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Gerald C Koch
01-13-2012, 12:10 PM
Here is a developer that uses TEA as the chief alkali. pH of the concentrate is 10.4 and of the dilute developer 9.5.

Distilled water (50°C) 500 ml
Potassium sulfite (anhy) 225 g
Hydroquinone 40.0 g
Phenidone 5.0 g
Triethanolamine 400 ml
Potassium bromide 15.0 g
Disodium EDTA 25.0 g
Distilled water to make 1.0 l

This formula is said to produce negatives that are very close to those of Agfa Studional (Rodinal Special). Use dilutions and times as specified for Studional.

albada
01-13-2012, 02:07 PM
I use a 6x7 format camera and enlarge Delta 3200 to 10x15, 13x18 and 18x24, what do I care about grain? Sure, using 135 format with its faster lenses would gain me 2 stops, but I really like the 6x7 view finder for night shots.

Rudeofus: You're doing night shots? And shooting into the sun? Sounds like you want to push, and have lower contrast to tame highlights. Here's a formula which does both. It's a lower priority for me, but I stumbled across it half by accident (as usual), and it might be something you'd like to tweak for your goals. If you expose and develop for midtones, it'll push the shadows for you. Unfortunately, fog is higher (with TMY-2 anyway).



Propylene glycol ............. 25 ml
Sodium metaborate ......... 1.2 g (1.05g is needed to convert the ascorbic)
Ascorbic acid ................. 2.8 g
Phenidone ..................... 0.15 g
Propylene glycol to ......... 30 ml final volume

Dilute 1+32 with water containing 35 g/L of sodium sulfite. Target pH is 8.2. Try 8 minutes at 20C.


You can probably get by with 25 ml or maybe even 20 ml final volume of concentrate, but 30 ml is what I used on my first and only try. I'm guessing that the lower contrast (and shadow-pushing) is due to poor buffering causing compensation.

Edit: I just ran the numbers through, and propylene glycol volumes of 16 ml (initial volume) and 20 ml (final volume) should work fine. This would yield a 1+49 dilution.

Mark Overton

Rudeofus
01-13-2012, 03:36 PM
Rudeofus: You're doing night shots? And shooting into the sun?
Here are my pet projects:

Shoot image with silhouette trees (birds, leafs optional) with dramatic clouds and sun in the back ground. Let Tri-X display its beautiful grain structure in the clouds but turn the sun into something more than just a bright patch in the sky, see first attachment (Rollei 35S, Tri-X @ 800, HC-110).
Shoot moon in partially cloudy sky, try to record clouds and moon with detail, see second attachment (RZ67, Delta 400, Ilfosol 3). I could not see one bit of detail recoded in the moon, although it was only 100 times as bright as the bright edges of the clouds.
Shoot obscene macro with stacked lenses, suddenly Delta 3200 is a slow film in broad daylight, see third attachment (RZ67, Delta 3200, Ilfosol 3). A dev giving me extra shadow detail would be helpful, grain be damned.
Shoot working men in their work place, which is frequently poorly lit and obviously doesn't allow for strobes. The image in the fourth attachment (RZ67, Delta 3200 @ 6400, HC110) was ok, but not everywhere you find as much light, especially at the location where the welders work at night.


Before the usual barrage of "use this dev" and "the contrast is too high" starts: prints 1 and 2 are heavily dodged&burnt at different gradations, so what you see is what there is in the neg. If I can find something which puts real detail around the sun and inside the moon I'd happily take it.

Xtol and DD-X give me one extra stop compared to my HC-110. If I find something which gives me a 2-3 stops of extra shadow detail at the expense of a lot of extra grain, I'd happily take it. Before anyone says you can't get 2-3 extra stops of shadow detail: Gerald Koch means you can (http://www.apug.org/forums/viewpost.php?p=1204411), the detail must be somewhere in the film already.


Unfortunately, fog is higher (with TMY-2 anyway).
Have you tried adding anti foggants to your recipe? Ron has recommended KBr and benzotriazole before and at least KBr is easy to get.


Sodium metaborate ......... 1.2 g (1.05g is needed to convert the ascorbic)
I have gotten everything from that recipe except for Sodium metaborate. I did get Borax and NaOH and have the strong feeling I can use these two instead but I'm not sure. Can someone confirm this or show me another way how to make metaborate from Borax?

