Holographs
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Martin
Holographs
I guess the effect of colloidal developers greatly depends on parameters like silver concentration and emulsion hardness. At the time we were testing several developers, the batch of PFG-03M we had was extremely soft. Handling that emulsion became quite challenging. Even most rubber gloves seemed to leave marks on that film. Incidentally, that emulsion was gradually (over a period of several months) converted from a soft into a hard, Agfa-like, emulsion. I later learned this was due to formaldehyde hardening.In the meantime Slavich claimed to have considerably hardened their layer. See e.g. Zacharovas et. al, "Recent Advances in Holographic Materials from Slavich", SPIE 4149, p.78: "PFG-03M - Red Sensitive. (...) In order to attain the maximum performance from this material we have increased the hardness of the emulsion by 3 times. This now permits the holographer to use machine processing and drying without adverse consequences. The sensitivity of the PFG-03M also has been increased."Given those "recent advances", we might well need to re-adapt our developers. Harder layers delay diffusion processes. Hence we might consider higher concentrated developers. If I am not misled GP-3 is the fastest of all the GP series. It is the one with highest amount of ammonium thiocyanate and, the increased quantity of potassium hydroxide makes it the one with the highest pH.
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Martin
Holographs
Sergey, I forgot to address the issue of wavelength shifting. My statement about re-adapting developers equally applies for GP-3. The color shift you reported clearly indicates too much solvent action (e.g. the amount of ammonium thiocyanate has to be reduced). Hence the wavelength shift. I suspect the whole series of colloidal developers will need to be reformulated with the new PFG-03 emulsion.
Thanks for your tests!
Thanks for your tests!
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Sergey Vorobyov
Holographs
It is interesting question - the quantity of thiocyanate in 1 l of work solution of MM Color is 2g:50 = 0,04g and in 1 l of work solution of GP-3 is 45g:30 = 1,5g. To 38 time more! But MM Color work as more active developer (you right). I try study out in this. There are present some exceptive chemicals in MM Color. For example, potassium brom and thiocyanate. First have impede dissolve of AgBr but second special insert in developer for active dissolve of crystals of AgBr.
GP-3 (and GP-2) is classic of physical developer. Main process there - diffusion transfer of atoms of AgBr from nonexposed crystals to exposed crystals when form very small and sphery grains of metal Ag. It is fine process and many cristals of AgBr stay in layer. So, after fix this AgBr go away from layer and thickness of layer will be reduce. The color of imade will be more orange (the wavelenght will be shorter). If nonfix hologram after develop, the color of image will be red.
Zacharovas don't work in "Slavich". He work in "Geola". And I don't know about work of hardening of emulsion PFG-03m although I go to "Slavich" every week. But my experiments show - when emulsion PFG-03 made hard, the DE is reduce. So, main feature of emulsion PFG-03 - this NONHARDNESS emulsion. Only this give good parameters.
I write many english words. Need small rest
GP-3 (and GP-2) is classic of physical developer. Main process there - diffusion transfer of atoms of AgBr from nonexposed crystals to exposed crystals when form very small and sphery grains of metal Ag. It is fine process and many cristals of AgBr stay in layer. So, after fix this AgBr go away from layer and thickness of layer will be reduce. The color of imade will be more orange (the wavelenght will be shorter). If nonfix hologram after develop, the color of image will be red.
Zacharovas don't work in "Slavich". He work in "Geola". And I don't know about work of hardening of emulsion PFG-03m although I go to "Slavich" every week. But my experiments show - when emulsion PFG-03 made hard, the DE is reduce. So, main feature of emulsion PFG-03 - this NONHARDNESS emulsion. Only this give good parameters.
