Which Halogen?

[Nomad]

Some progress has been made. I sensitised the two plates this evening, and it became clear that the albumen coating was pretty uneven. I think the conversion to Silver Iodide helped make this more obvious - the albumen mix on its own was very transparent and differences in the coating didn't show very well compared to the more milky look after sensitising.

I decided to try a contact print anyway. One plate was loaded into the camera, and the other was exposed under the UV lamp for 5 minutes, using a 5x4 negative, emulsion to emulsion. Another plate was placed on top to hold it down.

Here's a scan of the negative...

And the image inverted...

And here's the plate that resulted...

The negative was placed towards the right-hand side, so the dark stuff to the left is fogging from the lamp, through one layer of glass. This was a latent image. As with the wet test after making the albumen mix, the bits looked quite dark under the UV lamp, but still had the pale yellow colour when the room light was switched on for a moment after the UV exposure. Definitely no printing out.

The plate was developed in the Gallic Acid for about half an hour, with not much agitation (I got bored swishing it about after 10 minutes or so, and saw that the fogged area was starting to darken, so went for a break).

The photo of the plate was done using an LED lightbox and a cellphone. The only tweak was to adjust the colour balance (the white areas came out quite blue in the phone). Nothing else other than resizing.

Here's a crop of the more legible area of the image, with some adjustment of levels...

...and a 100% crop with no tweaking of the cellphone image to get a better look at the blotches...

Opinions on the blotches would be appreciated. Dust?

At first, I didn't see the image - I thought it was just the fogged area and some indistinct darkening under the negative. I was planning to clean it all off some time later to reuse the plate, so I was really pleased when I held it up to a better light and could see the outline of the horizon and the lines of hedges at the field boundaries.

I'll hopefully get a chance to expose the second plate tomorrow using the camera. I'm thinking of an exposure time of around 30-60 minutes.

 

[Photo Engineer]

Did you filter all materials using a fine mesh gold coffee filter? If not, dust and "bubbles" of material may remain in the material when coated.

Then too, you have discovered how difficult it is to coat these materials and get a uniform coating.

PE

 

[Nomad]

No, I don't have one of those - I'll look out for one. The blotches were evident on the albumen before sensitising. I did try filtering it through a filter paper, but it was desperately slow, so I ended up using a couple of layers of muslin, which was probably too open (went through very quickly), and may well have added some particles of its own. Just after coating, while they were still wet, I noticed some dust had landed on them. When I coat another plate, I'll cover it while it dries to see if there's anything in the liquid.

 

[nmp]

How did you sensitize - using brush or rod? I am wondering if there were any stray droplets of silver nitrate that formed little cores of silver halide.

 

[Nomad]

They were sensitised by immersing in a bath for about one minute. Gentle rocking motion, then lifted out a put into a bath of plain water (tap water). As I mentioned earlier, the blotches were visible on the albumen before sensitising (although I dare say more could might have been added later).

 

[NedL]

Very cool that you got ANYTHING on your first try. That's excellent!

This kind of latent image development usually needs some aceto-nitrate of silver added to the gallic acid, like mentioned in the instructions you linked to.

If you have an eyedropper, you can add a little at a time ( like 1/2 ml or even less ), then let the plate develop for 5 or 10 minutes, see if the image is intensifying, then add a little more if it's going too slowly. I think the only way to know for sure what a good plate looks like will be when you try to print them, but I think with some experience you will figure out how fast the image should appear and how dense it needs to be at the end to produce a plate that will print well.

Can't wait to see more!

 

[nmp]

So you did end up doing "dunk" sensitization. I was trying to figure out why almost all of the botches are darker - meaning they probably had higher level of silver halide - than the rest of the area.

Not bad for a first try on a brand new process, by the way.

 

[Nomad]

Ned, is the idea of adding aceto-nitrate of silver to alter the developer to match the plates being developed, or is it something that needs to be done with each plate, even if the developer is being reused? (In other words, does the additive deplete?)

Just developed plate 2. This was exposed in the camera for 45 minutes at the fixed stop of f/22. Early evening, quite sunny, weather web site said UV index was 1, which is pretty low. Here's the plate on the lightbox...