BradS
01-13-2012, 04:22 PM
I have gotten everything from that recipe except for Sodium metaborate. I did get Borax and NaOH and have the strong feeling I can use these two instead but I'm not sure. Can someone confirm this or show me another way how to make metaborate from Borax?

I had this same question a while back...I'm not a chemistry person so it took me several hours to figure this out but here's the way I see it....

2NaOH + Na2B4o7(10H2O) + 5H2O <-->> 4NaBO2(4H2O)

2 mols lye + 1 mol Borax (in water) is equivalent to 4 mols Kodalk in water

80g lye + 381.37g Borax (in water) is equivalent to 551.42g Kodalk in water.

Divide those last quantities in order to find reasonable amounts for your application.
Note: Kodalk is the trade name that Kodak used to use for Sodium metaborate.

Ryuji
01-13-2012, 04:26 PM
There are examples of poorly buffered developer concentrates. For example, the catechol-caustic formulae that were once popular. D-23 and that old standby D-76 are poorly buffered.

Do you realize that:

1. catechol itself is acting as a mild buffering agent. Plus, catechol caustic developer is by no means a good developer in light of modern industrial chemistry.

2. D-23 is moderately buffered by sulfite

3. D-76 original formula is actually reasonably buffered (2g/L borax for pH of 8.5-8.6ish, not a lot but not too bad for that spec.)

Rudeofus
01-13-2012, 04:28 PM
Thanks, Brad. Does this reaction happen automagically or does the Borax needs some help (heat, pH level, catalyst, ...) with decomposing into smaller compounds?

BradS
01-13-2012, 04:31 PM
Thanks, Brad. Does this reaction happen automagically or does the Borax needs some help (heat, pH level, catalyst, ...) with decomposing into smaller compounds?

I think it just happens when the constituents dissolve in water. Like I said, I'm not a chemistry person. I will say that using Borax and lye dissolved in water in this ratio has always worked for me.

Ryuji
01-13-2012, 04:44 PM
As I mentioned before, I don't think little Rudeofus with his admittedly highly limited knowledge of chemistry overall and photochemistry in particular will revolutionize film developers.


What I’m saying is that experiments only give you tiny dots in the vast knowledge space. Understanding the theories allows you to interpret the tiny dots so that you can get a lot more meaning out of it, while minimizing the risk of putting yourself in pitfalls. That is learning.



We don't have to beat XTOL. 99.99% of all users may judge Rudeofus-01 as complete disaster because it lasts 1 hour, develops few films[...]



Well, this response is not necessarily directed at you, but in general, look at the title of this thread and also count how many times things are claimed to be “better” or “improved” or whatever, from XTOL or DS-10. Some postings of the present thread sound different from what you said, you know...

Ryuji
01-13-2012, 05:06 PM
Ryuji says that solvent-effect is not proportional to dev-time, but I'll at least try a new concentrate that cuts the (separately added) sulfite in half and doubles dev-time and see what it looks like. It seems that when I try something, I often get a "surprise". :confused:

Ryuji: A few posts ago, you said that using TEA as the sole carrier in a concentrate is a poor idea. Yet PC-TEA uses this approach. What specific problems occur with doing that? If it's not feasible for a specific reason I'm interested in, then I'll drop that pursuit.


Second point first: triethanolamine is very viscous and it is not easy to meter accurately without wasting a lot of stuff. It also solidifies easily at the low end of typical winter storage temperatures. Then, as you saw, triethanolamine is a free base and you need to add a balancing amount of acid to make a useful buffering system, as TEA’s buffering capability is essentially limited to 7.4 to 8.2 range. But then the extra TEA and acid used for this purpose is not serving a useful function other than bulking up your stock solutioon.

Now sulfite. With DS-10, you can probably get away with 40g/L sulfite with little change in granularity, speed or tone curve. Between 10 and 40g/L the result will be film dependent. It’s probably the same with XTOL. If you use too little sulfite in these developers, one of the first thing to measure is loss of speed.

