Accelerants for Gainer's Vitamin C/phenidone developer

<p>As noted in some previous threads, I've been playing around

 

with mixing my own developer from scratch for the first time,

 

inspired by Patrick Gainer's article in Photo Techniques on

 

using organic solvents to create oxidation-proof stock

 

solutions. I've had a lot of help from forum members, and I'm

 

now quite happy with the results I'm getting, so I thought I'd

 

share some findings. <p>

 

<p>As per Gainer, I've been heating 100 ml of propylene

 

glycol, then adding 10 g (2.5 tsp) of ascorbic acid and 0.25 g

 

(1/8 tsp) of phenidone. As reported in <a href = "http://www.

 

photo.net/bboard/q-and-a-fetch-msg?msg_id=008IXZ">another

 

thread, </a> I found I had to take care not to heat the glycol

 

above 250 F, or it would start to smell. The odor didn't

 

affect the results and wasn't a big problem for film

 

development, but I want to use the solution for a paper

 

developer as well.</p>

 

<p>I've been using 20 ml of this glycol solution to a liter of

 

developer on Tri-X, using different alkaline solutions as

 

accelerant. The choice of accelerant appears to be very

 

important. I've been corresponding with Steve Murray, a forum

 

member, and our results are similar, though he dissolves the

 

phenidone in alcohol instead of glycol, as per <a href = "

 

http://unblinkingeye.com/Articles/VitC/vitc.html"> Gainer's

 

article on unblinkingeye.com.</a></p>

 

<p>As noted in <a href = "http://www.photo.net/bboard/q-and-a

 

-fetch-msg?msg_id=008Fh7"> this thread, </a> I got very grainy

 

results whenever I used sodium carbonate as the accelerator,

 

alone or combined with borax. The results were so striking

 

that I doubted that it was carbonate I had. It wasn't the kind

 

of sharp grain one would get from, for instance, Rodinal. It

 

was resolution-destroying grain. This wasn't due to

 

overdevelopment or overexposure. I developed one film to lower

 

contrast and got the same result. The carbonate produces a

 

striking increase in zone 1 speed - it makes Tri-X more

 

sensitive than anything else I've seen. Steve saw that speed

 

increase too.</p>

 

<p>Excluding the carbonate and using 2 tbsp borax to a liter

 

of water as the accelerant produced my first good results.

 

Grain is not exactly fine, but not bad either. Development

 

time was about 10 mins at 70 F, which holds for the other

 

formulas below as well.</p>

 

<p>In an attempt to reduce grain, I next tried 2 tbsp sodium

 

sulfite (about 50 g) plus a teaspoon of borax. That reduced

 

grain and actually seemed to improve accutance. Results looked

 

similar to Acutol 1+9.</p>

 

<p>Next try: 2 tbsp sulfite + 1/2 tsp borax (2.5 g). Very fine

 

grain, good sharpness. Looks similar to Xtol. </p>

 

<p>Last try: 2 tbsp sulfite and nothing else. Grain not quite

 

as fine as the previous formula, otherwise OK. Obviously, the

 

sulfite is the main accelerant in the two formulas above, but

 

the borax is necessary for the best result. <p>

 

<p>So 2 tbsp sulfite + 1/2 tsp borax with 20 ml of glycol

 

solution in a liter of water at 10-11 mins, 70 F, seems to be

 

a great combo for Tri-X. If I run out of either borax or

 

sulfite, it's not a big deal - I can just use 2 tbsp of the

 

other.</p>

 

<p>Steve tried the sulfite/borax formula on 4x5 Tri-X, and

 

found much finer grain than with the carbonate versions. He

 

compares it to D-76.</p>

 

<p>A couple of caveats:

</p>

<ul>

 

<li>Others report good results with carbonate.</li>

 

<li>I don't have a scale, so I've been using teaspoons and

 

tablespoons instead.</li>

 

<li>I used NYC tap water for all the solutions.</li>

 

<li>Temperature control hasn't been perfect, since my

 

apartment is now hotter than the working solutions. I used

 

rudimentary water baths in some cases, but temperatures may

 

have varied by up to 2 F during development.</li>

 

