassium Carbonate,1 kg of Pyrocatchin etc.

I still have two bags of Xtol I bought on a business trip to North America in 2003, I guess I've just got used to using Pyrocat HD I like the results I get with it, I find the negatives print easily. It's no better than Xtol and equally it's no worse, it's just a different approach using a staining developer.

Ian