You need to understand that, D-23, D-76, XTOL are originally intended for replenished use in deep tank processing. 80 to 100g/L of sulfite is used to keep the developer stable in these applications (of course, in case of XTOL, this failed and later dropped). It is also important to realize that, XTOL was initially offered with dilution up to 1+3 for some films, and it would’ve needed some sulfite even in the diluted working solution.

Actually, the notion of “silver halide solvent effect” is overly inflated in some books written for darkroom enthusiasts and online forums, especially in the context of fine grain effects.

I once had a jug of replenished developer, which was a variation of DS-10, in my darkroom. It worked very nicely and it was practical, with very minimal wastage, unlike one shot use.

Ryuji
01-13-2012, 05:16 PM
Thanks for this. I've printed it out and stuck it to the wall of my cube. It reminds me a little of of George Box's explanation of the scientific process(*).

(*) George Box, Stuart Hunter and William G. Hunter, Statistics for Experimenters, Wiley & Sons, 1978

Yeah thanks for mentioning the nice classic book. Yeah it is important to identify the target/objective/goal to analyze or solve, before doing anything... otherwise things will go Iraq.....

I should probably print up a bunch of 3x5 cards with this and put them everywhere around me.

Ok whaaat am I doing on apug. I will log out in a few minutes.

Ryuji
01-13-2012, 05:27 PM
Here are my pet projects:
Xtol and DD-X give me one extra stop compared to my HC-110. If I find something which gives me a 2-3 stops of extra shadow detail at the expense of a lot of extra grain, I'd happily take it. Before anyone says you can't get 2-3 extra stops of shadow detail: Gerald Koch means you can (http://www.apug.org/forums/viewpost.php?p=1204411), the detail must be somewhere in the film already.


No, you can’t. As you expected to hear.

Gerald Koch likes to dig snippets from old literature and that is all good, but you need to be careful whether it is applicable by today’s standard. Hypersensitization worked when the silver iodobromide crystals were not as thoroughly sensitized chemically. Today’s emulsion technology, including the conventional grain technology like Plus-X and Tri-X, are highly sensitized for maximum efficiency of forming latent image sites that are accessible to developers. This is even more so with TMY-2. So, there is no room to boost sensitivity beyond what’s designed into the emulsion.

Rudeofus
01-13-2012, 05:37 PM
What I’m saying is that experiments only give you tiny dots in the vast knowledge space. Understanding the theories allows you to interpret the tiny dots so that you can get a lot more meaning out of it, while minimizing the risk of putting yourself in pitfalls. That is learning.
I hold a doctor's degree in EE and so believe me I have seen&done science and know the difference between my blindfolded dive into the field of photo chemistry versus real research work. And let's be honest: having family, kids and a job is not a good starting point for a new entry into a different science field anyway, one evening of dark room work is all I get per week. Luckily I don't have to deliver on my (photographic) promises and definitely not in a tight time frame (which makes photography so much more entertaining than my real job). I will probably start with Mark's last recipe and try it on that roll of Tri-X which I have shot @ISO1600, let's see what that film does after 12 minutes in that soup and let's compare it to the Tri-X @ ISO800 in HC-110.

I'd still like to find out at some point what I need to do to a developer so I can shape the shoulder of the characteristic curve in the high density range, and of course it would be interesting why Rodinal/HC110 yield slower film than Xtol/DD-X.

PS: For all those poor souls who would also like to try Mark's mixture but metaborate substituted with borax&lye in a 250 ml tank, here are the (hopefully) correct quantities:


Propylene glycol ............. 6 ml
lye ................................ 0.058 g
Borax ............................ 0.277 g
Ascorbic acid ................. 0.7 g
Phenidone ..................... 0.0375g (wow! )
Propylene glycol to ......... 7.5 ml final volume

Dissolve 9g of Na2SO3 in 200 ml of water and add the stock solution, then fill up with water to make 250ml. Double all the above listed amounts for roll film (500ml).

albada
01-13-2012, 06:06 PM
PS: For all those poor souls who would also like to try Mark's mixture but metaborate substituted with borax&lye in a 250 ml tank, here are the (hopefully) correct quantities:

A quick note: That concentrate formula only works if you have sodium metaborate powder (not mixed in water). For what you're doing, I suggest adding all ingredients directly to water, starting with the sulfite, and omitting the propylene glycol. For your initial testing, you don't need to create a PG-based concentrate, although it would be handy for running multiple tests.

