Concentrated D-76, How do I go about making it?

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Hamster

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After moving to a new job in a new city, I am now rebuilding my darkroom. The problem I am having now is I don't have enough room to keep all my chemical, beakers, etc... I share my bathroom/darkroom with two other people! So I must find way to economise on space somehow, and keep things tidy enough to not annoy my housemates.

Now the most sensible thing to do is I would go and buy off the shelf concentrate developer, and mix my fixer from powder, however, I find out to my suprised that store-bought concentrated developer is VERY VERY expensive (a small bottle costs the equavalent to my co-worker's weekly wage!), apprantly due to high import tax in this country. So with D-76 being my usual developer, would any of you here know how to go about making a concentrated solution? Making regular strength D-76 is difficult enough as it takes a long time to dissole all the components, I would assume making concentrate would require a differnt solvent in lieut of water.

Another alternative would be to go with PMK or something like that but since my film supplies are very uncertain (the only BW film regularly available here is "Lucky SHD 100"), I need to use something that is tried and tested, so once again I am stuck with D-76.

Mixing from powder is also difficult, as I also share the kitchen and water here comes out of the tap in a green/orange colour (lots of iron in the pipes), so I must buy bottled water and dilute just prior to use. I rekon I will get the chance to mix chemicals once every two months or so and I developed ~2 rolls a week.

I know that darkroom practitioners have managed to get things done in very adverse conditions, so I am determined to get things going dispite difficulties.

Any suggestion would be appreciated.
 

Nick Zentena

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Instead try making D-23. Mix it up dilute at the time you need it. It's just two chemicals to stock. Sure it's only a 60 year old formula but some times you need to go with the youngins :D No concentrate to keep around. Just the two chemicals. When you need it make up just enough for the one session.
 

srs5694

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You could try Gainer's PC-TEA or PC-Glycol. I don't know of any Web site describing them, but their formulas are given (there was a url link here which no longer exists) among other places. They're both simple to make and highly concentrated.

Whatever you make, given your description of your tap water, I'd definitely use store-bought water!
 

Gerald Koch

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You didn't mention where you are now living. Trying to make even a 2X concentrate would be iffy. First check to see what is available locally. Otherwise, I would suggest mixing something like D-76H from scratch each time you wish to develop film. If you have to mix it in the bathroom. Yes, it's rather a bother but it will be fresh. D-76 lasts about 3 months.
 
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Hamster

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Well I am living now in China. I have check the store bought, locally produced liquid concentrate and also the pre-packaged powder stuff. However, their chemical purity is really questionable (I had bits of rust in one bag, bits of year old newspaper in another), and batch-to-batch consistancy is nearly non-exsistant (more than 20% variation in net weight of the powder content). I have managed to get hold of some reagent grade stuff thru work, but it seems what they consider "Analytical Reagent" here is also questionable (problems with discolouration, moisture, etc... My last two 500g bottles of sodium sulfite had fingernail sized specks of dried paint in it!). I presume this is because stuff like Metol, Hydrolquinone were not produced in large quantities and they sits on shelves for too long.

My previous way to ensure consistant output was to mix large batches, filter and pray, so I end up with a large collection pre-mix stock solution and they take up lots of space.

The only good news is that bottled distilled water is cheap (about 20 US cents/litre) and "A.R." grade chemical is also cheap (approx 1.50 US for 100g bottle of Metol). Stuff that are not so critical like sodium sulfite I can buy from darkroom supplies store for 30 US cents / 500g. They also stock Metol and Hydroquinone, but they package them in clear plastic bags! So they have been sitting in the sun when they really need to be in the dark. Funny enough the F-5 fixer powder that they had were packed in neat light-tight foil package. I really want to know what they were smoking at the factory where they were produced. The fact that they also stock expensive imported stuff confirms my suspicion that I am not the only person with this problem.

I have had good experiances with PMK as I can easily find good chemical for it, however it does not seems to play nice with "lucky film", which account for about 60% of my throughput.

Maybe I should just pre-measure dry chemical powder and store them in film cans, and then make stock solution as required. But then it is time consuming as they need to be added in the right order and then the mixing process on average takes about 10-15 minutes + plus waiting time for the stuff to setttle down to the right temperature. I am sure those of you who had the pleasure knows the agonising wait for the chemical to lose the last few degrees before it gets down to 20*C. That's why I am interested in making liquid concentrate.

Perhaps another possibility is to use an replenishing scheme, so I would have 1 large working solution bottle and 1 replenisher bottle. I tried it with D-76, however my past experiance with doing this had not been great, replenishing 1 Liter bottle is not particularly suitable if I want to maintain a decent consistancy.

