Hydroxylamine for B&W photography

[Fausto Saporito]

Hello,

In the Encyclopedia of Photography (1974), hydroxylamine hydrochloride is listed as a vigorous developer but unpractical because it releases nitrogen and this destroys the gelatine.

Nevertheless, I did an experiment, using the SP810 tray (almost open tray), with this very simple recipe:

Water 300mL
Hydroxylamine hydrochloride 2g
TEA 20mL
Sodium hydroxide 1,5g
WTM 500mL



The film used is an ortho lith film (Wephota FO5) @ ISO3 developed for 3 mins (20C)

 

[Raghu Kuvempunagar]

Very nice result @Fausto Saporito. Thanks for sharing. Looking at the pic you shared, I assume you observed no damage to the gelatin.

 

[Fausto Saporito]

Very nice result @Fausto Saporito. Thanks for sharing. Looking at the pic you shared, I assume you observed no damage to the gelatin.

Thanks.
Exactly, the negative is without any damage. Maybe it's this kind of lith film, or the tray development because it's not totally close so the nitrogen can disperse. My next test is with a Fomapan with longer development times.

 

[Raghu Kuvempunagar]

Exactly, the negative is without any damage. Maybe it's this kind of lith film, or the tray development because it's not totally close so the nitrogen can disperse. My next test is with a Fomapan with longer development times.

Nitrogen is formed at the site of reduction. So even in a tray, the gas will diffuse through the emulsion. I guess it's the rate of formation of Nitrogen that plays a key role in emulsion damage. Large bursts of gas are more likely to damage than a slow and steady release. Maybe the dilution you are using is mild enough to prevent the formation of large bursts of gas. If I had a chance I would try even milder dilution in a tank. But that would require the working solution to be stable for at least ten minutes. How long does the working solution remain stable?

 

[Fausto Saporito]

Nitrogen is formed at the site of reduction. So even in a tray, the gas will diffuse through the emulsion. I guess it's the rate of formation of Nitrogen that plays a key role in emulsion damage. Large bursts of gas are more likely to damage than a slow and steady release. Maybe the dilution you are using is mild enough to prevent the formation of large bursts of gas. If I had a chance I would try even milder dilution in a tank. But that would require the working solution to be stable for at least ten minutes. How long does the working solution remain stable?

Yes, Raghu, I agree with your idea. I didn't perform yet any tests about stability. I'll do some tests and I'll post the results.

 

[Fausto Saporito]

Some notes about stability: I prepared some concentrate in this way,

Water	300 mL
Hydroxilamine hydrochloride	20 g
TEA	200 mL
Sodium hydroxide	15 g

after 24h in a half-full bottle, I took 50 mL and developed as above. Everything seems ok. As soon as the negative is dry, I will post a scan.
I put too much water in the concentrate but I was not sure about the hydroxylamine solubility. It seems very soluble, so next concentrate will have less water in it.
I couldn't find any reference about solubility in TEA, otherwise, I could skip entirely the water and this should be better for keeping purposes.

 

[Raghu Kuvempunagar]

Some notes about stability: I prepared some concentrate in this way,

after 24h in a half-full bottle, I took 50 mL and developed as above. Everything seems ok. As soon as the negative is dry, I will post a scan.

Good to know that the concentrate is stable for at least a day. TFS. If the working solution, which is much more diluted than the concentrate, is also stable for an hour, it will be very useful. I am quite eager to know your results on Fomapan when you try it.

 

[Fausto Saporito]

Good to know that the concentrate is stable for at least a day. TFS. If the working solution, which is much more diluted than the concentrate, is also stable for an hour, it will be very useful. I am quite eager to know your results on Fomapan when you try it.

Today I will try a stand development, it will be interesting By the way, I am not sure if this developer is suitable for other kinds of films, i.e. non-lith. Maybe a bigger quantity of hydroxylamine and sodium hydroxide, but I would add also some potassium bromide to avoid fog.

 

[Raghu Kuvempunagar]

I am not sure if this developer is suitable for other kinds of films, i.e. non-lith. Maybe a bigger quantity of hydroxylamine and sodium hydroxide, but I would add also some potassium bromide to avoid fog.

Apparently Hydroxylamine is superadditive with Phenidone. A suitable combination might work well for other films without requiring a lot more Hydroxylamine than you used, if you decide to go down that road.

 

[bnxvs]

https://www.gbiosciences.com/image/pdfs/protocol/BC80_protocol.pdf

Hydroxylamine∙HCl is soluble in polar solvents such as water, ethanol, methanol, glycerol and propylene glycol

It seems to me that the easiest way is to dissolve the required amount of hydroxylamine in the glycol and add TEA. There will be a good "base" for further experiments, incl. with the addition of other developing agents. IMHO.

 

[Raghu Kuvempunagar]

Reading Haist I get an impression that Hydroxylamine developers, at least the working solutions, may not be very stable. Haist says "Hydroxylamine is an excellent developing agent at high pH, but it is relatively unstable, especially in the presence of metal ion impurities." Interestingly and somewhat ironically, he mentions an interesting application for Hydroxylamine: "The combination of two developing agents often helps to increase the stability of the developing solution. Hydrazine or hydroxylamine acts as a preservative in color developers where the quantity of sulfite must be kept low. Many of these and other compounds may be used with low levels of sodium sulfite."