I write many english words. Need small rest
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Martin
Holographs
"It is interesting question - the quantity of thiocyanate in 1 l of work solution of MM Color is 2g:50 = 0,04g and in 1 l of work solution of GP-3 is 45g:30 = 1,5g. To 38 time more! But MM Color work as more active developer (you right). I try study out in this. There are present some exceptive chemicals in MM Color. For example, potassium brom and thiocyanate. First have impede dissolve of AgBr but second special insert in developer for active dissolve of crystals of AgBr."MM-Collo1 comes closer to a developer like FMG-1 (one of the very best Russian colloidal developers):Phenidone............0,3g
Metol..................2g
Hydroquinone......... .5g
Sodium sulfite........40g
Potassiumcarbonate....20g
Potassium thiocyanate..3g
Sodium tetraborate...........15g
Potassium bromide................2g
1-phenyl-5-mer5captotetrazole...0,2g
Distilled water..................1L
The interesting part both with FMG-1 and MM-Collo1 was - in contrast to the GP developers - they actually produced smaller grains. So instead of an orange/red layer, we got a yellow emulsion (indicating grain sizes around 10 nm). Since a yellow layer absorbs less light at shorter wavelengths, bright green reconstructions could be achieved.
"GP-3 (and GP-2) is classic of physical developer. Main process there - diffusion transfer of atoms of AgBr from nonexposed crystals to exposed crystals when form very small and sphery grains of metal Ag. It is fine process and many cristals of AgBr stay in layer. So, after fix this AgBr go away from layer and thickness of layer will be reduce. The color of imade will be more orange (the wavelenght will be shorter). If nonfix hologram after develop, the color of image will be red."I see. So why would one carry out fixing? Just for color tuning? In my view fixing (with regards to noise and printout) will not contribute to any improvements.
"Zacharovas don't work in "Slavich". He work in "Geola".
And I don't know about work of hardening of emulsion PFG-03m although I go to "Slavich" every week."So you are involved with the production of PFG-03?I was wrong in my former statement about formaldehyde hardening I veriefied that. I erronously based my statement on a mail I received from Jeff Blyth, in which he pointed to Hans Bjelkhagen: "Hans B is in quite close technical contact with Slavich and he tells me that the wrapping paper they had been using had been causing the trouble."
The trouble was that wrapping paper containing formaldehyde. Over a certain period of time this led to an ever increasing layer hardness. In the context of SHSG processing (mostly а la Usanov), it became very difficult to achieve consistent results. "But my experiments show - when emulsion PFG-03 made hard, the DE is reduce. So, main feature of emulsion PFG-03 - this NONHARDNESS emulsion. Only this give good parameters."I can confirm this with the batch of PFG-03 we had. After several months, when we exposed the then quite hard emulsion (almost like 8E75), diffraction efficiency was greatly reduced.
Metol..................2g
Hydroquinone......... .5g
Sodium sulfite........40g
Potassiumcarbonate....20g
Potassium thiocyanate..3g
Sodium tetraborate...........15g
Potassium bromide................2g
1-phenyl-5-mer5captotetrazole...0,2g
Distilled water..................1L
The interesting part both with FMG-1 and MM-Collo1 was - in contrast to the GP developers - they actually produced smaller grains. So instead of an orange/red layer, we got a yellow emulsion (indicating grain sizes around 10 nm). Since a yellow layer absorbs less light at shorter wavelengths, bright green reconstructions could be achieved.
"GP-3 (and GP-2) is classic of physical developer. Main process there - diffusion transfer of atoms of AgBr from nonexposed crystals to exposed crystals when form very small and sphery grains of metal Ag. It is fine process and many cristals of AgBr stay in layer. So, after fix this AgBr go away from layer and thickness of layer will be reduce. The color of imade will be more orange (the wavelenght will be shorter). If nonfix hologram after develop, the color of image will be red."I see. So why would one carry out fixing? Just for color tuning? In my view fixing (with regards to noise and printout) will not contribute to any improvements.
"Zacharovas don't work in "Slavich". He work in "Geola".
And I don't know about work of hardening of emulsion PFG-03m although I go to "Slavich" every week."So you are involved with the production of PFG-03?I was wrong in my former statement about formaldehyde hardening I veriefied that. I erronously based my statement on a mail I received from Jeff Blyth, in which he pointed to Hans Bjelkhagen: "Hans B is in quite close technical contact with Slavich and he tells me that the wrapping paper they had been using had been causing the trouble."
The trouble was that wrapping paper containing formaldehyde. Over a certain period of time this led to an ever increasing layer hardness. In the context of SHSG processing (mostly а la Usanov), it became very difficult to achieve consistent results. "But my experiments show - when emulsion PFG-03 made hard, the DE is reduce. So, main feature of emulsion PFG-03 - this NONHARDNESS emulsion. Only this give good parameters."I can confirm this with the batch of PFG-03 we had. After several months, when we exposed the then quite hard emulsion (almost like 8E75), diffraction efficiency was greatly reduced.
