Highly concentrated stock developer solutions from powder?

MattKing · Dec 7, 2014

I've been thinking about what is available "off the shelf" in the world of developers, and started wondering about one possibility - is there any way to make a pre-packaged powder print developer that one could mix up into a highly concentrated (something like 1+7 or 1+19) stock solution, a litre at a time.

First some background.

I, like many others, have limited storage and working space, and do darkroom work in batches.

I do not have any space available to dedicate to storage of quantities of chemicals, and with the space available I really don't forsee being able to mix up my own from scratch.

As I am in Canada, it can also be more difficult to get many things shipped, although in my case I can have some things shipped to a US address.

I am quite comfortable with mixing up chemicals from pre-packaged powders.

My favourite working volume is two litres at a time.

Right now, I am using Kodak PolyMax T as my print developer, but its continuing availability is uncertain, and shipping to Canada is prohibitive. When I cannot reliably get it any more, I expect that I would look either to Liquidol or 130 Paper Developer, but Liquidol has the same or similar shipping challenges, and my preference for mixing up 2 litres at a time means that I'm forced to either pay a lot for many small packages of the 130 or mix up up a large quantity of the stock solution at a time (I don't really have the space).

A perfect solution would be a package of powder that is easy to mix to a litre of concentrated stock that might give me 4 - 10 printing sessions.

It might be possible for me to obtain something like TEA in 1 litre quantities, if mixing powders into that might solve the problem.

I could forsee this being useful with film developers and fixers too.

Ian Grant · Dec 7, 2014

For best keeping properties you can make up a concentrated 2 part developer. That may be possible with a commercial print developer packaged in 2 parts.

However all the major companies use a combination of Carbonate & Hydroxide in their concentrated liquid print developers, this allows a higher concentration than would be possible with Potassium Carbonate alone. Potassium salts are used in preference to Sodium where higher concentrations are required as they have greater solubility.

Ian

Gerald C Koch · Dec 7, 2014

I have used the following developer almost exclusively for the past few years. The keeping properties are remarkable. I have one un-opened bottle that is over 7 years old and shows no signs of oxidation. Even an opened bottle will keep for months. The concentrate contains the phenolates of both Metol and hydroquinone and in this respect is similar to Rodinal in concept.

Kalogen*

Distilled water (50°C) ……………………………………………… 750 ml
Metol …………………………………………………………………………………………… 12.5 g
Sodium sulfite (anhy) ………………………………………………… 150 g
Potassium bromide …………………………………………………………… 7.5 g
Benzotriazole, 1% …………………………………………………………… 50.0 ml
Hydroquinone ………………………………………………………………………… 45.0 g
Sodium hydroxide …………………………………………………………… 22.5 g
Distilled water to make …………………………………………… 1.0 l

Method of Preparation

Weight out the Metol and sodium sulfite. Dissolve a pinch of the sulfite in the water before adding the Metol. When the Metol is dissolved add the rest of the sodium sulfite and the other ingredients in the ordergiven. A precipitate will form with the addition of the hydroquinone. This is to be expected and it will dissolve with the addition of the sodium hydroxide. Transfer the solution to a 1 liter glass bottle, stopper and allow it to stand for
4 to 5 days. During this time a small amount of impurities will precipitate out and the solution will become lighter in color. Filter the solution and transfer it to several 4 to 8 ounce glass bottles and label. When prepared correctly the solution will be clear with a light pinkish tan color.

Storage

Stored in full, tightly capped bottles, the stock solution will keep indefinitely at room temperature. Partially filled bottles should remain good for at least a year. Should any crystals form due to storage at low temperature, they may be redissolved by warming and shaking the bottle.

Usage

For films

The concentrate is diluted 1+49 to 1+99. Average development times are 6 to 11 minutes @20C for the 1+49 dilution and ~14 for the1+99 dilution.

For Papers

The concentrate is diluted 1+11 to 1+15 with water. Development time is 1½ to 3 minutes at 20° C. The developer produces pure black tones with most neutral tone papers. Image tone may be adjusted by varying the amounts of potassium bromide and benzotriazole.

* Modified extensively from the original and copyrighted as part of a larger work by myself.

NedL · Dec 7, 2014

Matt, I take it you dump the used print developer after each session? So the goal is to only store a concentrated one liter bottle between sessions, and you use 2 liters when you print.