Not much to see, and I thought I had nothing while peering at it under safelight, until I saw the diagonal delineating a difference in density which wasn't related to my uneven coating. That's a roof line. (The perspective is receding to the left.) Positive image...

It's probably difficult to see what's going on here, although easier for me because I know what the subject looks like. If you look in the area where the digit 2 is written, there's a lighter feature down and left of it. This is a window frame. Here's a crop of this area with some enhancement...

The window frame is quite clear, now. Also, in the dark roof occupying most of the upper half, it's possible to make out some horizontal linear features which are the lines of tiles on the roof.

The development process for this was the same as before - half an hour, with some swishing about for 10 minutes or so before being left. This plate is a bit thinner than the contact printed one, which suggests that I would perhaps need more exposure in that particular light to match that achieved using the UV lamp. (I'm hoping to be able to use the lamp as a way of characterising the sensitivity such that I have a guide for my exposure estimates with the camera.)

I clearly need to work on the coating technique - it's very uneven. Next time, I think I'll pour more albumen on and try tilting the plate to let it drain. I'm still not sure if the stuff is viscous enough. The better-exposed parts of both plates were where the albumen was thickest, and I'm wondering if letting the plates drain will result in an overall thin coating. I'll try it and see how it goes.

The other thing to do is try to track down what's causing the blotches. Since I suspect it's dust that's settling on the albumen before it's sensitised, I'll see what I can do to mitigate that, perhaps with some sort of cover.

On the plus side, the basic proportions in the mixtures seem to work, and my guesses for exposure weren't too far off (close enough to have an empirical reference to work from). Both plates are very thin, so I need to gradually work towards getting better density. I think the first step with this is to see if the coating is also thicker as well as more even. If it is, then I should get an improvement in density, or at least get the better density that I have so far over more of the plate.

These are probably technically the worst photos I've ever made, but they are rather satisfying nonetheless.

 

[Photo Engineer]

The major problem is coating quality.

PE

 

[NedL]

Oh definitely a result. No trouble seeing that something is there, even in the first one.

At least with calotypes - the kind that are washed after sensitizing, like you did here - the aceto-nitrate of silver causes "physical development" of the negative and it supplies most of the silver for the dark areas on the negative. My calotypes don't really start to develop until I add a little AN. The amount added controls how fast development takes place. I like to aim for about 30 or 40 minutes, and I usually start with about 1/2 ml of AN and then wait 5 or 10 minutes to get a sense of how much more needs to be added. Then, normally I'll add another 1/2 ml, but sometimes it needs more or less depending on how fast the image is coming up. As long as the gallic acid doesn't decompose ( and you'll know.. a thin black residue will start to show on the plate and in your tray ), there's no need to hurry the process. Better to add the AN a little at a time and keep everything under control. But usually the image starts to show pretty quickly after adding the AN. My guess is that you will be surprised how much stronger your plate negative is after you try it. You might - possibly - even find that you're overexposing.

FWIW, and I have no idea if this is right for albumen plates, I use 1.4g gallic acid in 200 ml DH20, and the AN of silver is: 6% AgNO3 and 9% acetic acid. I didn't compare these with the article you linked, so I'm not sure how similar they are. I use all of it 1-shot. I don't think the gallic acid solution will store very well.

Alan Greene recommends having two waste streams: one for silver nitrate waste, including gallic acid used for development. The second for fixer waste. There could be a chance of creating SO2 otherwise, I don't know how likely that is but I keep them in separate waste jugs for this reason. Also, at least with calotypes, a pinch of alkali sodium carbonate in the hypo can prevent SO2 forming if acid is carried over from development. I got a small whiff of rotten egg ( hydrogen sulfide? ) one time, and after that I started adding a pinch of washing soda and haven't ever smelled it again.

Wow. Keep going!

 

[NedL]

Just looked at "practical photography on glass and paper", and he's using a stronger AN solution, about 9% AgNO3 and 20% acetic acid, but the process is also different... he mixes it together in equal parts with gallic acid, and pours it over the plate... then dunks the plate in water when the image has intensified enough. That sounds a bit tricky to me. I'd be tempted to try adding the AN a little at a time ( agitating the tray ) and approach the final density more slowly!