 

[Fausto Saporito]

I trie

https://www.gbiosciences.com/image/pdfs/protocol/BC80_protocol.pdf


It seems to me that the easiest way is to dissolve the required amount of hydroxylamine in the glycol and add TEA. There will be a good "base" for further experiments, incl. with the addition of other developing agents. IMHO.

Thanks a lot. It's definitely a good idea. As soon as I finish this batch of "concentrate", I'll do in this way.

 

[Fausto Saporito]

Reading Haist I get an impression that Hydroxylamine developers, at least the working solutions, may not be very stable. Haist says "Hydroxylamine is an excellent developing agent at high pH, but it is relatively unstable, especially in the presence of metal ion impurities." Interestingly and somewhat ironically, he mentions an interesting application for Hydroxylamine: "The combination of two developing agents often helps to increase the stability of the developing solution. Hydrazine or hydroxylamine acts as a preservative in color developers where the quantity of sulfite must be kept low. Many of these and other compounds may be used with low levels of sodium sulfite."

I tried a stand development, for 60 mins using 15mL of concentrate, so it means

Hydroxylamine 0,6g
TEA 6mL
NaOH 0,45g

in 500mL of water.

I agitated only at 30min for 10 secs.
The result is weird, and maybe it's related to the exhausted developer or the impurities in the tap water I used.

This is a mobile photo of the drying negative and because of the "transparency" effect of the FO5 film, is not so easy to see the image. But there is a yellowish/brownish tint that maybe is related to a spent fixer/bath?

Tomorrow I'll post a scan.

Anyway, I will try again with a fresh stop bath and fresh fixer.

 

[Raghu Kuvempunagar]

It would help if you share the pic of the negative that you got with regular agitation, i.e. the one whose scan you shared in the first post.

 

[Fausto Saporito]

It would help if you share the pic of the negative that you got with regular agitation, i.e. the one whose scan you shared in the first post.

This is the scan.
Sorry for the bad quality overall, but I thought it was a totally failed experiment and I didn't put too much care into handling the negative.
There are no filters applied here, no corrections at all. just the simple scan.

There's more fog, IMHO and this can depend on the longer development time I suppose. But comparing the highlights, for example, with the same subject developed with henna, are quite good and not blown-out (i.e. you can see the weather markers on the top of the camera here).

 

[Raghu Kuvempunagar]

T.H. James on Hydroxylamine:

"it yields somewhat lower contrast and lower emulsion speed than the simplest organic agents of its type. It is however, capable of producing relatively fog-free development of good quality. Satisfactory prints can be made on both chloride and bromide papers with hydroxylamine. It is not a practical developer for ordinary bromide film, but only because the nitrogen evolved during development disrupts the gelatin layer. Even this can be avoided by working at pH values of 11 or less, but then the time required for development becomes excessive for ordinary purposes."

 

[Fausto Saporito]

T.H. James on Hydroxylamine:

"it yields somewhat lower contrast and lower emulsion speed than the simplest organic agents of its type. It is however, capable of producing relatively fog-free development of good quality. Satisfactory prints can be made on both chloride and bromide papers with hydroxylamine. It is not a practical developer for ordinary bromide film, but only because the nitrogen evolved during development disrupts the gelatin layer. Even this can be avoided by working at pH values of 11 or less, but then the time required for development becomes excessive for ordinary purposes."

Yes, I think with ordinary films it's not a good or proper choice. But, for my specific target, a lith film which is generally used to copy negatives or create contrast masks, it's quite good to obtain continuous tones.
This is a 4x5 FO5 @ISO3 developed for 15mins in 25mL of concentrate with reduced agitation (10secs every 3 mins).

 

[Raghu Kuvempunagar]

Hydroxylamine (Hydrochloride) makes a potent developer with a little bit of support from p-Aminophenol (super additivity?). This formula gives a developer that develops Orwo UN54 @EI:100 to normal contrast in 8 minutes @20C:

HP-2 Developer
Water: 400ml
Sodium Hydroxide: 2.5g
Hydroxylamine Hydrochloride: 2g
TEA: 1 small TSP
Sodium Sulphite: 5g
p-Aminophenol: 0.1g
Water to make: 500ml

There is no emulsion damage due to Nitrogen released during the development. Agitation was continuous for the first minute and ten seconds every minute there after.

 

[Fausto Saporito]

Thanks for the recipe, that's interesting, I am trying something similar with phenidone, to make a concentrate, but it seems high levels of hydroxylamine and TEA react in a weird way, creating a sort of paste.
Are the above quantities for a working solution, correct?

 

[Raghu Kuvempunagar]

Are the above quantities for a working solution, correct?

Yes, single use working solution. Use immediately after mixing.

I've substituted p-Aminophenol with Metol (0.1g) and Phenidone (0.025g) separately in the above formula and found that they also work fine. It could be a good starting point if you want to explore further as Hydroxylamine is known to be superadditive with Phenidone but the optimal ratio is not known.