Accelerants for Gainer's Vitamin C/phenidone developer

[jorge_oliveira2]

Steve

 

What you did is equivalent to POTA - a very low contrast developer, with a significant loss of film speed, but will allow for a very wide luminosity range without blowing highlights.

 

It would take something equivalent to a nuclear blast to blow highlighs - seriously, that's what POTA was conceived for.

 

Phenidone is not suitable for single agent devs (except POTA like), For this usage, you should try metol or others.

[sjmurray]

Thanks, Jorge.

 

It seems what we have in Peter's formula is a nice hybrid between the very elegant and super efficient vit c formulations of Patrick Gainer, and Peter's addition of sulfite to decrease grain. Its still very "efficient" in that the vit c allows a miniscule amount of phenidone or metol to develop film.

[peter_svensson]

Steve,

I really can't take much credit for adding sulfite to the phenidone/ascorbic formula. Patrick himself suggests it in Photo Techniques. Xtol, Mytol and E-76 already contain this combination, so no leap of inspiration is required. Dissolving the developing agents in organic solvents, now that's SMART.

[jay_de_fehr]

Peter, thanks for the quote:

 

"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. "

 

But, is the above true for Metol as well?

[nicholas_t.]

Photo.nets been down all morning for me so I've been usable to respond.<p>

Peter, I'd like to remind you that I didn't say <i>adding sulfite turns "a simple, well crafted developer" into its opposite</i>. I said that <i>a unique, <u>simple</u>, well crafted developer is turned into something, which is not</i>. They are different things (you figure it out). Like I said, I add sulphite to some of my developers too, paper ones. However, and this is to respond to Jorge too, it's not original. And I'd like to qualify it by saying if it works for you, great, but what it means is that you are essentially changing something unique (a sulphite-free ascorbate based developer) into something which is not (do I even have to say?..).<p>

AFAIK, ascorbate developers with a minimum of sulphite are surface acting developers.<br>

How many of these kinds of developers are there around which <b>don't</b> use sulphite in the ingredients? Not many (a handful?).<br>Why? Because, they <b>have</b> to. They have no choice, there is no alternative for these developers in terms of choice of a preservative mainly. But, also some people like the effects sulphite has on the development, lowered apparent grain, but this is offset by lowered apparent sharpness.<p>

I think, in many ways, with these new developers we are getting ahead of ourselves. Patrick has figured out how starve off the ionisation of developers and has created a series of developers in this mode where sulphite is not needed; now, we can look at what the actual role of sulphite is in the development process--on our own terms. This is because we don't need it anymore. I personally think this is an advancement in developer technology, probably the second real <i>public</i> advancement, in the last few decades (the first being the popular use of Vitamin C in developers).<p>

In terms of grain, I've used borax over carbonate and combinations of the two... Yes, there is a slight grain advantage with borax, but, it is subtle. In fact the most grainless developer I use has no sulphite or Vit C. I can't say this is for sure because all of the developers I use a relatively grain-free. To me, squeezing the last nth of a percentage of grain out of a developer is not a big deal. Getting good tones is more important and having something look sharp is important too--to me. BTW, I've also got experience in printing exhibition fibre prints (to 20x24in) made in D76 too, so I do have something to qualify this comparison.<p>

I suppose what I find interesting about these new alcohol based developers is what is <i>truly</i> new and a real advancement in terms of photographic technology. To me, adding sulphite to a developer, calling less grainy, is not a real advancement. In my mind, the habit of adding sulphite to developers for the dissolving action defeats the whole purpose of propylene glycol based developers. Why not mix D76 and be done with it?

[peter_svensson]

Nick,

I see what you mean now, but it doesn't matter to me if the developer I use is unique or not - it's not collecting art.

 

"I personally think this is an advancement in developer technology, probably the second real public advancement, in the last few decades (the first being the popular use of Vitamin C in developers)."

 

Very true.

 

"In fact the most grainless developer I use has no sulphite or Vit C."

 

Well, that's interesting! Is it the staining developer you mention above?