 

[Nomad]

I think I'd rather go with the weaker solution and add it in small amounts (I'll make up a little bottle to try it). I'm not really into something that's fast and needs to be arrested, especially if the judgement on density needs to be made quickly under safelight. Noted on the sign of Gallic Acid going off. I'm reusing at present, so, if adding AN makes a difference to the next plate(s), I'll see how it then fares with the one(s) after that regarding whether it needs replenished with more AN (AgAN?)

No rotten egg smell so far - I wash the developed plate in a second dish with gently running water, then into the fixer.

 

[NedL]

Hi Nomad,

Burbank has a whole chapter on this process. He calls the variation you tried Couppier's modification. Also his instructions just use a few drops of silver nitrate solution as an intensifier in the gallic acid ( instead of AN of silver). Interesting reading!

Various instructions for development with gallic acid -- for other processes -- use silver nitrate to speed things up and intensify development and acetic acid to slow things down and keep highlights clean. Aceto-nitrate of silver is a sort of "shortcut" to add both at the same time.

When you read instructions for old processes, it's often possible to try them without using the more hazardous components. For example, elemental iodine was often used as an "indicator". It adds color, and when it has been completely converted during the sensitizing step, it indicates the sensitizing is done because the color is all gone. So it's convenient but not strictly necessary. I think you can manage to clean the plates without hydrochloric acid too. I'm a little skeptical about using gallic acid as a preservative.... if you end up experimenting along those lines, you might try tannic acid instead and see if it improves the keeping of the plates.

I still think I read a description of this process somewhere that had very long development times, replacing the gallic / AgNO3 developer every hour or two over a period of 10 or 12 hours. Not sure where I read that.

 

[cliveh]

On the subject of halogens, has anyone ever made an image using fluorine?

 

[pdeeh]

Fluorine and silver compounds very unstable.
There's a thread somewhere with comments by Gerald Koch describing why you can't.
Read it recently

 

[Photo Engineer]

Using Fluorine is not possible!

PE

 

[NedL]

Gustave Le Gray used potassium fluoride and potassium cyanide in his waxed paper calotypes. I'm pretty sure I remember seeing sodium fluoride as an ingredient in some early calotype instructions as well. Many early calotype "recipes" included small quantities of obscure and often very toxic or dangerous ingredients, mostly of dubious value!

 

[pdeeh]

(there was a url link here which no longer exists)

 

[Photo Engineer]

There are 3 main Fluorides of Silver. None are used in photography for imaging.

PE

 

[Nomad]

Hi Nomad,

Burbank has a whole chapter on this process. He calls the variation you tried Couppier's modification. Also his instructions just use a few drops of silver nitrate solution as an intensifier in the gallic acid ( instead of AN of silver). Interesting reading!

I think the bit about a few drops of AgAN is actually in the next section, about the albumen honey process (no blank line between the two). However, as I alluded in an earlier post, it seems that all sorts of methods will work to some extent. So it might be a fair bet that the 'few drops' idea would still work unless there is some specific interaction that only happens with the honey, or with Potassium Bromide / Sodium Chloride (or some combination of those).

I guess one of the problems with these old texts is that there is no direct comparison between the methods, or much in the way of explanation regarding why particular combinations are used. In typical Victorian gentleman-scientist style, they are usually simply touted as 'the best'. With my rather (okay, very) poor knowledge of chemistry, I'm in no position to work out what the differences might be, so I kinda have to just pick something, see how it goes, report here, learn from the comments, and try to work out what can be done to make improvements and/or changes. If anything, I'm trying to keep things fairly simple, and preferably not too hazardous.

Various instructions for development with gallic acid -- for other processes -- use silver nitrate to speed things up and intensify development and acetic acid to slow things down and keep highlights clean. Aceto-nitrate of silver is a sort of "shortcut" to add both at the same time.

Interesting - like a monobath.

When you read instructions for old processes, it's often possible to try them without using the more hazardous components. For example, elemental iodine was often used as an "indicator". It adds color, and when it has been completely converted during the sensitizing step, it indicates the sensitizing is done because the color is all gone. So it's convenient but not strictly necessary. I think you can manage to clean the plates without hydrochloric acid too. I'm a little skeptical about using gallic acid as a preservative.... if you end up experimenting along those lines, you might try tannic acid instead and see if it improves the keeping of the plates.

