H&W Control in Glycol/Glycerin

[lamerko]

Hello,
I've been wanting to play with the H&W Control developer for a while now. I have the following formula:

Solution A:
Water - 50.00 ml
Sodium sulfite - 1.00 g
Hydroquinone - 0.16 g
Sodium carbonate - 4.60 g
Phenidone - 1.10 g

Solution B
Water - 50.00 ml
Sodium sulfite - 8.00 g

Add solution A to solution B, then add water to make 132 ml of concentrate.

Expectedly, even so the resulting concentrate would have a short life. Since my tests will take time, I would like to make a more stable concentrate. I understand that glycerin is a good solvent for some ingredients such as carbonate, borax and an unknown amount of sulfite. Also, glycerin has a close to neutral pH, mixing well with glycol.
Can I make a mix of glycerin and glycol to dissolve everything in? The unknown for me is in the sulfite - I can't find anywhere what its limit value for dissolution is. Also, will the glycerin protect against oxidation like the glycol or will it make the whole thing pointless?

 

[Rudeofus]

Glycerine will protect well against oxidation, but it will most likely not dissolve Sodium Carbonate or Sodium Sulfite. It will likely dissolve the Phenidone and most likely also the HQ.

Another issue is the Sodium Carbonate in aqueous solution: over time it will gather Carbon Dioxide from air, and this will convert the carbonate to bicarbonate ---> lower pH. You should think about converting this formula to use potassium salts of carbonate and sulfite, which are much more soluble than their sodium counter parts (c.f. Rodinal).

So here would be my approach:

1. Dissolve the Phenidone and the HQ in either Glycerine, in Propylene Glycol or in Diethylene Glycol. Typical patent literature for such concentrates frequently list the latter as "most preferable", no idea why, but they probably knew their subject. You will have to heat up the solvent to dissolve the devs in reasonable time. This will be your new "Concentrate A"
2. Convert the Sodium Carbonate to equimolar amount of Potassium Carbonate.
3. I have found no reasonable source for Potassium Sulfite, but Potassium Metabisulfite is moderately easy to buy. I have no idea, why this is. You can still get the equivalent of Potassium Sulfite by mixing Potassium Metabisulfite and Potassium Hydroxide.
4. Now make a concentrated aqueous solution of the right amounts of Potassium Metabisulfite, Potassium Hydroxide and Potassium Carbonate, this will be your new "Concentrate B". The more concentrated you make this, the less air will dissolve, and the longer this "new concentrate B " will last.

 

[lamerko]

Thanks for the reply.

I settled on glycerine as it seems like it would be a better solvent than I had thought up to this point. It's really hard to find the information you need about everything, but the English version of Wikipedia says that the solubility of sodium carbonate in glycerol is 98.3 g/100g (155 °C), which is twice that of water - 43.6g/ 100 ml (100 °C). Also, the English version of Wikipedia says that sodium sulfite is soluble in glycerine, but unfortunately no specific values are given. In the Alfa Chemistry data sheet I found the following: Soluble in 1.6 parts water, about 30 parts glycerol; sparingly soluble in alcohol." I have no idea what that means exactly. I don't know if it's related, but in Fisher for sodium metabisulfite it says "Other solubilities: freely soluble in glycerol". Actually, can't I do a partial swap of sulfite with metabisulfite if it's hard to dissolve the whole amount?
Regarding the H&W Control formula - the final concentrate is only one part - A and B are mixed. Or they just want not to put the whole amount of sulfite in the beginning, but only a tiny part. Tomorrow I will go through the local store to buy some glycerine and test how much sulfite it dissolves

 

[mshchem]

I used this stuff 50 years ago when I was in high school. Where in the world did you find the formula

 

[lamerko]

I want to test a bit on microfilm. I came across a small amount of Kodak 1461 and 3461 (ImageLink HQ). Searching for information on the Internet, I came across interesting results with this developer, unknown to me until now. I have everything I need for it, but I really wouldn't expect a good life on the concentrate.

 

[mshchem]

I think that Adox film with their special developer may be similar to H&W Control film and developer.

 

[Alan Johnson]

I used this stuff 50 years ago when I was in high school. Where in the world did you find the formula

<title>Photographic formulas from The Frugal Photographer

web.archive.org

He closed the store last year.

 

[mshchem]

<title>Photographic formulas from The Frugal Photographer

web.archive.org

He closed the store last year.