The only idea I have is expensive: a liter bottle of hc-110. I've only tried it a couple times but it made nice prints. I think it was 1:30 with a little washing soda thrown in -- I found the recipe here on APUG somewhere. So a liter bottle would supply you for 15 print sessions. Not a very practical idea.

Edit: Jerry's recipe is a better idea, gives you a liter of real paper developer concentrate and 6-8 print sessions.

hdeyong · Dec 7, 2014

I don't know about the paper, but I agree on the HC-110 for film. Extremely concentrated, (I use it 1-49), very good results, infinite shelf life and cheap when you figure out cost/roll.
One 1L bottle on your shelf, takes up little space.

MattKing · Dec 7, 2014

hdeyong said:
I don't know about the paper, but I agree on the HC-110 for film. Extremely concentrated, (I use it 1-49), very good results, infinite shelf life and cheap when you figure out cost/roll.
One 1L bottle on your shelf, takes up little space.

HC-110 is a great solution, but only for those who have local sources, or can deal with the fact that many of the online sources that used to ship the 16 ounce bottles to Canada will not ship the new 1 litre bottles to Canada.

Speaking more generally, lots of people have made good suggestions, but they don't really adress the parts of the problem that I and many others like me face. Gerald Koch's solution would be perfect if it was practical for me to mix my own. It is not, so I cannot use his solution.

I don't lack work arounds. What I was wondering though was whether there could be a pre-packaged solution that would meet the needs of all of us who are space challenged, unable to mix from scratch, and have difficulty getting some things shipped.

NedL · Dec 8, 2014

I realized after I replied that you were looking for a pre-mixed powder, sorry about that.

I use LPD, perhaps most known for how long it lasts ( in both stock and working strength solution ) and high capacity. It comes in a little can containing powder to make one gallon. I recall -but you'd need to research and make sure this is correct- that the liquid version they sell is twice as concentrated. That might mean that you could mix up a 2 liter batch from a singe can. So if you could use a 2 liter bottle instead of a 1 liter bottle, it might be possible to make it that concentrated. ( I'm also assuming the liquid version Ethol sells is dissolved in water, which might not be true! )

I really don't think this is a great idea though: you'd use 400ml to make 2 liters of working developer, so you'd only get 5 print sessions, and it seems like an incredible waste to use 2 liters of LPD for only one print session. The capacity of those 2 liters is over 100 8x10 prints! This is not the way LPD is designed to be used... it's meant to be kept between printing sessions and re-used, which does not suit your purpose at all. After typing all that I think all I've done is given you something to cross off the list

Gerald C Koch · Dec 8, 2014

NedL said:
Jerry's recipe is a better idea, gives you a liter of real paper developer concentrate and 6-8 print sessions.

I forgot to add that when diluted 1+11 the composition of the working solution is very close to that of D-72 diluted 1+2. You can use this figure to calculate the number of prints per liter of solution.

Gerald C Koch · Dec 8, 2014

The stumbling block here is not being able to mix one's own solutions. There are two Ryuji paper developers that use ascorbic acid rather than hydroquinone. If you mix them just before use you can leave out the chelating agnets. The only unusual ingredient would then be the developing agent Dimezone. All the rest; sodium sulfite, sodium carbonate, and potassium bromide should be easy to obtain. I have bought Dimezone from chemtechinc which from another post will ship to Canada.

Another possibility would be to use prepackaged D-76 and just add sodium carbonate (washing soda from the laundry aisle at the supermarket) before use. By increasing the pH of the working solution a film developer can be converted into a paper developer.

Neal · Dec 8, 2014

Dear Matt,

Dektol. It's cheap. It lasts essentially forever unopened. You only need room for 3 1L bottles after you've tossed the first nights dilution.

Good luck in your quest,

Neal Wydra

MattKing · Dec 8, 2014

Neal said:
Dear Matt,

Dektol. It's cheap. It lasts essentially forever unopened. You only need room for 3 1L bottles after you've tossed the first nights dilution.

Good luck in your quest,

Neal Wydra

And it would be even better if it came packaged as, for example, an envelope containing 10 individual packets, with each packet containing enough powder to make up 700 ml of stock Dektol (yielding 2.1 litres of working strength at 1+2 dilution).