 

"To me, squeezing the last nth of a percentage of grain out of a developer is not a big deal."

 

Trust me, I'm not after that either. The grain differences I saw wouldn't be expressed in terms of nths of a percentage. I used an 8x loupe to evaluate the film, that's all.

 

"To me, adding sulphite to a developer, calling less grainy, is not a real advancement."

 

I didn't say it was. But as you can see above, others are finding as I do that to take advantage of the real advance here, the organic-solvent stock solution, we prefer to back-track a little and put the sulfite back in the mix.

 

"Why not mix D76 and be done with it?"

 

Easy: I can't store enough D-76 to process 60 films in a soda can. Even if I could, I wouldn't use it up before it spoils with no warning. Besides, D-76 is sensitizing etc. etc.

 

Jay, I suspect I suspect Patrick's comment holds true for the metol and ascorbic as well, except that the ratio is 1:10 instead of 1:40.

 

What camera do you use, btw?

[jay_de_fehr]

Thanks, Peter. I use a Mamiya RB67 for MF, and an 8x10 Deardorff for LF.

[nicholas_t.]

Peter, I totally understand where you are coming from and can relate esp the part about how concentrated you can get this developer. Sandy King apparently managed to dissolve a %20 VitC solution in Propylene Glycol--twice normal strength! I suppose my point is that when making variations of this developer I think it's important to rememeber the geneology of it at the same time--where it comes from and why this is so.<p>

Yes, the Gainer staining developer (HQ/P) is my favorite. My second favorite is the Vit C, Metol, and Carbonate developer ("original" in unblinkingeye). So simple, and it works equally for both film and paper. Actually I think I like them equally :-)<p>

[sandy_king]

Just a few thoughts on some of the preceding messages.

 

First, I have done quite a bit of experimentation with Patrick Gainer's PC-TEA formula. (9g ascorbic acid plus 0.25 g phenidone in 100 ml of TEA. At the 1:50 dilution it has working pH of about 9.1, which is slightly higher than D76, and is a very energetic developer. For my work with alternative processes PC-TEA with the 1:50 dilution is almost ideal because it gives a lot of contrast with short development times. For silver printing I would suggest a dilution of 1:75 or so. My only complaint about the formula is that as is it gives fairly high B+f values so I suggest adding about 0.2 g or potassium bromide to the stock solution, which will reduce B+f with Ilford FP4 sheet film from around log 0.28 to about log 0.12, with no loss of emulsion speed. And about the same with Ilford Delta 100. I think Patrick has some other ideas about reducing B+f but adding bromide is my solution and it works fine without reducing emulsion speed.

 

Second, regardless of what anyone may have written about speed enhancement with certain formulas or chemicals it remains a fact that when one develops negatives to the same CI the difference in effective emulsion speed is primarily built into the film. Based on comparisons of Ilford FP4+ and Delta 100 film between D76, PC-TEA and Pyrocat-HD, using light-integrated exposures, I have found that the relative speed of both emulsions produced by the three developers to be very close: about ISO 80 for D76, 100 for PC-TEA, and 120 for Pyrocat-HD. Real increases of emulsion speed of more than 1/4 or 1/2 stop with any film/developer combinations are simply not realistic.

 

About adding sulfite to the PC-TEA mix. It may make the developer slightly more active and reduce grain but I doubt very much that there will be any increase at all in effective emulsion speed. And the negative side of adding sulfite is that you will get grain etching, and less apparent sharpens. Granted, the differences both ways may be insignificant visually but etching is what sulfite does and the trade-off in sharpness is well-documented in the literature.

 

Sandy King

[jordan_w.]

Does anyone know what the 'accepted' explanation is for the grain reduction seen when borax is used as an alkali vs. other alkalis? (like carbonate, hydroxide, etc.)