Thanks for sharing. I remember this stuff favorably

 

[lamerko]

So... I bought 1 kg of glycerin. This is very densely. I tried to dissolve a certain amount of sulfite and carbonate - the carbonate dissolved, but the sulfite very little. I decided to add some propylene glycol to reduce the viscosity - I had no success with the dissolution. I had to add water. With a total amount (glycerin, glycol and water) of 315 ml, I was still unable to completely dissolve 21.4 g of sulfite. The conclusion is that sulfite is mostly insoluble in glycerin and glycol. I saved the strange mixture that resulted - I will try it in 2-3 days. Interestingly, even a small amount of glycerin in water raises the viscosity significantly. Maybe I will make a second attempt, I will dissolve the sulfite in 150 ml of water and the rest in 165 ml of glycerin/glycol. Maybe so mixed, it will be more stable because of the higher viscosity.

 

[Randy Stewart]

In the first posted formula, I cannot identify any reason to prepare a "B" solution of sodium sulfite, particularly as the same chemical is in "A" already. Perhaps this picked up a typo along the way. If you want to prepare divided solutions to preserve the developers and give long storage life. I suggest that you mix everything but the two developing agents in one solution, and isolate the two developers dissolved in a second solution of polyethylene glycol, which will not absorb dissolved oxygen. Use small, glass bottles for storage, not plastic bottles.

 

[lamerko]

It's a pretty old formula. I guess it was a practice in his day to start with a "pinch of sulfite" to protect the developing agents during dissolution. My guess for the two solution procedure is that to dissolve 16g of sulphite in 100ml of water (at a limit of 27g) would take time with agitation which would also dissolve oxygen at the same time. This won't matter at all if I dissolve the Phenidone and Hydroquinone in glycol - then the separate step with the sulfite is pointless.
Yes, there is always the option of leaving the Phenidone/Hydroquinone in a separate PG solution to be added immediately before work. But I was wondering if the sulfite can be dissolved in an anti-oxidation solvent.
Regarding my experience with glycerin - there was probably some kind of reaction and actually my concentrate didn't work well. I guess the super adaptive Phenidone/Hydroquinone combination is broken. Probably something happened with the sulfite - the fragments that cannot be dissolved in the concentrate are partially insoluble even in a working solution (1+15 parts of water). I declare my first attempt a complete failure

PS: I've never seen a film so screwed up in processing. It looks like there is some silver deposit inside the emulsion. I have no explanation. It kind of looks like it's not fixed, even though I soaked it in two different fresh fixes for maybe a total of about 20 min.

 

[koraks]

I cannot identify any reason to prepare a "B" solution of sodium sulfite

Solubility may play a role. Sodium sulfite is moderately soluble in water; the limit is around 27g/100ml at 20C. There's also sodium carbonate, some (surprisingly much) phenidone and a bit (surprisingly little) hydroquinone in sol. A. Combined, it's possible that this won't easily dissolve and/or crystallize out if temperatures drop during winter.

But I was wondering if the sulfite can be dissolved in an anti-oxidation solvent.

Ask Kodak and they might tell you how they came to formulate the original syrupy HC110 and also why it was challenging to manufacture - which is why it's not around anymore!

I guess the super adaptive Phenidone/Hydroquinone combination is broken.

What surprises me most in this formula is that I'd expect the amounts of phenidone and hydroquinone to be swapped. Anyway, it's an oddball developer so who knows it may be as intended. I wonder how much the hydroquinone actually does in there.

It looks like there is some silver deposit inside the emulsion.

Sounds like dichroic fog. Yeah, that's a massive failure alright.

I've never seen a developer concentrate made with glycerin. It's always glycol. Maybe there's a good reason for this.

 

[Rudeofus]

What surprises me most in this formula is that I'd expect the amounts of phenidone and hydroquinone to be swapped. Anyway, it's an oddball developer so who knows it may be as intended. I wonder how much the hydroquinone actually does in there.

If you look at Michael R.'s formulas here on photrio, he used such a combo with 1-2g Phenidone/Dimezone-S and a very low amount of secondary developer. This gave him a very straight H&D curve with very low but controlled contrast, a very big improvement over POTA. H&W control could well follow the same strategy.

 

[Alan Johnson]

At this time March 9 24 there is still some old stock Bluefire HR developer for sale on UK ebay, I believe it is similar to H&W Control. It is sold as 2 powders to be made up to a concentrate of 1L in water. The instructions say:
"Correctly made up concentrate stored in full tightly capped PET or glass bottles, with little or no air space in the neck has a shelf life of two years"
It recommends topping up each bottle with water after use and recalculating the volume required for the next film, etc. so you get to process 65 films with 1L concentrate.
So H&W control is likely similar, the formula is on the former website of the seller of the Bluefire brand products, some say the film was similar to Copex Rapid.
I have had mixed results with Adox CMS20 in H&W Control, some streaking, the Adox/Spur proprietary developers are to be preferred.