<li>I don't have a densitometer. I have compared Zone VIII

 

exposures to a calibrated Stouffer step grade to evaluate

 

contrast, aiming for density appropriate for a diffusion

 

enlarger.</li>

 

<li>I also don't have a working scanner, so I'm afraid I can't

 

really demonstrate results.</li>

</ul>

 

<p>A footnote:

</p>

 

<p>The time it takes for borax to dissolve in working

 

temperature water annoyed me a little, so I thought that now

 

that I'd arrived at the formula I want to use, I might as well

 

try dissolving borax in hot glycol, so I just need to add the

 

quick-dissolving sulfite when it's time to develop.</p>

 

<p>I dissolved 1 tbsp borax in 50 ml of hot glycol. It went

 

easily enough after some stirring. I combined that with the

 

vit /phenidone solution to create the borax-only formula

 

above. Result: blank film. Something happens to the borax in

 

glycol, inactivating it. That, or the relatively high

 

concentration of glycol in the working solution interfered

 

with development.</p>

 

<p>Of course, borax dissolves easily in hot water, so I may

 

end up using a concentrated stock solution of that.

</p>

 

 

<p>Other directions this can be taken: adding more sulfite or

 

possibly table salt to reduce grain further, possibly at the

 

loss of speed and accutance. The 50g of sulfite that I used

 

approximates D76 1:1. In Photo Techniques, Gainer suggests

 

using 100g of sulfite + 2 g borax. Borax + table salt should be

interesting to try - might tell us if the fine grain the sulfite

produces is due to solvent action or something else.</p>

 

<p>Gainer also suggests using triethanolamine, a liquid

 

organic base, both to replace the glycol and as the

 

accelerant. Others have reported good results with this on

 

this forum, but I wanted to stay away from it, since it may

 

not be as safe as glycol and it smells. Again, those are

 

mainly concerns when the stock is used for paper developer,

 

which I hope to report on later.</p>

 

<p>Also for safety reasons, I haven't tried sodium hydroxide

 

as an accelerant.</p>

 

I applaud Peter's efforts. The resulting "Gainer/Svensson" formula has worked great for me testing Tri-X (35mm, sorry, I haven't done the 4x5 yet, Peter). Looking at scans side by side matched for contrast and brightness shows Peter's version much finer grained than any version I've tried using sodium carbonate as the activator, even in combination with borax.

 

Looking at the formula for Mytol (the home brew version of Xtol), the Gainer/Svensson formula is quite similar to a 1:3 dilution. The proportions are close, except Mytol uses Sodium Metaborate (Kodalk) instead of Borax, and adds Sodium Metabisulfite, apparently a silver solvent used in D-25 to make it fine grained. I don't think its necessary in Peter's formula. Its already very fine grained and sharp.

 

As Peter mentioned, I am getting similar results using the earlier Gainer formula with the phenidone dissolved in 90% alcohol. That formula has somewhat less phenidone than the glycol version and I may increase it some. I can't wait to try it on 4x5 tri-x and tmx in a Jobo drum.

 

This stuff is easy to mix small quantities up when you need it and it mixes at room temperature. The ingredients are cheap. 20 Mule Team Borax works just fine. Using teaspoons and tablespoons is just as accurate and consistent too.

 

Great job Peter!

Borates are well known to react with glycols to produce boronate esters that will be completely useless as bases. That is probably what is happening when you heat borax with propylene glycol although I have never read about it occurring with this particular combination. It shouldn't happen at room temperature and definitely shouldn't happen if there is a lot of water around. Your formulas sound interesting though. Keep it up!