[kelly_flanigan1]

Interesting thread!<BR><BR><a href="http://www.udmercy.edu/crna/agm/phenvitc.htm">Here is an Paper by Michael P. Dosch<BR><BR>"Storage life of photographic developers: Phenidone-ascorbic acid, and metol-hydroquinone types"<BR><BR>"What are the practical time limits for the individual darkroom?"</a>

[patrick_gainer]

Hooray! The words wrap!

 

Steve, I would have told you that phenidone in that concentration would have done nothing, and would have but for the fact my modem broke and I had to install a new one. The working solution of most of my developers has about 0.05 grams of phenidone per liter.

 

My experiments with ascorbic acid included a Q&D comparison between it and hydroquinone as process developers. A simple but effective such developer is a bunch of hydroquinone, a bunch of bromide, and a bunch of lye in a buchet of water. Almost any size bunch will do a very good job of developing line art on Ortho Lith film. Substituting ascorbic acid for the hydroquinone gives similar results. I think I also used a bunch of sulfite. I was after general characteristics, not a perfected formula.

It is definitely the ascorbate that does the work. If phenidone were oxidized, you would see red or pink. It's oxidation to that point cannot be reversed by hydroquinone or ascorbate. Apparently it has at least two stages of oxidation, the first of which can be cured.

Each molecule of ascorbate has two hydrogen atoms that it eagerly gives up to any "free" radical, which may be one that is only temporarilly free due to ionization. I'm talking over my head here to some extent. Each gram of ascorbic acid is capable of reducing about enough silver halide to make enough silver to make an average density of 1 on 38 rolls of film or 8 X 10 sheets. I think I'm repeating myself.

Anyway, I have nothing against trying whatever pleases your heart. Just do it in a logical manner, with comparisons to whatever the concoction is supposed to be better than. You now have available a means of making sulfite-free developers that will last long enough in working solutions to do a test. If you want to see the effects of sulfite, start at zero and add a very small amount at a time until you get what you want, compared to Rodinal or D-76 or any other that you can buy or for which you have the formula.

 

I know that a sulfite-free PQ developer will develop film. So does Nicholas "Jacko" Twist. It doesn't look like the results of any other PQ developer. Substituting ascorbate for hydroquinone does give results that, superficially t least, look like others. Adding 1/2 teaspoon of sulfite to a liter of PQ will make the results look like other PQ developers. Adding that much sulfite to a PC developer has no noticeable effect.

I remember a few years ago the favorite terms of reviewers were "seminal" and "terminal". I would rather be called seminal. Not just because I had 6 kids.

[kelly_flanigan1]

Having a pH measuring device is a usefull too. With pH's above 9.5; superadditive combos work better; were the combined rate is quicker than each component. An added fluke to home brew; is that some brews dont last long; so one's results will vary verus another chaps; due to the developer pooping out. The developing agent ELON is Kodak's trade name for p-Methylaminophenol sulfate; DuPont's trade name is RHODOL; METOL is used by Agfa; and old GAF.

[jorge_oliveira2]

Jordan

 

Again, from Michael G.'s posts:

 

"Borax was used in fine grain developers not only to act as a mild

"activator", but also as an emulsion hardener to prevent swelling.

Boric acid is used in some fixers for the same reason - as a hardener."

[jorge_oliveira2]

Kelly

 

I've seen somewhere that using lower pH in super addictive pairs will increase edge effects due to regeneration of the main agent (P or M) beeing slower and promoting local exaustion.

 

Xtol's pH is 8.2 IIRC.

[peter_svensson]

"If phenidone were oxidized, you would see red or pink. It's oxidation to that point cannot be reversed by hydroquinone or ascorbate. Apparently it has at least two stages of oxidation, the first of which can be cured."

 

Well, I was in the darkroom prinring yesterday, using a tray of phenidone/ascorbic developer right next to a tray of Neutol WA 1+7 (normal dilution), and my observations match your prediction.

 

I used 40 ml of the glycol stock to a liter of water, plus two tablespoons of carbonate, one tablespoon of sodium ascorbate, and half a teaspoon of bromide. In terms of contrast, development speed, D-max and image tone the PA matched the Neutol perfectly, but it lacked the tray-staining oxidation products of the Neutol (presumably from hydroquinone).