 

[koraks]

@Rudeofus thanks for adding this insight; I did think along the lines of POTA, but didn't know much of a benefit would be had by adding anything on top of the phenidone.
I do note that the film he got that nice and straight curve with was TMX, which is pretty straight-lined to begin with (although he got some pretty wild S-curved behavior from it with XTOL). I wonder what happens if you used this on, let's say, x-ray film.

 

[Rudeofus]

@lamerko if you are still looking for a decent concentrate formula and are willing to experiment with alternative routes, then I would suggest this one laid out by Pat Gainer. It basically follows the same trajectory as H&W Control and as Michael R's developers, but uses TEA as solvent together with Phenidone and Ascorbic Acid to do the development work. As you see in one of the first charts: you can fine tune negative contrast by adjusting the amount of Ascorbic Acid in your mix.

If pH of this soup turns out too low or too high, you have a few options: You can dissolve Sodium Metaborate in Propylene Glycol to make something alkaline but non-prone to aerial Carbon Dioxide. I haven't tried it, but you may even be able to premix TEA+Phenidone+Ascorbic together with PG+Metaborate into a single concentrate. If you want to lower pH of the resulting mix, then PG plus Boric Acid would do the trick.

There's a good chance, that with this technique you can make a developer very close to H&W control with two one long lasting concentrates, and with some luck with just one.

 

[lamerko]

This is an interesting task. But first I need to find out if this formula will work for me.
I have collected various microfilms from different manufacturers, and now I am waiting for the Kodak 1461/3461 to arrive. I understand from various posts that H&W Control may work particularly well with these films. So I'll mix it in water first to see if it works at all.
Regarding TEA - for some reason it is prohibited for free sale in Bulgaria. I was able to get 1 liter from a local dealer - haven't opened it yet, but it seems the viscosity isn't that high - maybe it's with an admixture of DEA.

 

[Alan Johnson]

https://www.drugfuture.com/chemdata/Sodium-Sulfite.html#:~:text=Properties%3A%20Efflorescent%20crystals.,glycerol%3B%20sparingly%20sol%20in%20alc.

This site has 1 part sodium sulfite dissolving in 30 parts glycerin, so to dissolve the formula 9 grams would require at least 270 ml glycerin.

 

[Rudeofus]

I was able to get 1 liter from a local dealer - haven't opened it yet, but it seems the viscosity isn't that high - maybe it's with an admixture of DEA.

From what I have read, there are different purity grades of TEA, and some have quite a bit of DEA. Since that liter of "whatever TEA you have now" will go a long way with PC-TEA type developers, and since you can adjust pH with Boric Acid or Sodium Metaborate, you might as well dial in the process with "whatever TEA you have".

 

[Corn_Zhou]

Hi, I calculated the formula to be seperated into two solutions:

Part A
Hydroquinone 0.4g
Phenidone 2.75g
Glycol to 100mL
Part B
Potassium Sulfite 45% 67g
Potassium Carbonate 15g
Distilled Water to 100mL

1+1+50=HW control working solution
*Note I use Potassium salts in B because the solubility problem of Sodium salts, one can just add more water is sodium salt is what he has and opt for a dilution of 1+2+50 or more

Alternatively I found a formula proposed by JayDefhr:
Part A
Phenidone 6g
Ascorbic Acid 1g (2g improves development eveness as I experimented)
Glycol to 100mL

Part B
20% Sodium Carbonate solution

Dilution:1+2+100
It works basically the same as HW control

 

[lamerko]

The alternative formula is interesting - I'll do a comparison between the two.
I imagine that potassium sulfite can improve many things when it comes to concentrates. The problem is that this chemical is absolutely banned in the EU, I guess in many other countries too. Not because it's poisonous or dangerous, but because of regulations regarding drug precursors and explosives. I guess I could mix 10.68g of KOH and 21.18g of potassium metabisulphite in 35.13ml of water, but I'm not sure what would happen - here the KOH comes in at 85% purity and my calculations probably won't be right.

 

[Corn_Zhou]

The alternative formula is interesting - I'll do a comparison between the two.
I imagine that potassium sulfite can improve many things when it comes to concentrates. The problem is that this chemical is absolutely banned in the EU, I guess in many other countries too. Not because it's poisonous or dangerous, but because of regulations regarding drug precursors and explosives. I guess I could mix 10.68g of KOH and 21.18g of potassium metabisulphite in 35.13ml of water, but I'm not sure what would happen - here the KOH comes in at 85% purity and my calculations probably won't be right.

