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Sodium Sulfate is one of the best anti-swell agents for gelatin.
PE
PE
Thanks, Thomas, I am fully aware that "stand development" (I put it in quotes because agitation does take place every so often) combined with weak dilutions can reduce contrast in a neg. The important point is, though, that not all developers respond to this in the same way, I would imagine a strongly buffered developer does this much less than a poorly buffered counter part, all other things the same. Rodinal is known to work extremely well with stand development. Its other big plus is that it is very well characterised after so many decades of heavy use. There are, however, hopefully some additional ways of achieving a flatter curve in the highlights which also work with devs more suitable for e.g. Delta 3200 (I have nothing against TMZ except that it doesn't come in 120 format).
I posted the link, because Ryuji said it was very difficult to alter the tone curve because it was very much a characteristic of the film used. I counteracted that comment by showing that you can override the tonality of some films (TMY-2, Tri-X 400, FP4+, TMX, Acros, Delta 3200, which have long straight curves) and create a shoulder by slowing down agitation. I do it myself every single time I develop film.
I have done some testing of PC-TEA where the developer is dilute but quite high amounts of sulfite added and I could not get grain as fine as Xtol(or DS-10,Mytol,E-76).It seems to me quite likely that the high phenidone(or derivative), ascorbate and borate in these latter contributes to the fine grain.Therefore the concentrate has to be high in phenidone,ascobate and borate.The chemistry gets to the limits of what is known,esp wrt the formation of glycol borate complexes and their dissociation,when making these concentrates.It's quite a project.
Well, the sensitometric data shown at your link does show some visible difference in the curve, but if you compare that to the shoulder of Verichrome Pan or Panatomic-X (which are generally referred to as films with shoulder) or even Delta 3200 or TMZ, you are not even halfway there. I would not state that effect as if you can switch one type into another.
The best way to obtain the "shoulder effect" in film characteristics today is to use paper emulsion with toe, and use print developer that does not trim the toe.
@Mark: you recipe worked, I developed for 12 minutes (attempted 2 stop push), agitated every 1/2 minute and got reasonable looking negatives. I'll try to print a few of them on Wednesday and will report what I find especially with regard to speed and highlights. Please note that I am aware that exposing film with the builtin meter of my Rollei 35s, pushing it two stops and then looking at the result is not the recommended way of evaluating a developer
I have done some testing of PC-TEA where the developer is dilute but quite high amounts of sulfite added and I could not get grain as fine as Xtol(or DS-10,Mytol,E-76).It seems to me quite likely that the high phenidone(or derivative), ascorbate and borate in these latter contributes to the fine grain.Therefore the concentrate has to be high in phenidone,ascobate and borate.The chemistry gets to the limits of what is known,esp wrt the formation of glycol borate complexes and their dissociation,when making these concentrates.It's quite a project.
PPS: Mark, some of the substances you specified come with varying amounts of H2O bound to the crystal grid. For now I assume you mean Na2BO2 * 4 H2O when you specify "Sodium metaborate". Please tell me if this is indeed the case.
Chemistry can be a bitch sometimesThe sodium metaborate I use is what PhotoFormulary.com sells, and I thought it was anhydrous. I just looked up the MSDS on PhotoFormulary's web-site (http://stores.photoformulary.com/images/store_version1/MSDS_Sodium_Metaborate_4_Mol.pdf), and it's the dihydrate version. Surprise! That MSDS says the molecular weight of NaBO2*2H2O is 101.83, instead of the 65.80 that I've been assuming all this time. Wow. Thanks for bringing this up.
From what I have understood the main problem with water in stock solution seems to be that water dissolves oxygen which hurts the developer. If you have only trace amounts of water I can't imagine how this would hurt. The 1.2g metaborate dihydrate of your recipe contain about 0.4g = 0.4ml of water, in 30ml of propylene glycol this is a trace amount in my book.That means I've been mixing some H2O into my concentrates. Not a good idea. Fortunately, I've determined the correct amount of sodium metaborate (dihydrate) experimentally in my developers, so they won't need to change. But I'll think about heating any concentrate to drive out H2O.
One question for the experts: If so much Na2SO3 is added to the mix, is it necessary to add some chelating agent like Na2-EDTA (Ryuji, I don't care about long term storage now) or Dequest (if I can get this anywhere here), or is iron only a problem with color film?
One more question: I set up a stock solution of metaborate from borax and lye in water. Is this stock solution reasonably stable or does it decompose somehow? If I let all the water evaporate from this mix: can I expect sodium metaborate crystals? If yes, what amount of water can I expect in these crystals?
According to PE they are not unrelated because Na2SO3 carries iron as impurity, and you confirmed that further down in your post. If ascorbate is part of most of the formulations here and highly sensitive to iron then Mark should seriously think about adding Na-EDTA, Calgon, Dequest or whatever.1. why are you talking about chelating agent in relation to sulfite? They are unrelated issue.