I really am running out of ideas, so you gurus here please help me!
 

Gerald Koch

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I suggest the following formula. The development times are the same as for D-76 either FS or diluted. It contains one less ingredient and is therefore a bit easier to make.

D-76H
Distilled water (50°C) ................ 750 ml
Metol ................................. 2.5 g
Sodium sulfite (anhy) ................. 100 g
Borax ................................. 2.0 g
Distilled water to make ............... 1.0 l
 

MichaelBriggs

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Hamster said:
....

They also stock Metol and Hydroquinone, but they package them in clear plastic bags! So they have been sitting in the sun when they really need to be in the dark.
.....


Few photochemicals are light sensitve. (An intensifier with silver nitrate is an example of a light sensitive photochemical.) I haven't tried putting my developers in direct sunlight for many days, but ambient light shouldn't do any harm. The main need for storing developing agents is keep them away from oxygen. Mixed developer will keep a long time in full glass bottles.

If you can find some quality ingredients, mixing you own isn't hard. I suggest buying largish quantitities of metol and hydroquinone and transfering them to better containers than thin plastic bags that may be permeable to oxygen. If you don't have a scale, you can measure the chemicals by volume, with some loss of accuracy. D-23 only has two ingredients, besides water. D-76H (listed by Gerald), three.
 

Ryuji

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Hamster said:
Perhaps another possibility is to use an replenishing scheme, so I would have 1 large working solution bottle and 1 replenisher bottle. I tried it with D-76, however my past experiance with doing this had not been great, replenishing 1 Liter bottle is not particularly suitable if I want to maintain a decent consistancy.

Which replenishing technique and replenisher formula did you use?

Making concentrated D-76 is very difficult if not impossible. Sulfite solubility limit is not much above, and Metol won't dissolve easily either. Ascorbate based developers, like DS-10 can be made 5x concentrated (to be equivalent of full strength, or 10x concentrated if 1+1 is your usual strength) with necessary modifications, but then DS-10 and SHD-100 are not very good combination.

DS-12 is said to be a good match for Lucky 100 speed film (as well as other films that don't work very well in DS-10), and it can be made 5x concentrate without any modification, and higher with suitable modification.

Either case, if you have to make a concentrated developer, Dimezone S is the best agent to use, with ascorbate or hydroquinone. Metol is hard to use in a concentrated developers. Then you'll have to replace sodium salts with potassium salts, but this often disturbs the pH and requires adjustment, especially in carbonate developers. And potassium salts are more expensive. So for small darkroom users I'd say trying to make a highly concentrated developers may not be worth the effort.
 

Ryuji

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I'd keep developers in dark when not in use. Dry form may not be so significant, but I'd avoid light when developer is in solution (incl. concentrate) form.
 

gainer

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A rather simple developer that you can mix as you need it from only ascorbic acid (vitamin C), sodium carbonate and either metol or phenidone is as follows:

1 liter water.
1 tsp washing soda. (5 grams)
1/2 tsp ascorbic acid powder. (2 grams}
1/8 tsp metol. (0.25 grams)
1 teaspoon = 5 ml. I don't know if that is standard everywhere.
Use it as D-76. For example, HP5+ for 8 minutes at 21 C.

It mixes quickly and should be cheap even if you use high quality chemicals. It is more consistent than you might expect. Make it stronger to use with paper.
 
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Hamster

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Thanks for all the reply.

The replenishing scheme I was using was to replace 30ml D-76 with fresh stock solution per roll from the 3rd roll onwards. I got this advise from a Chinese language darkroom technique book.

A question for Mr. Gainer, where can I find a good source of ascobic acid, I had wanted to experiment with one of your formulars a couple of years back, but I didn't manage because Ascobic acid is quite expensive from Chemical Supply store, 4 US for 25g. The formulae you gave above seems very attractive, can you let me know the Chemical name for "washing soda"? I have to translate these names into Chinese otherwise the chemical suppliers will get it wrong.

I have tried experimenting with D-76H also just prior to my move here, seems to work well at 1:1 dilution as well, but then I am back to my original problem of not enough space as I need to mix 4x 500ml bottle per month.

Many thanks.
 

gainer

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Hamster said:
Thanks for all the reply.

The replenishing scheme I was using was to replace 30ml D-76 with fresh stock solution per roll from the 3rd roll onwards. I got this advise from a Chinese language darkroom technique book.