I haven't tried any of the developers with phenidone yet, using Metol/asc. acid/borax/sodium hydroxide instead, and I haven't tried the PG version, because apparently metol doesn't dissolve in PG the way that phenidone does. I've been using it mostly with generic/rebranded films like Arista Edu. films in 100/200/400 versions, and Photowarehouse's Ultrafine film. I've been getting good film speed, and fine grain (not as fine as Xtol). I shoot MF in 6x7, and rarely enlarge beyond 8x10, so grain isn't really a problem. I like the idea of making up a large quantity of stock solution, for consistency, and when I get some phenidone I'll try that, but I also like the idea of a sulfite-free developer, so I think I'll avoid the sodium sulfite formulae. By the way, I used the same formula double strength as a print developer, and it worked very well! Thanks for all of your work, and for sharing your results, you're a valuable resource.<div></div>

Jordan:

Thanks for the info about the esters - that would explain it, I'm sure. When I tried dissolving even more borax in glycol, the solution turned quite viscous, probably consistent with esterisation.

 

Jay:

That's a beautiful print. It looks a little warm on my monitor, which is what I'm getting with the print developer I'm trying, probably due to the bromide necessary for the proper contrast. I want warm tones, so that's not the problem.

 

The problem is that the solution only lasts a couple of hours in the tray. I used 60 ml of glycol (three times the film concentration) and two tablespoons of sodium carbonate to a liter. My next try will probably be adding some sulfite to see if I can extend the useful life, or possibly adding more ascorbic acid.

Thanks, Peter. I like the warm tone too, but the print was selenium toned.The developer only lasts a few hours for me as well, and it is very soft working. Pat Gainer recommended a one shot print dveloper, but I haven't tried it yet. I'm trying to use up my Edwal Ultra Black before it goes bad. The short tray life doesn't bother me too much, because the stuff is so cheap, but I do worry about the contrast reduction as the developer exhausts. I'd like to get it up to 8 hours of tray life, which would provide enough of a margin to print safely for 4-5 hours without mixing a new batch, which is pretty normal for me. I get two sessions out of a 1:15 working solution of Ultra Black. Thanks again for the valuable information.

I don't know where the grain is coming from, unless you are one of those who habitually decreases film speed. Overexposure is definitely a source of large grain. I have not had any success using sulfite as a preservative of ascorbates. Ascorbic acid is a more active antioxidant than sulfite, and so preserves the sulfite..This editor is still not wrapping my text, so I'm only guessing at what I;m writing. Gotta go now.

I've just done some tests wirg Patrick's TEA formula. First, a note: I'm not sure what I'm using is TEA (the bottle only states 'neutralizer', and it's sold as a TEA replacement).

 

TEA over here (and in other parts of the world) is under weapons control, since it can be used to make the very nasty mustard gas... (do a google for triethanolamine bomb mustard)

 

First test - basic formula but 85cc of 'TEA', 12.5cc of phenidone dissolved in alcohol, 1+50 dillution - very active, pH higher than borax.

 

Second test - 1+50, increased ascorbic A to 15g/100cc. pH is lower than borax, still quite active.

 

Third test - As above, but added some 25g/l of sulfite to the working solution. Increased activity by some 30%, finer grain.

 

Fouth test - dillution 1+60, all else equal - very nice negs with PX @200, 8min agitation 2/2 min @20C.

 

If the 'TEA' + absolute ethanol mix keeps as long as the PG formula, this is the homemade acorbate HC-110! (but finer grain, sharper).

 

Some of the tests above were made also with Fortepan 100, and I did not make prints yet (used a 10X loupe to judge grain).

Guys;

 

Marvelous work. Really nice.

 

I would like to caution you that volumetric measurments of chemicals, particularly organics is chancy due to changes in crystal habit. As the crystal type changes, the density changes.

 

I have had metol and HQ come in powder and needle form, and Na2CO3 come as crystals and beads.

 

So, if you have any repeatability problems, you might want to consider using gravimetric measurements for the materials. I always weigh everything. If you insist on volumetric measurements, I suggest that you get a mortar and pestle and grind every solid ingredient to an even consistancy. Clean the mortar and pestle between each chemical that you grind. Re-calibrate your measurements with the ground materials. Grinding them to an even powder will increase their density.

 

Take care mixing. Hot glycols are nasty. Don't burn yourselves. Have fun.

 

Again, a great piece of work.