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They are not really concerned about iron. (MQ and PQ developers are not very sensitive to iron, manganese and copper impurities, where ascorbate developers are super sensitive.)
I referred to your quote about sudden death of Xtol and your dislike of Na-EDTA and got the impression that these are related. Since I already have Na-EDTA I would like to use it as chelating agent and think I can do this as long as I don't keep the mix for more than a day or so.2. In ascorbate developers, dealing with trace amount of iron impurities from any possible source (including water source and sulfite stock) is crucial for reliability, not just keeping property. I would not use an ascorbate developer without this measure, even for one-shot use, period.
Do you mean an hour after mixing the soup or that the change from good to mostly inactive happens within this time frame? I have read up on the Xtol sudden death syndrome and the conclusion seems to be that ascorbic acid oxidizes and does this faster if iron or calcium ions are present.You should study how "sudden death of XTOL" happened. It can happen in just a matter of an hour or two, and it does not discolor the solution at all.
Just for the record: stefan4u used Calgon in his working formulation of C41 color developer, which is used before the iron heavy bleach hits the film. It seems iron and/or calcium cause more trouble in color processing than just stains, so the problems may be closer related than you think. Anyway, I'm afraid I won't go out and modify Marks recipes before I get my hands on a semidecent pH meter (soon, I promise).3. Color process is a different problem. You have a lot of iron compounds in bleach bath. In some reversal processing, they need be thoroughly removed or it will turn into stain (very problematic in print processing). But the problem is different in ascorbate developers.
I would love to and would welcome decent references here. But first things first, as you may have read we have just established that I used only 3/4 or the metaborate that Mark recommended. It was my first run of home brew developer, luckily it yielded usable results so I am highly motivated to go on with these experiments. The darkroom cookbook will arrive tomorrow so my knowledge of photo chemistry will at least quadruple over the next few weeks4. You should really get some decent industrial chemistry references. Borate buffer is not a part of elementary chemistry but it is very common in industrial chemistry, and it is definitely important in understanding b&w film developers (as well as making your own). You should have data on concentration dependency, temperature dependency, etc. at your fingertips. Carbonate, phosphate, triethanolamine, diethanolamine, etc., are also important and useful. Those references will also have a chart on the hydration of the compound with respect to temperature and pressure.
One more question: I set up a stock solution of metaborate from borax and lye in water. Is this stock solution reasonably stable or does it decompose somehow? If I let all the water evaporate from this mix: can I expect sodium metaborate crystals? If yes, what amount of water can I expect in these crystals?
According to PE they are not unrelated because Na2SO3 carries iron as impurity, and you confirmed that further down in your post. If ascorbate is part of most of the formulations here and highly sensitive to iron then Mark should seriously think about adding Na-EDTA, Calgon, Dequest or whatever.
My answer is the same. EDTA makes it worse.I referred to your quote about sudden death of Xtol and your dislike of Na-EDTA and got the impression that these are related. Since I already have Na-EDTA I would like to use it as chelating agent and think I can do this as long as I don't keep the mix for more than a day or so.
If you really study cases of sudden death of XTOL you know the answer yourself.Do you mean an hour after mixing the soup or that the change from good to mostly inactive happens within this time frame?
Calcium has nothing to do with it. Iron, manganese, copper, these are the problems. And you see, XTOL has a copious amount of DTPA, which is significantly more powerful than, but of generally of the same type of chelating agent as, EDTA. If DTPA isnt good enough, EDTA is not good at all. Neither is NTA.I have read up on the Xtol sudden death syndrome and the conclusion seems to be that ascorbic acid oxidizes and does this faster if iron or calcium ions are present.
Are you ok with a developer that *may* die in an hour after mixing? I am not.Again, these issues seem very important for devs which are sold commercially and/or stored for prolonged time frames but this is not an issue for my experiments yet.
What are you talking about??"Sudden death of Xtol" is a popular topic but I don't remember it being reported for freshly mixed Xtol.
There is no logical and semantic connection between each of your clauses above.Just for the record: stefan4u used Calgon in his working formulation of C41 color developer, which is used before the iron heavy bleach hits the film. It seems iron and/or calcium cause more trouble in color processing than just stains, so the problems may be closer related than you think. Anyway, I'm afraid I won't go out and modify Marks recipes before I get my hands on a semidecent pH meter (soon, I promise).
Are you ok with a developer that *may* die in an hour after mixing?
Chemistry can be a bitch sometimesI incorrectly assumed you meant the tetra hydrate NaBO2*4H2O so it looks like your recipe still yields results even if the metaborate content is off by quite a bit. Using the same weight of tetra hydrate instead of dihydrate adds only 3/4 of the metaborate to the mix.