A question for Mr. Gainer, where can I find a good source of ascobic acid, I had wanted to experiment with one of your formulars a couple of years back, but I didn't manage because Ascobic acid is quite expensive from Chemical Supply store, 4 US for 25g. The formulae you gave above seems very attractive, can you let me know the Chemical name for "washing soda"? I have to translate these names into Chinese otherwise the chemical suppliers will get it wrong.

I have tried experimenting with D-76H also just prior to my move here, seems to work well at 1:1 dilution as well, but then I am back to my original problem of not enough space as I need to mix 4x 500ml bottle per month.

Many thanks.
Ascorbic acid is Vitamin C but not all forms of Vitamin C that you might find at the druggist are ascorbic acid. The Chemistry Store, at www.chemistrystore.com, should have a much better price. Washing soda is sodium carbonate, which is also available at The Chemistry Store. Considering shipping cost, it might be as well if you saved up and got a pound of ascorbic acid and 5 pounds of sodium carbonate all at once. That should last at least a year, and shouldn't cost any more than 30 US + shipping. If you can get erythorbic acid easier or cheaper, it will do the same as ascorbic acid. It is the same as isoascorbic acid, which is the mirror image of ascorbic acid. Your body knows the difference, but the film does not.
 

srs5694

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Hamster said:
A question for Mr. Gainer, where can I find a good source of ascobic acid, I had wanted to experiment with one of your formulars a couple of years back, but I didn't manage because Ascobic acid is quite expensive from Chemical Supply store, 4 US for 25g. The formulae you gave above seems very attractive, can you let me know the Chemical name for "washing soda"? I have to translate these names into Chinese otherwise the chemical suppliers will get it wrong.

I'm not Mr. Gainer, but I do happen to know the answers, so: Ascorbic acid is also known as vitamin C. You may be able to find some vitamin C powder in a pharmacy, supermarket, or health food store (if such things exist near you). Vitamin C tablets might work, but you'd need to crush them, and they'll contain other ingredients that might or might not cause problems in a photographic developer, so it's better to go with a powder if at all possible. Washing soda is sodium carbonate monohydrate, and it's usually referred to as such in formulas. In the US, it's available quite inexpensively as Arm & Hammer Washing Soda, which is sold as a laundry product. Lots of people use that form without problems, but you can get (presumably) purer grades of it from chemical supply houses.
 

srs5694

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Looks like Patrick and I were typing our replies at the same time! One comment: The Chemistry Store is an excellent source of some supplies for US-based customers. Hamster said he was living in China, though, and I suspect the cost of shipping the chemicals from the US (Florida, to be precise) to China would be too great.
 

Gerald Koch

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srs5694 said:
Looks like Patrick and I were typing our replies at the same time! One comment: The Chemistry Store is an excellent source of some supplies for US-based customers. Hamster said he was living in China, though, and I suspect the cost of shipping the chemicals from the US (Florida, to be precise) to China would be too great.
They have moved to South Carolina.
 
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Hamster

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gainer said:
A rather simple developer that you can mix as you need it from only ascorbic acid (vitamin C), sodium carbonate and either metol or phenidone is as follows:

1 liter water.
1 tsp washing soda. (5 grams)
1/2 tsp ascorbic acid powder. (2 grams}
1/8 tsp metol. (0.25 grams)
1 teaspoon = 5 ml. I don't know if that is standard everywhere.
Use it as D-76. For example, HP5+ for 8 minutes at 21 C.

It mixes quickly and should be cheap even if you use high quality chemicals. It is more consistent than you might expect. Make it stronger to use with paper.

I just checked my bags of chemicals and I already had everything I need to mix this up. All I needed is to wait until I get to work next week and have access to the "cocaine scale".

I will experiment in the weeks ahead and I will let you know if this works well with "Lucky film".

I think I will make a 4x concentrated solution to start with, as 0.25g of metol/phenidone is quite difficult to measure out. Also any idea on the solubility limit of Washing Soda? If I remember correctly, I think Vitamin C is very soluable and dissolving a few grams of metol should be no problem.

Many thanks for everyone!
 

Ryuji

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Hamster said:
The replenishing scheme I was using was to replace 30ml D-76 with fresh stock solution per roll from the 3rd roll onwards. I got this advise from a Chinese language darkroom technique book.

That system is the old Kodak recommendation and not very good. If you use one of their new replenishing system (its described in one of Kodak publications, and it's also described on my web site), the result is very consistent.

If you are in China, I wouldn't deal with Chemistrystore or anything like that. Much of ascorbic acid manufactured today, especially cheap ones, are coming from China.
 