 

Ron Mowrey

Here's a print from Edu. 100 developed in the developer I noted in my earlier post.<div></div>

Steve, just a note

 

Metabissulfite is added to Mytol to lower pH, decreasing grain and activity. I got about the same effect increasing the quantity of ascorbic A in the 'TEA' formula.

Here's one from an Arista Edu. 400 neg.<div></div>

Jorge, thanks for the info about Sodium Metabisulite.

 

Rowland, I do have a triple beam balance. I have also noticed the differences in weight per volume with the crystaline vs. the granular forms of Metol. I think the sodium sulfite, ascorbic acid, and borax are pretty consistently measured with tablespoons and teaspoons, weighing in at about 2 grams per one half level teaspoon for the Vit C and borax, and I get 48 grams a level tablespoon for sodium sulfite.

 

Patrick, for some reason leaving out the carbonate and adding some sulfite seems to decrease grain. My negs have not been overexposed nor over-developed. Whenever I use sodium carbonate the grain gets bigger. With larger negs its probably not that big of an issue, as Jay has noted, but with 35mm, especially with 400 speed films and up, grain is noticeable in the prints, and grain structure makes a difference in overall aesthethics.

 

Why are so many people against using some sodium sulfite anyway? We're using half of what's in D-76 and its many variations. Just wondering.

Off the top of my head, about sulfite.

 

It is a weak silver halide solvent and an accelerator.

 

Both of these properties can give bad, adverse effects under certain circumstances. A single bad experience can scare people away from an otherwise useful technique.

 

I say, if it works for you, use it!

 

I also understand your observations with volumetric vs gravimetric measure. Sulfite for example, seems to be very stable in form and therefore in weight per unit volume.

 

Ron Mowrey

Oops, correction: I meant one level tablespoon of sodium sulfite is 24 grams. Two TBS is 48 grams in the one liter mixture.

Peter, thanks for the <i>heads-up</i> about the borax in glycol. Noted.<p>

I use sulphite in my paper version of the Gainer staining developer. It makes making paper developer quick and easy. Add one and a half TBS' sulphite to a TBS of Carbonate and 30mls of staining developer per litre. Easy lasts days in a plastic jug in working solution. However, by adding sulphite to HQ and phenidone, I aren't exactly inventing anything. The sulphite activates the superadditivity in the HQ and the phenidone, it also preserves it. By adding sulphite to Vit C and phenidone what is being added here? Both are superadditive without it. There is no need for a preservative, you don't need it with propylene glycol. Mushed grain? perhaps...<p>

What is being taken away? A unique, <u>simple</u>, well crafted developer is turned into something, which is not.

Well, Nick, I think the point of my little dissertation above is that using the chemicals I've tested, adding sulfite gave the best results as I see them. I know it's not needed as a preservative. It does seem to be necessary for the finest grain. I really don't see why adding sulfite turns "a simple, well crafted developer" into its opposite.

 

Jay, about the paper developer: Patrick may be hors de combat because of his computer problems, but his wisdom is with us in the form of earlier postings. I just found this at the end of my first thread about this developer:

 

"Here is another consideration: for a given amount of phenidone, The rate of development will increase with ascorbate concentration at a decreasing rate. The change in rate after the ascorbate is 40 times the phenidone by weight is negligible. IOW, adding more ascorbate after that ratio will increase the capacity of the developer without appreciable change of rate. Going the other way, if you want to decrease rate but fear the loss of capacity, decrease the amount of phenidone but increase the amount of ascorbate to a ratio of 80:1. This sounds unorthodox, but I'm not Greek, so it's OK. "

 

Of course! The film developer's ratio of phenidone to ascorbic acid is designed for maximum activity for the amount of chemical. But in a paper developer, we need more capacity. So I would bet that adding an excess of ascorbate (or base + ascorbic acid) would cure our capacity problem. I may try it today. It may even be that adding ascorbate to exhausted developer may revive it.

 

Patrick: It's a great loss if you can't participate. Have your tried writing your comments in the Windows Notepad or a word-processing application, then pasting them into the photo.net text box?

Nicholas

 

I have to disagree on this one (well, again?)