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Sergey Vorobyov
Holographs
Yes, MM Colo have resemble to FMG developer. I used this developer many yeas ago. I find his formula
and remember that quality
of holograms was some like as after MM Colo developer. And those holograms had more red color and some reduce bright! I workd in Research Institute then and analyse many developers: GP-2, GP-8, SP-4, FMG-1, FMG-2 and other. The developer FMG was invent for photoplates PE-2, first Russian commercial
photoplates for record reflect holograms (the photoplates Mikrat VRM was before, but they was bad quality). They need to physical develop and FMG was recommend for it.After it "Slavich" begin manufacture series of photoplates for golography - PFG-01 (for transparent holograms, red laser), PFG-02 (color emulsion, bad properties, don't manufacture now), PFG-03 (for record reflect holograms, red laser) and PFG-04 (for record DCG-holograms, green laser). Optimal developer for PFG-03 was GP-2 develoder. The photoplates PFG-03m exist now - it modification of PFG-03 and GP-3 developer is better for it.
The midnight now. I continue tomorrow.
and remember that quality
of holograms was some like as after MM Colo developer. And those holograms had more red color and some reduce bright! I workd in Research Institute then and analyse many developers: GP-2, GP-8, SP-4, FMG-1, FMG-2 and other. The developer FMG was invent for photoplates PE-2, first Russian commercial
photoplates for record reflect holograms (the photoplates Mikrat VRM was before, but they was bad quality). They need to physical develop and FMG was recommend for it.After it "Slavich" begin manufacture series of photoplates for golography - PFG-01 (for transparent holograms, red laser), PFG-02 (color emulsion, bad properties, don't manufacture now), PFG-03 (for record reflect holograms, red laser) and PFG-04 (for record DCG-holograms, green laser). Optimal developer for PFG-03 was GP-2 develoder. The photoplates PFG-03m exist now - it modification of PFG-03 and GP-3 developer is better for it.
The midnight now. I continue tomorrow.
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Sergey Vorobyov
Holographs
I made mistake yesterday - "Mikrat VRM" used for record transparent holograms. The LOI-2 was making for record reflect holograms before PE-2. But they had small sensitivity and need to special sensitization (by TEA) before recording.The purity of chemicals has big action to quality of holograms. We all use different chemicals for holography, so we can take different results. It's curious that my experiments show conversely: the color of layer of emulsion more yellow for GP-3 then for MM-Collo 1 (and FMG). Of course, the color of emulsion depends from size of grains of silver.“I see. So why would one carry out fixing? Just for color tuning? In my view fixing (with regards to noise and printout) will not contribute to any improvements” – can’t translation your idea. Non-fix holograms can darken up on big or long light. And yellow color of image nicer, I think.“So you are involved with the production of PFG-03?” – I co-operate to “Slavich” many years and we make common work for optimization emulsions (old and new) and chemical of holograms. I try testing each new emulsion PFG-03.Yes, it big problem - wrapping paper. The long contact between paper and emulsion bring slow hardness and edge fog effect – after develop the edges of plate have black color. Advisable time of store of photoplates no more then one month. Two paths to elimination of these effects – store photoplates in refrigerator or store photoplates without paper. There are try use metallization paper for pack photoplates in “Slavich”, but humidity in pack was enlarge.
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Martin
Holographs
"The purity of chemicals has big action to quality of holograms. We all use different chemicals for holography, so we can take different results."Moreover, different degrees of emulsion hardening might produce different results.
"It's curious that my experiments show conversely: the color of layer of emulsion more yellow for GP-3 then for MM-Collo 1 (and FMG). Of course, the color of emulsion depends from size of grains of silver."So we agree a yellow layer is what we are searching for - since this produces less absorption for shorter wavelengths: for example images that reconstruct in green will show increased brightness.
I understand colloidal (and physical) development might provide a means to actually achieve smaller grains than the original grains of the unexposed emulsion. "Non-fix holograms can darken up on big or long light."