Does it make it worse because the iron bound by it is still or even more chemically active (like it is supposed to be in Ammonium-Ferric-EDTA) ? Or are there other effects I have not thought/learned about?My answer is the same. EDTA makes it worse.
Would Dequest 2010 be better? I have a possible source for it here in Europe (Tronds knows about this).Calcium has nothing to do with it. Iron, manganese, copper, these are the problems. And you see, XTOL has a copious amount of DTPA, which is significantly more powerful than, but of generally of the same type of chelating agent as, EDTA. If DTPA isnt good enough, EDTA is not good at all. Neither is NTA.
Ryuji, the instances I have read about were about XTol from which 5l were mixed some time before and which then went from active to inactive within an hour. I am sure the "Sudden Death of Xtol" has been discussed extensively over the many, many years Xtol has been sold commercially and I take your word that this happened to a few people right after opening the concentrate.Are you ok with a developer that *may* die in an hour after mixing? I am not.
Of course, many people eat raw cookie dough and dont get sick. Some get sick but they tell themselves that the dough was old, and never seriously consider the real known risk just because the chance isnt that large.
What are you talking about??
*Sudden* death of XTOL is about freshly mixed XTOL.
I made up the developer above, call it D316 after the post number.It could be made by heating to 70C in a water bath.The 45g/L sulfite I weighed out is about 4 heaped teaspoons.The measured pH was 8.1.My experience agrees with Ryuji. As an example, here's a formula that gives grain matching XTOL under my 22x loupe, yet has low concentrations of phenidone and other components. This formula is for a concentrate yielding either 5 liters or 1 liter of working solution:
Working volume ----------> 5L .......... 1L
Propylene glycol .............. 75 .......... 15 ml
Sodium metaborate ......... 11 .......... 2.2 g
Ascorbic acid ................... 22.5 ....... 4.5
Phenidone ....................... 0.25 ....... 0.05 g
Propylene glycol to .......... 100 ........ 20 ml (should need to add only 5/1 ml)
pH = 8.0. Use 20ml per liter (1+49 dilution) into water containing 45 g/L sodium sulfite.
Develop for twice XTOL's times.
Mark Overton
A simple web search yields quite a few reports but so does a search for "front focus" for just about any auto focus lens which could be attached to a Canon EOS body. I am confident that Kodak would have recalled and reformulated Xtol if this was a problem likely to happen to many customers of their product. What this means for us, though, is that we have to be careful with ascorbate based developers. We don't have the complete recipe for Xtol (the patent may not include improvements which have been kept as trade secrets) so we have no real insight how Kodak dealt with the potential sudden decay of ascorbate.I have never seen a first hand account of XTOL "sudden death". I have heard of it being DOA when freshly mixed from early batches. Kodak revised the packaging to prevent this problem.
Can it have any effect on B&W developer ingredients that we should be aware of? Any potential interactions with the fixer if we don't rinse well enough after dev? Does Dequest also catch other ions like calcium, manganese or copper or whatever may show up as impurity in the raw chems and bite our precious dev?Iron sequestered by EDTA is much less active than free Iron, but it can still act as an oxidant and we see this in color bleaches that use EDTA or EDTA like compounds. Dequest OTOH, inactivates Iron so effectively that I have seen it decolorize Ferric salt solutions and deactivate bleaches.
The problem is that metaborate comes with different amounts of water so there was no way to be sure. There was a procedure for producing (there was a url link here which no longer exists) but again, no indication was given how much water is bound per molecule or how one would influence that amount. It looks like I should use (there was a url link here which no longer exists) as it seems the best option for me right now.Perhaps it's the same stuff. I noticed that the decahydrate that I used is also written as Na2*B2*O4*4H2O, which merely doubles everything, and might be what you have. Here's a data-sheet showing both formulas: http://www.borax.com/pdfs/dist/DataSheet.Borates.SodiumMetaborate4Mol2010.pdf
I made up the developer above, call it D316 after the post number.It could be made by heating to 70C in a water bath.The 45g/L sulfite I weighed out is about 4 heaped teaspoons.The measured pH was 8.1.
HP5+ was developed in D316 for 2x the Xtol 1+0 time.
HP5+ for comparison was developed Xtol 1+1.
The EI I would use for sun/shade conditions, average metering, was D316=EI 320, Xtol 1+1 = EI 400.
Attached scans are of 0.1 inch square sections of negative scanned on an Epson V700 at nominal 4800dpi, sharpened equally.
Conclusions:
Xtol 1+1 gives finer grain and slightly higher speed.
D316 wrt its concentrate composition and dilution is practical and economical, probably near optimal.
Concentrate is a good developer but cannot be made so as to give as fine grain as Xtol,though close.
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