 

It's been known for decades that sulfite helps the ascorbic acid development process. From a posting by Richard Knoppow re Xtol at R.P.D.:

 

" The solvent action may make some latent image centers more readily

accessible to the developer and thus increase the rate of development,

particularly in the lower-exposure-level regions. It is possible also

that some internal latent image is made accessible. James obtained

significant increases in emulsion speed for incomplete development by

adding sodium sulfite to an Ascorbic acid developer. The increase

amounted to as much as tenfold in some cases." [Theory of the

Photographic Process, 3rd ed. p.368] "

I have never found any such increase in effective film speed at low or high contrast due to adding sulfite unless there was also hydroquinone in the developer. If I could get that tenfold increase, I would be able to use 400TX or HP5+ at 4000 instead of the 400 I do use.. In any case, the addition of sulfite has little or no effect on life of the developer. I'm going to have to use Notepad, I guess.

My question at this point is what if we left out the ascorbic acid? Is 50 grams of sodium sulfite doing all "work" as an accelerator and preservative? If so, then we have something like D-76 1:1 with phenidone instead of Metol. I do think the sulfite's silver-solvent properties must be reducing the grain size. I guess that's my next test.

Steve

 

If you leave out the ascorbic, it's no longer a'd-76' style developer, in the sense that you would have two developing agents, one doing the actual work (metol or phenidone) and the other one as an helper (hydroquinone or ascorbic) in a super addictive pair.

 

But beyound any doubt, sulfite is makig the grain finer. It's not clear wich is the mechanism, but my guess is a combination of:

 

- The developer is more active, so shorter dev times -> less gelatin swelling;

 

- The increased activity allows for a lower pH -> again, less gelatine swelling.

 

- Some (but in my case not much - I use some 25g/liter, did not test less) solvent action on silver halide.

Was James using a synergistic pair like ascorbic acid and phenidone or metol? I find it very hard to believe a tenfold increase in E. I. I have upon occasion used the automatic bracketting on my Elan IIe with the midpoint set on the box ISO. Barring unusual lighting, the box ISO is correct when I use the camera as a point and shoot.

 

As for paper developers, I'm doing strange things. I have so many partially filled bottles of experimental developers, all put up (as we say in the country) in glycol and/or TEA, that I dump the ones I'm never going to use in a big jug and mix an ounce with a quart of water and add a tablespoon of borax and 1/2 teaspoon of lye. This makes a pretty good general purpose developer for either RC or FB papers.

 

If you remember the old approach of making solutions of metol and hydroquinone developers and combining them in various proportions for different effects, you may want to try making separate solutions of ascorbic acid, hydroquinone and phenidone in propylene glycol. You can make 20% solutions of ascorbic acid or hydroquinone, and at least 2% of phenidone. When you use hydroquinone, you will need some sulfite, but start with a little and add more until you get the max density. For alkali, I use the borax-lye mostly because my tap water is hard and makes lots of calcium carbonate when I use carbonates. The stock solutions will last a long time.

Since I do not have the book - that's why I've cited Richard's K posting - I cannot answer your question.

 

But I've found that PA devs becomes more energic and finer grained with the addition of sulfite two times - first with PG and now with 'TEA'.

 

So, for me at least it's the preferred choice.

Jorge, my understanding of D-76 is that the hydroquinone serves to extend the life of the developer, basically replenishing the used up metol. Apparently the ph is too low (I think that's it) for the hydroquinone to actually work as a developer. Hence, the D-76H formula uses no hydroquinone and a slight increase in Metol (2.5g)to achieve the same result. Also, D-23 is just Metol and sodium sulfite and works quite well. It just uses a ton of each and I rather like the more efficient use of chemicals to achieve the same result. That's why I am attracted to Patrick's formulas in the first place.

OK, I just now developed some more of the test roll I used for the last test of Peter's formula. This time I left out the ascorbic acid. Otherwise it was two TBS sodium sulfite per liter, one half tsp of borax and some phenidone as per Patrick's original formula. Same time and temp: 70 F for 10 min. The negs were nearly clear. Just a faint image appears. I guess the ascorbic acid is essential even with all that sulfite.