I do have some Iodine tincture, which is, apparently, ethanol with roughly equal proportions of Iodine and Potassium Iodide making up about 5%.

The plate cleaning does seem a bit convoluted in the Burbank: soak in caustic potash, then Nitric Acid, wash, a few drops of Hydrochloric Acid and rubbed with cotton dipped in Iodine tincture. It's not clear to me what that's supposed to do that can't be done with something like wash, rinse, and wipe with cotton wetted with IPA. Unless the former chemicals react with the surface of the glass in some way to help adhesion? Maybe dissolve any stray cotton fibres?

I used Sodium Citrate as a preservative when I made the original batch of albumen for prints, and that seems to have worked. I still have the tub in the fridge after about 6 years, and it isn't mouldy or anything, although there is something on the surface now. I haven't opened it yet, on the assumption that it's probably well past its best anyway, and may well be somewhat malodourous.

I still think I read a description of this process somewhere that had very long development times, replacing the gallic / AgNO3 developer every hour or two over a period of 10 or 12 hours. Not sure where I read that.

Aye, way too long. Half an hour or less is much more tolerable.

 

[Nomad]

I'm considering using liquid egg white rather than the albumen powder (now that I've seen it in the local supermarket). It's pretty cheap at £3 for 15 egg whites. The only thing is, it has guar gum added (and nothing else), which is apparently to make it easier to whisk into a foam.

From what I can glean from the Wikipedia article, guar gum is made up of galactose and mannose, is non-ionic, hyrdocolloidal, and loses its viscosity at extreme pH. Am I right in thinking that this stuff shouldn't have an adverse effect on an albumen mix for photographic use?

My thoughts are...

The sugars should be okay if it's okay to add honey, sugar water, etc. If anything, they might help prevent cracking and the like (although I don't know how the addition of other sugars affects the albumen, so can't say whether these would have the same effect).

It doesn't dissolve in water, which I think means it would be in suspension (hydrocolloidal, yes?). I take that to mean that there shouldn't be an adverse effect on the albumen with regard to it dissolving during washing, etc.

If any acetic acid in the sensitiser or developer was concentrated enough to count as extreme pH, a the loss of viscosity at that stage (if it could happen) should be okay because the albumen has already dried.

If anything, there is a possible concern that it might affect the albumen settling back to a liquid after whisking into a foam (I assume it's there to make meringues and the like easier).

Okay to use, or a bad idea?

 

[NedL]

I have no idea. Hopefully someone who makes albumen prints can chime in, I know some of them use powdered or other store-bought albumen.
We have egg-laying ducks, so if I try this it will be with freshly laid eggs. I wish I had time to try it right now.... you've really piqued my interest!

 

[MattKing]

We have egg-laying ducks, so if I try this it will be with freshly laid eggs. I wish I had time to try it right now.... you've really piqued my interest!

I can just see the thread title now:
"For greater success using the _______________ process, you first need a few egg laying ducks".
Even though I don't use any Alternative processes ("Silver Gelatin" being the possible exception") this remains one of my favourite sub-fora.

 

[NedL]

Here is an extract of the albumen negative process instructions from Plain Directions for Obtaining Photographic Pictures Upon Albumenized Paper and Glass... 1855. It is a little difficult to figure out who the author is of the different sections in this book. John Croucher wrote the first section, and the second section indicates that it is "by Gustave Le Gray" but when you read it, it is clearly a summary of waxed calotype methods from Le Gray's writings in French and Le Gray is not the author. In the text, it refers to "The editors". I'm not sure who actually penned the sections on the albumen negative process.

I also left in the section on producing positive albumen prints on paper.

Note development times from "1 to 2 hours", always with some aceto-nitrate of silver added to the gallic acid.

It might be a good idea to change the subject of this post to indicate it is about the Albumen Negative Process on Glass.

 

[Nomad]

To keep this thread broadly on-topic, I have started a new thread dedicated to the albumen process aspects of this discussion, which can be found here...

(there was a url link here which no longer exists)