 

In my previous attempt at making a paper developer, I used sulfite instead of ascorbate and observed that the developer exhausted quickly - after two hours or so, it didn't reach D-max any more. With ascorbate, the developer slowed down appreciably after three hours or so, but it still had no problem reaching giving a good black at the end of the printing session. I tried adding another half tablespoon of ascorbate to see if things would speed up, but there was no discernible effect. Same with a half a tablespoon of carbonate (Ok, I had no real reason to believe the pH had gone down, I just thought I'd try).

 

So I guess the phenidone was irreversibly oxidized by then. And yes, the solution had an attractive peachy color.

 

It did about 25 sheets of 8.5x11 RC in a liter over five hours (I was taking it easy.) That's not a lot, considering you say:

 

"Each gram of ascorbic acid is capable of reducing about enough silver halide to make enough silver to make an average density of 1 on 38 rolls of film or 8 X 10 sheets."

 

So maybe much of the exhaustion was due to atmospheric oxygen. Maybe I'll try adding some sulfite next time.

[sjmurray]

This is a really great discussion! I've learned a lot. I have a couple question about phenidone. Anybody know how long will it last dissolved in 90% alcohol?

 

Can I literally use auto-store bought antifreeze to dissolve it in instead of technical grade Ethylene or Propylene glycol?

 

Thanks, Steve

[jorge_oliveira2]

Steve

 

As per Patrick's suggestion, I've mixed more than once 2% phenidone with very pure alcohol adding a pinch of hydroquinone, dissolving it and then the phenidone.

 

Since 250cc (I use both for film and paper) always finishes before it wears out, I really do not know how long it lasts, but it's in the few months bracket.

 

I've tried phenidone in PGlicol and it was less active from the beginning (see a recent post by Sandy King in which he found out the same).

 

As a side note: I've mixed 100c phenidone + hydroquinone in very pure alcohol, left it in a partially filled plastic bottle for 3 months, without loss of activity or change of color. Today my paper dev used this stock solution to which I've added benzotriazole for cold blacks. I add carbonate and sulfite at dev time, using spoons.

[patrick_gainer]

Peter,

Yes. I forgot to mention that 0.09 grams of oxygen uses up as much ascorbic acid as those 38 rolls of film. Two molecules of silver bromide use one molecule of ascorbate or ascorbic acid to make two atoms of silver, one molecule of dehydroascorbic acid, and two molecules of HBr. pH goes down. One atom of oxygen oxidizes one molecule of ascorbate or ascorbic acid, making one molecule of water and one molecule of dehydroascorbic acid. It is important to have an excess of ascorbate if you want the developer to last a long time in open tray. The initial speed of the developer will not be much greater with 80:1 or greater ratio of ascorbate to phenidone, but the loss of ascorbate due to oxidation will not cause such a severe loss of activity. Probably, to replenish your tray of print developer, you could add ascorbic acid with enough alkali to restore the pH.

[jorge_oliveira2]

Patrick's posting reminded me of one point I consider important when adding sulfite (be it PA or PQ):

 

Add and dissolve the sulfite first, so oxygen is scavenged before adding the active part.

[peter_svensson]

Ok, so I went out and invested $2 in some Diamond Crystal Kosher Salt, which supposedly has neither silicates nor iodine. I added the equivalent of 8 tsps per liter to the borax-only formula above. Result: no discernible difference (except in taste!).

 

Jorge,

That's very interesting, both about the borax inhibiting grain and about the alcohol. Is that ethyl alcohol you're using? I was unable to find Sandy's post.

 

Nick,

What activator do you use with the staining formula? Mostly asking out of academic interest, since I've promised myself not to use hydroquinone in my experiments.

[jorge_oliveira2]

Peter

 

I'm using absolute ethanol - it's easy and cheap to buy this stuff over here (Brazil). Patrick recommends methanol as sold in gas stations; Patrick, can you elaborate?