I think in that case you would be better off making a Part B based on Sodium Sulfite and Sodium Carbonate but more dilute, like twice as dilute and use a 1+2+100 dilution.

 

[lamerko]

The drama continues
I made a new concentrate as follows:
In 50 ml of water (deionized), at 50C/122F, I dissolved 9 g of sodium sulfite (limit value 27.0 g/100@20 ml). Then I added the carbonate to the same solution. I dissolved Hydroquinone and Phenidone in 50 ml of glycol. I mixed the two solutions and added water to 132 ml. Everything dissolved, the concentrate looked good. I stored it in a dark glass jar, which I left in a room at a temperature of about 16C.
After only one day, this concentrate began to crystallize. I have no idea why - the amounts of the chemicals are small enough for their limit values...
I decided to test the concentrate anyway despite the crystallization. A little while ago I received Kodak Imagelink HQ Microfilm - I had never worked with one, but as far as I understand, the film is rated around EI 12. I did two tests (on the first one I accidentally opened the film back to the light) at EI 12-25- 50. I got extremely thick negatives (will try to get something out of them). But at least the result is not a complete failure like the previous one. Processing: 18 min at 21C, 30 seconds initially, three turns every minute. Apparently, the processing time was too much (I got it after searching the internet for results). Maybe my stirring is too intense. The next samples will also include EI100...
What should I really expect from Kodak Imagelink HQ? What is its actual speed?

Interestingly, the composition of this developer includes very minimal amounts of chemicals. One liter of working solution contains only:

Sodium sulfite	4,29 g
Hydroquinone	0,08 g
Sodium carbonate	2,19 g
Phenidone	0,52 g

For comparison, there are 30 g of sodium sulfite and 1.5 g of phenidone in POTA. Development times in POTA are 12-14 minutes, but a whole stop is wasted. So I assumed 18 minutes for H&W Control was normal...

 

[Corn_Zhou]

The drama continues
I made a new concentrate as follows:
In 50 ml of water (deionized), at 50C/122F, I dissolved 9 g of sodium sulfite (limit value 27.0 g/100@20 ml). Then I added the carbonate to the same solution. I dissolved Hydroquinone and Phenidone in 50 ml of glycol. I mixed the two solutions and added water to 132 ml. Everything dissolved, the concentrate looked good. I stored it in a dark glass jar, which I left in a room at a temperature of about 16C.
After only one day, this concentrate began to crystallize. I have no idea why - the amounts of the chemicals are small enough for their limit values...
I decided to test the concentrate anyway despite the crystallization. A little while ago I received Kodak Imagelink HQ Microfilm - I had never worked with one, but as far as I understand, the film is rated around EI 12. I did two tests (on the first one I accidentally opened the film back to the light) at EI 12-25- 50. I got extremely thick negatives (will try to get something out of them). But at least the result is not a complete failure like the previous one. Processing: 18 min at 21C, 30 seconds initially, three turns every minute. Apparently, the processing time was too much (I got it after searching the internet for results). Maybe my stirring is too intense. The next samples will also include EI100...
What should I really expect from Kodak Imagelink HQ? What is its actual speed?

Interestingly, the composition of this developer includes very minimal amounts of chemicals. One liter of working solution contains only:

Sodium sulfite	4,29 g
Hydroquinone	0,08 g
Sodium carbonate	2,19 g
Phenidone	0,52 g

For comparison, there are 30 g of sodium sulfite and 1.5 g of phenidone in POTA. Development times in POTA are 12-14 minutes, but a whole stop is wasted. So I assumed 18 minutes for H&W Control was normal...

My personal EI-time combo was ISO 25 and 8:30@20℃ with normal agitation.
As for the solubility issue, you can double the volume by adding more water/glycol and cut the dilution in half which is not too inconvenient due to the very high dilution suggested above.
H&W control had higher working pH than POTA which boosts the activity of the Phenidone-Hydroquinone combo, making it a high-speed, low contrast developer.

 

[cptrios]

I just got some Imagelink HQ myself and decided to try it out with HW Control (following the recipe on the Frugal Photographer as best as I could). Some aspects were promising but, as seems to have happened with lamerko, there was pretty heavy fog. In HC-110, it was perfectly clear!

HW Control on the left, HC-110 in the middle, Caffenol CLCN on the right (none of the actual frames are the same exposure here - just looking at the emulsion):


Anyone have any ideas? I mixed in all distilled water, by the way.