So maybe my request is really about nothing more than packaging.

Neal · Dec 9, 2014

Dear Matt,

Dektol stock solution will last for many months in fully topped up bottles. Admittedly, I only mix chemicals with distilled water, but I find Dektol just keeps going. It is not my normal developer so it sits for a long time between uses and even the working dilution has never failed me. Occasionally I have to add a little stock solution to perk it up but the stuff just keeps going.

Neal Wydra

adelorenzo · Dec 9, 2014

I was given an old Ansco developing kit that came with a tea-bag sized packet of developer. Too bad it was only about 50 years old.

I did notice that Photographer's Formulary sells their various developers in kits that make 1 L of stock including their Dektol version. Maybe try their version of 130 developer? Beau Photo can probably bring them in if you ask. The also carry HC-110 BTW.

MattKing · Dec 9, 2014

HC-110 I can get locally. Polymax-T or Liquidol or any of the other highly concentrated liquid solutions are a problem.

Because of my proximity to both local and US sources, I have lots of work arounds that I can access. But lots of people don't.

The purpose of this thread was more to suggest something that would fill what I perceive to be a market need (as well as expand my options) than it was to solve my immediate problems. But I appreciate everyone's input.

Photo Engineer · Dec 9, 2014

Gerald C Koch said:
I forgot to add that when diluted 1+11 the composition of the working solution is very close to that of D-72 diluted 1+2. You can use this figure to calculate the number of prints per liter of solution.

Gerry, this developer uses NaOH and benzotriazole and therefore I would not ascribe to it any resemblance to D-72 in working properties including tone, capacity, curve shape and etc. I hate to be a purist.

Usually, to approach a paper developer, you need to stay at a dilution of about 1:9, but I have been working on a 1:19 paper developer and a film developer. It does take more or less exotic ingredients though.

PE

Gerald C Koch · Dec 9, 2014

Photo Engineer said:
Gerry, this developer uses NaOH and benzotriazole and therefore I would not ascribe to it any resemblance to D-72 in working properties including tone, capacity, curve shape and etc. I hate to be a purist.

Usually, to approach a paper developer, you need to stay at a dilution of about 1:9, but I have been working on a 1:19 paper developer and a film developer. It does take more or less exotic ingredients though.

PE

I should have been a bit clearer what I meant was the amounts of Metol and hydroquinone in the working solution are very similar to D-72. This would determine the print capacity. It is not uncommon to add either sodium or potassium hydroxide to carbonate based print developers to enable a more concentrated solution. Both Ilford and Kodak have done this. Benzotrizole was added to insure a neutral black tone with the papers that I use. This is sometimes necessary even with D-72 since MQ developers sometimes produce an olive tone with some papers. However, I have used this developer for several years both for film and paper. I have always be happy with the results with both media and have entered prints in several shows. Had I any reservations as to the formulation I would not have posted the formula. But further testing with the aid of a densitomer would have been desireable.

The amount of sodium hydroxide was calculated to just convert both developing agents to their phenolates without having any excess hydroxide. Very similar in this respect to Rodinal.

BTW, I don't know if anyone has mentioned it but Agfa recommended the use of Rodinal as a print developer. So this is another option besides HC-110.

Comparison of Kalogen 1+11 with Kodak D-72 1+2

Kalogen D-72
--------- --------
Metol ………………………………… 1.04 g 1.0 g
Sodium sulfite (anhy) ……… 12.5 g 15.0 g
Hydroquinone …………………… 3.75 g 4.0 g
Potassium bromide …………… 0.625 g 0.67 g

nworth · Dec 9, 2014

Liquidol is another possibility. It is an excellent cold tone developer with excellent keeping properties. It may not be as concentrated as you would like, but the stock solution is more concentrated than the usual developers you find. It is also more expensive than mixing your own.

Making very concentrated print developers is difficult because of the high concentration of sodium carbonate required. The Kalogen formula uses sodium hydroxide to get around that problem. You can also substitute potassium carbonate, which is more soluble, for sodium carbonate to make a somewhat more concentrated stock solution.