 

Sandy's post is on this thread: 'Borax or sodium carbonate in the Gainer Vitamin C developer', second paragraph of his post.

[rowland_mowrey]

Guys;

 

I have not been following this as closely as I should, but I have seen the comments about salt being used for improving grain and carbonate seemingly increasing grain. Here are some tips.

 

Sodium sulfite is a mild silver halide solvent, and as such can improve grain. Sodium chloride is a silver halide solvent too, but is not very effective at low concentrations, as it also precipitates silver to make silver chloride. Therefore, if one were to want to use salt in a manner similar to sodium sulfite, I really am not sure if it would work well at all.

 

In addition, sodium chloride, used in paper developers might act as a restrainer as many paper emulsions are silver chloride or silver chlorobromide. Even bromide can harm such an emulsion at high levels. OTOH, the solvent effects of sodium chloride are higher with paper developers than with film emulsions.

 

The bottom line is that the action of NaCl can be unpredictable. I have seen it do nothing, increase contrast, and fog paper emulsions. With film, I have seen it do nothing or increase contrast IIRC.

 

If you leave out bromide, I have seen such developers cause an interesting effect similar to solarization or the Sabbatier effect. A kind of re-reversal, but this doesn't always happen either. Depends on emulsion and developer.

 

Just some things to look out for passed on to you all in case you see these effects while experimenting.

 

I also recommend using Ethanol rather than Methanol for safety sake. Methanol fumes and liquid are rather nasty in higher concentrations. If I have a choice, I use Ethanol. And, BTW, 95% is just as good as absolute, and a lot less expensive, but don't use denatured alcohol. The denaturing ingredient can cause bad effects in film, I have heard. Don't use rubbing alcohol. That is isopropyl alcohol (IPA). The fumes can make some people quite ill. There are no lingering aftereffects AFAIK. I am one of those affected by IPA. It causes dizziness and flushing of the face along with a pounding headache if I inhale the fumes.

 

For those of you that live in areas with citrus crops, please be aware that borate ion is poisonous to citrus trees.

 

For those using carbonate, here is a thought. Going into a stop bath releases carbon dioxide proportionally to the level of acid in the stop and level of carbonate in the developer and is also a function of the thickness of the gelatin layer. I have actually seen what appears to be grain, but is in fact tiny bubbles in the film due to production of carbon dioxide in the stop bath. In one case, in a deep tank process, the bubbles formed as the film was coming up out of the tank and the decrease in hydrostatic pressure caused the bubbles to enlarge and blister the film. Some films actually had the emulsion layer blown off the support by the bubbles increase in size. The correct hardener level in the film can help eliminate the problem, but it is something I thought you might want to hear about.

 

OTOH, carbonate increases development rate due to higher alkalinity, and therefore might increase grain. Has anyone considered Sodium Hydrogen Phosphate, Sodium Dihdrogen Phosphate, or Trisodium Phosphate? These are higher in activity than carbonate.

 

The approximate series is as follows in alkalinity. Organic Amines, Borates, Sodium bicarbonate, Sodium Carbonate, NaH2PO4, Na2HPO4, Na3PO4, and NaOH. Potassium equivalents are slightly stronger than their sodium analogs. I say approximate because some borates are stronger than bicarb, there are some pretty basic organic amines, etc.

 

Hope this information is of help to you all.

 

Ron Mowrey

[nicholas_t.]

I use an equal amount of Borax and Carbonate in a stock solution. 100mls makes 1ltre of working solution. The formula is simple, 1tsp of each per litre in working solution or 10tsp (3TBS+1tsp) per litre of stock solution. This roughly equal to a standard metaborate solution (pH10) in activity and is safer to mix up than the Borax/Lye version.

[peter_svensson]

Ron,

The issue with carbonate in stop bath is a good point, and I'm surprised no one's asked me before which stop bath I use. Actually I use a water stop, mostly because I use TF-4 fixer, so the grain I get from carbonate wouldn't be due to that.