Ryuji

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Hamster said:
I think I will make a 4x concentrated solution to start with, as 0.25g of metol/phenidone is quite difficult to measure out. Also any idea on the solubility limit of Washing Soda? If I remember correctly, I think Vitamin C is very soluable and dissolving a few grams of metol should be no problem.

If your intention is to keep the concentrate, I don't recommend that. That developer has very poor keeping property and you are running some risk if you don't mix it fresh immediately before use.
 

gainer

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Concentrated solutions in water do not keep very long, especially if you include the carbonate. If you can find triethanolamine TEA for short), 100 grams of ascorbic acid and 2.5 grams of phenidone will dissolve in hot TEA to make a liter of stock solution. First mix the ascorbic acid with about 100 ml of very hot water. Add the hot TEA to that mixture and then the phenidone. It takes a while to dissolve. You may dilute 1 part of this with 50 parts of water to make a working solution that you may treat as D-76. The stock will last a long time.

If you cannot get TEA but can find propylene glycol, You may make the solution as above with glycol, but it requires adding an alkali to the working solution. 5 grams of sodium carbonate per liter of working solution is one possibility.
 

gainer

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P.S.
By "hot TEA" I meant about 150 F. or 65 C.
 
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Hamster

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Oh bugger, didn't realise that it doesn't keep well, I already had the 4x concentrate mixed up and ready to go by the time I read you posts. I'm too impatient to wait for the "cocaine scale" so I just measured the volume with an 10ml measuring cup, it was so satifying to see the metol fizzes when I put them in. So I'll stay up all night and develope my backlog of film as soon as my housemates wakes up in the morning. let's hope the concentrate will last 6 hours.

Just a quick comment re: Ryuji, Vit C coming out of China.

Yes there is a lot of the stuff coming out of China, but also a lot of industries were foreign owned and they usually sign agreement with the government where they were charged a lower tax rate for import of raw materials and pays no VAT if the majority of their products were to be exported. If they were to sell to the local china market, they will be taxed and VAT and the trouble associated with it make it not worthwhile to sell in China market, and in any casem Chinese consumer were too price sensitive to buy "export standard" stuff even if duty and VAT factors were not included.

This is why if you come to China, you will fina a lot of the "better quality" Made in China "for export" stuff you find back home actually not available for retail in China at all.

So in the case of vitamin c powder and other chemicals, I can find only stuff produced by the state-run pharmacutiacal/chemical concerns, but the "cheap" made in China stuff that you can buy in shops outside china are not actually available in China! Quite ironic really.
 

dancqu

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Hamster said:
"Lucky SHD 100" ...
Any suggestion would be appreciated.

That film should do well in FX-1 and or Beutler's.
Those two are similar to Rodinal and a few other high
acutance developers on the market. Also they are
similar to Ansco 120/Beer's A print developers.
Or, compound the 120 and use as a lower
sulfite-carbonate film and
paper developer.

All you need is metol, sulfite and carbonate. You'll
have a fine film developer and a fine print developer
all in the same bottle or bottles. Keep your stock or
concentrates in small bottles equipped with
caps which stay snug.

I suggest a 1/4 gram metol and 1 gram each sulfite
and carbonate per roll. For fixer, sodium thiosulfate will
do nicely. Four chemicals and you are up and running
with respected developers for film and paper. Dan
 
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Hamster

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Just to let everyone know that I have had some good results with Mr. Gainer's formular, works kind of like D-23, I trial it on FOMAPAN PRO 100 and ILFORD PAN F. At 21*C, I added 10% more time for the "box" D-76 value, but I only did 3 rolls and my darkroom is very basic, so don't take my word for it. Next thing to do is to try it on Lucky Film.

Also I just ready Ruyuji's website, maybe I should try adding half a tab asprin and see how well this concentrate will keep.

Think I will try Dan's suggest too, something that works well with Lucky SHD 100 would be very interesting for my needs.

Manythanks for everyon for this very informative discussion, I have solved my problem and I very much appreciated you help.
 

Ryuji

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Hamster said:
Also I just ready Ryuji's website, maybe I should try adding half a tab asprin and see how well this concentrate will keep.

I'm afraid that aspirin is acetylated form of salicylic acid, and it is not effective for your purpose. Also, adding something to an existing developer may disturb the pH, and this can have a quite sizable effect on your developing time and image quality. When I design a new developer, I do some calculation first, but at some point down the road I always have to do cut and try with a pH meter and reduction potential meter. Then actual film strip test.
 
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