NedL · Dec 9, 2014

I thought to myself, "What's APUG for if not for things like this?". Seems like with a worldwide network of photographers, we ought to be able to organize shipping, etc... But then I went to the USPS website to look into international shipping. The prices aren't bad but there are pages of regulations including "no toxic materials" and "no hazardous materials" without specifics of what is included in those categories. After reading all that I'd be afraid of getting into some kind of trouble if I shipped a bottle of liquidol to Matt! Which seems absurd on the face of it, but maybe that's why companies are scaling back on what they will ship.

cliveh · Dec 9, 2014

http://www.ilfordphoto.com/products/product.asp?n=38

MattKing · Dec 9, 2014

cliveh said:
http://www.ilfordphoto.com/products/product.asp?n=38

Ilford Multigrade developer is great. But for those of us who don't have a local source, the reality is if you decide to buy one 500ml bottle from B&H for $7.99, you are also faced with:

Gerald C Koch · Dec 9, 2014

Michael R 1974 said:
Jerry, have you experimented with throughput/capacity, consistency, and tray life of Kalogen vs D-72? I would have expected a print developer using a hydroxide alkali to be relatively weakly buffered vs standard print developers typically loaded with carbonate.

I lack a working densitometer so wasn't able to make those evaluations. I personally do not overwork a print developer. But visual inspection indicated a capacity of 20 - 30 8x10 prints per liter. As I mentioned I have used this developer to make display prints without any problems

In actuality a developer like Kalogen or Rodinal does have some buffer capacity. The phenol derived developing agents are weak acids in their reaction.

A bit of background. The formula I posted is partially based on one proposed by Paul L Anderson in 1914 as a replacement for Rodinal which was not obtainable during WWI. The formula also appears in Anderson's book The Technique of Pictorial Photography. Anderson was a prominent photographer of the time but not very good at chemistry. I reformulated the developer to improve its keeping qualities by adjusting the sodium hydroxide concentration to a scientifically based amount. Other adjustments were to the ratio of Metol to hydroquinone, bromide content and the addition of benzotriazole. I did keep the original name for lack of a better one. A similar developer appears in the Focal Encyclopedia of Photography. So a concentrated MQ developer like this has a long history. They are always described as universal developers for both films and papers.

Doremus Scudder · Dec 10, 2014

MattKing said:
Ilford Multigrade developer is great. But for those of us who don't have a local source, the reality is if you decide to buy one 500ml bottle from B&H for $7.99, you are also faced with:

Matt,

Have you tried ordering from West Coast sources, such as Freestyle? I don't know about their policies about shipping the B.C., but they're a heck of a lot closer and the shipping will be commensurately less. There must be sources in Seattle as well. FWIW, shipping costs for me (Oregon) from Photographer's Formulary in Montana are roughly equal to what you post from B&H. Shipping costs are really skyrocketing.

Best,

Doremus

Gerald C Koch · Dec 10, 2014

Michael R 1974 said:
Thanks for the extra information. To go back to your earlier post in which you noted at one time Agfa recommended using Rodinal as a print developer, do you recall what the recommended dilution was?

I couldn't find a direct quote from Agfa literature but a search of the web gives the dilution most stated as 1:10 which I assume is 1+9.

MattKing · Dec 10, 2014

Doremus Scudder said:
Matt,

Have you tried ordering from West Coast sources, such as Freestyle? I don't know about their policies about shipping the B.C., but they're a heck of a lot closer and the shipping will be commensurately less. There must be sources in Seattle as well. FWIW, shipping costs for me (Oregon) from Photographer's Formulary in Montana are roughly equal to what you post from B&H. Shipping costs are really skyrocketing.

Best,

Doremus

Doremus:

As I've mentioned, I have lots of work arounds available to me, because I have unusual access to US sources (I live just blocks away from a border crossing) and I also have local sources for some options. But those options are not available to a lot of people.

Something like Gerald Koch's Kalogen, in a ready to mix powder, would be wonderful for them.

Will S · Dec 11, 2014

So, I'm probably missing something here, but why not just mix before printing? I do that with amidol and it takes roughly three minutes as opposed to maybe 1 minute for something like ansco 120 or ilford warmtone. Yea, it has 3 or four dry chemicals to mix, but everything is done at room temperature. I used to make up a couple of gallons of ansco 120 and it would last a good while too. For film, rodinal or pyrocat-hd in glycol keep a really long time.

Thanks, Will

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