Hi all,

I tumbled to 2 papers from Jacqueline Belloni
Radiation Physics and Chemistry, 67:291

Photography: enhancing sensitivity by silver-halide crystal doping

The paper describe the use of HCO2- (10e-6 Mol / 1 AgBr Mol) to cover holes and increase film sensitivity (by over 5 times)

It is also in nature:

Belloni, J., Tréguer, M., Remita, H. and de Keyzer, R., 1999. Enhanced yield of photoinduced electrons in doped silver halide crystals. Nature 402, pp. 865–867.

I've read the 1st one, pretty interesting. If you cant access these journals, you can email me in

narigas-2006 AT bol DOT com DOT br

(no spaces, just to avoid spam...)

cheers

I've read most all of that.

The methodology was sold to Agfa but never was commercialized.

I have been told that Ms Belloni has taken out a law suit against Kodak over the 2 electron sensitization, but since the Kodak method uses an Osmium salt, I cannot see how she can compare the two.

It is my understanding that there are practical problems preventing the use of her method. At least, Agfa was never able to make it work.

What you have described seems different than what she used. I thought she used formalin which is CH2O. Could you clarify this or is my memory failing? What is the chemical name.

Thanks.

PE

Hi all, I tumbled to 2 papers from Jacqueline Belloni
Radiation Physics and Chemistry, 67:291 Photography:
enhancing sensitivity by silver-halide crystal doping

The paper describe the use of HCO2- (10e-6 Mol / 1 AgBr Mol)
to cover holes and increase film sensitivity (by over 5 times)

It is also in nature: Belloni, J., Tréguer, M., Remita, H. and
de Keyzer, R., 1999. Enhanced yield of photoinduced electrons
in doped silver halide crystals. Nature 402, pp. 865–867.

I've read the 1st one, pretty interesting. If you cant access
these journals, you can email me in narigas-2006 AT bol DOT
com DOT br (no spaces, just to avoid spam...) cheers

Formate ion. "is introduced as Silver formate" (AgHCO2)."
That from Dr. Chapman in an article in Photo Techniques,
Nov/Dec 2001. Good explanation but no methods of
application. Agfa had it and did nothing. I Wonder
who now holds the patents? Dan

Hi PE,

the dopant is HCO2, from that article:

'When the dopant is included in AgBr at the relative concentration of 10−6 mol HCO2−per mol Ag+, the emulsion is completely stable in the dark. When illuminated, its absorbance immediately at the end of a 2 s exposure is five times that of the undoped emulsion where the yield is Φeff=0.2 atom/photon absorbed. Then it increases slowly up to a plateau and after 15 min the absorbance is twice that just after the exposure (Fig. 3) (Belloni et al., 1999). The first step is assigned to the fast hole scavenging by formate during the exposure ( Fig. 2b). In the second step, each formyl radical CO2− resulting from the hole scavenging transfers slowly an additional electron to a silver cation, so doubling the gain (Fig. 2c). This photoinduced bielectronic transfer is strictly proportional to the number of photons absorbed down to the shortest exposure times.'

I think I'll try to put a bit of neutralised formic acid on it, what do yous think?...

Also, sorry to get too late on the matter but I am a novice'...

Many thanks.

Well, as you note, it is silver formate or formic acid.

Either would work, but sodium formate, being slightly alkaline might form silver hydroxide thereby neutralizing the effect. This is, BTW, 2 electron sensitization. The problem is this; why did Agfa not bring it to fruition, and I feel that this may be due to inherent problems.

Kodak had enough problems getting their version to work. It is tough science. I'm sorry but I rememberd it as formalin, but I should have known better because it is obvious that some sort of silver interaction is needed. It is as you say, formic acid.

PE

The 'problem' as I heard it is that the formate ion won't stay put. Usable perhaps for a home emulsion maker, but not for commercial films that have to trickle through a dealer network to the end user.

The methodology was sold to Agfa (...)

See also
US 6,277,549.

... at the relative concentration of
10−6 mol HCO2−per mol Ag+,...

Ten to the minus 6. That is very nearly None at all.
Maybe a few drops of 10% in a liter of solution. How
about soaking a sheet of print paper and see what
happens?

I wouldn't worry about ph at that dilution. Silver
formate may be less soluble than one of the silver
halides thus making conversion an easy matter. Dan

If I wanna try it, Would yous think that i should soak some pure silver in formic acid than applying it to the gelatin or should just add the formic acid straight?

cheers

The formic acid should be added to the salt + gelatin before addition of silver when you make the emulsion. This is the only way to truly incorporate the silver formate into the emulsion.

And, ten to the minus 6 (10^-6) is common for many dopants. That concentration range is used for most dopants, as it is just right for causing the 'effect' desired on the overall grain.

The actual range is usually expressed as 1 * 10^-6 to 8 * 10^6 which gives a 'large' concentration range. If the figure used is incorrect, you can actually supress the effect. So, 10^-6 does not tell the whole story.

For example, I know of a chemical used at 3 - 6 * 10^-6 which varies contrasat, but at 10 * 10^-6 causes a huge speed loss and contrast loss. So, this is *critical* in most cases.

PE

I ran across this a while back, but I was (and am) still learning, so I'm not sure how to use this in my fledgling emulsion recipe. It appears that Kodak tried to add the formate at the end of the proccess, and that it was only effective at higher pBr (which I must assume is the negative log of the concentration of bromine ions?)

See
http://www.freepatentsonline.com/EP1271233.html

Kodak measures pAg or vAg as it is more accurate, and is more indicative of the actual conditions.

In any case, this method did not work out well and was abandoned AFAIK. Kodak uses an Osmate complelx.

PE

This would be just the thing for astro-photography. I currently bake the tech-pan film in a hydrogen atmosphere for 2 days to limit reciprocity failure. Even an emulsion which only lasted a few days would be useful as you would coat plates just prior to use. It sounds like this formate emulsion would be competitive with CCD technology, but much cheaper and MUCH higher resolution.

Regards - Jim Browning

There is a French patent on this that was leased to Agfa by the inventors. It was intended to improve speed IIRC. Jon Eikenberry, the inventor, was a respected Kodak Engineer and did fine emulsion work, but I don't remember if this was ever adopted. All I can say is - try it.

PE