Also, for measuring small sub-gram quantities, folks typically use percentage solutions. For example, I dissolved 1 g of phenidone into 99 g of PG, creating a 1% (by weight) solution. So instead of weighing out 0.01 g of phenidone directly, I weigh out 1 g of solution. Much more accurate with my digital scale that has two digits of accuracy.

Mark Overton

Ryuji
01-13-2012, 06:06 PM
I'd still like to find out at some point what I need to do to a developer so I can shape the shoulder of the characteristic curve in the high density range, and of course it would be interesting why Rodinal/HC110 yield slower film than Xtol/DD-X.


Creating a shoulder in curve is not an easy thing, because that is dictated by the emulsion. Films that have gentle shoulder are TMZ, D3200, Neopan 400 and D400, roughly in the order, from strong shoulder to weaker shoulder. So, choose one of these films and pair it with paper emulsion that has toe and use print developer that does not suppress that toe (such as DS-14). It also helps to develop the negative to a slightly lower contrast.

Why Rodinal yields low speed? That is the developing agent.

Why HC-110 yields low speed? That’s the balance of the developing agent and bromide, coupled with the other parameters of the developer. HC-110 has a lot of bromide in comparison to the active developing agent for that pH.

Thomas Bertilsson
01-13-2012, 06:16 PM
Creating a shoulder in curve is not an easy thing, because that is dictated by the emulsion. Films that have gentle shoulder are TMZ, D3200, Neopan 400 and D400, roughly in the order, from strong shoulder to weaker shoulder.

http://www.apug.org/forums/forum216/69617-shaping-tone-curve-rodinal-negative.html

This will help you shape your tone curve.

albada
01-13-2012, 06:19 PM
Chemistry question again: Does the order in which components are added matter? For example:

Order 1:
sodium metaborate
ascorbic acid
sodium sulfite

Order 2:
sodium sulfite
ascorbic acid
sodium metaborate

I know that order 1 will convert the ascorbic acid into sodium ascorbate, with sulfite added afterwards.
Will I get this same end-result with order 2?

Order 1 is what Rudeofus will get using a concentrate, and order 2 is what I suggested he do adding components directly to water. And that got me thinking if sulfite first-versus-last makes a difference...

Mark Overton

Ryuji
01-13-2012, 06:30 PM
Chemistry question again: Does the order in which components are added matter? For example:

Order 1:
sodium metaborate
ascorbic acid
sodium sulfite

Order 2:
sodium sulfite
ascorbic acid
sodium metaborate

I know that order 1 will convert the ascorbic acid into sodium ascorbate, with sulfite added afterwards.
Will I get this same end-result with order 2?

Order 1 is what Rudeofus will get using a concentrate, and order 2 is what I suggested he do adding components directly to water. And that got me thinking if sulfite first-versus-last makes a difference...

Mark Overton

That particular case, everything is reversible reaction and nothing leaves the system so it doesn't matter as long as the end product and pH meet your needs.

Don't worry about the order of sulfite - contrary to common wisdom the reaction of molecular oxygen and sulfite is so slow that any dissolved oxygen will be eaten up by ascorbate anyway.

Photo Engineer
01-13-2012, 06:32 PM
Mark it is always a good idea to add all or part of the sulfite first when you mix up a powder developer. This will scavenge the Oxygen dissolved in the water and make the results more even from mix to mix.

PE

Gerald C Koch
01-13-2012, 09:59 PM
D-76 suffers an increase in pH due to oxidation. This has been known for a very long time. Various modifications have been proposed to the original formula to provide better buffering such as D-76d which contains 8 g/l each of borax and boric acid. The change in activity led me to abandon the use of D-76 decades ago. I personally would not describe this developer as being reasonably buffered.

Gerald C Koch
01-13-2012, 10:12 PM
When mixing a developer it is always good practice to add the anti-oxidant before any alkali. Another case that I am awhere of when the order of mixing is important are certain developers that depend on the generation of bicarbonate ion for them to work properly. Here it is important that the carbonate be added before any acidic component such as sodium bisulfite.