With regards to archival stability, we did not notice any significant difference between fixed and non-fixed holograms. Actually, we exposed several non-fixed holograms to sunlight: subsequent to a short period of darkening, they remained stable for many years. From the little I know about colloidal development, this seems to confirm theory. Colloidal development is a "self-ending process". Ideally, all the unexposed silver grains are deposited on the exposed sites. So there would be no need for fixing anymore.
However, I am aware in that area there exist a great many mysteries. For example, following "classic" (the Lumiиre brothers), procedures, this kind of techniques involved very slow processing - rather hours than minutes. Then I heard about Valery Petrov's SP developer - though I unfortunately never learnt any details about its composition. It seems to be a colloidal developer that allows to develop a PFG-03 emulsion within 5 - 10 seconds! One might wonder whether such fast development is performed by agents like para-phenylendiamine.
"Yes, it big problem - wrapping paper. The long contact between paper and emulsion bring slow hardness and edge fog effect – after develop the edges of plate have black color."Yes, I still have some sheets of film that show that kind of fogging. Is there any method to clear those emulsions?
"It's curious that my experiments show conversely: the color of layer of emulsion more yellow for GP-3 then for MM-Collo 1 (and FMG). Of course, the color of emulsion depends from size of grains of silver."So we agree a yellow layer is what we are searching for - since this produces less absorption for shorter wavelengths: for example images that reconstruct in green will show increased brightness.
I understand colloidal (and physical) development might provide a means to actually achieve smaller grains than the original grains of the unexposed emulsion. "Non-fix holograms can darken up on big or long light."
With regards to archival stability, we did not notice any significant difference between fixed and non-fixed holograms. Actually, we exposed several non-fixed holograms to sunlight: subsequent to a short period of darkening, they remained stable for many years. From the little I know about colloidal development, this seems to confirm theory. Colloidal development is a "self-ending process". Ideally, all the unexposed silver grains are deposited on the exposed sites. So there would be no need for fixing anymore.
However, I am aware in that area there exist a great many mysteries. For example, following "classic" (the Lumiиre brothers), procedures, this kind of techniques involved very slow processing - rather hours than minutes. Then I heard about Valery Petrov's SP developer - though I unfortunately never learnt any details about its composition. It seems to be a colloidal developer that allows to develop a PFG-03 emulsion within 5 - 10 seconds! One might wonder whether such fast development is performed by agents like para-phenylendiamine.
"Yes, it big problem - wrapping paper. The long contact between paper and emulsion bring slow hardness and edge fog effect – after develop the edges of plate have black color."Yes, I still have some sheets of film that show that kind of fogging. Is there any method to clear those emulsions?
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Sergey Vorobyov
Holographs
Yes, nonfix hologram may be stable many time (after good washout). But direct laser beam to this photoplate and you look dark spot after short time.I worked to the next developers SP-4 of Petrov and Lumiere:
SP-4
Sodium sulphite (anhydrous)...........85 g
Hydroquinone.........8,9 g
Potassium hydroxide...7,2 g
Phenidone............0,3 g
Ammonium thiocyanate..22 g
Water...........before 1 l
Recommend water bath 5 min before develop.
Time of develop – 10 sec. (18C). Need test of time of develop for modern photoplates.Lumiere
Solution A
Pyrogallol.............1 g
Water...............100 mlSolution B
Potassium bromide.....20 g
Aqua ammonia (NH4OH)..67 ml
Water...............200 mlWork solution: 10 ml sol. A + 20 ml sol. B + 70 ml water.
Time of develop 10 min (near).About reduce of edge fog: many years ago I used next formula for antifog (for PE-2):
Trilon B (for softening of water – (Tetra sodium EDTA?))...50 g
FeCl3*6H2O............25 g
Potassium bromide...0,25 g
Water...................1l
Need make filter of ready solution.
Time of bath – 3 min. Next – water, 5-10 min and develop.
SP-4
Sodium sulphite (anhydrous)...........85 g
Hydroquinone.........8,9 g
Potassium hydroxide...7,2 g
Phenidone............0,3 g
Ammonium thiocyanate..22 g
Water...........before 1 l
Recommend water bath 5 min before develop.
Time of develop – 10 sec. (18C). Need test of time of develop for modern photoplates.Lumiere
Solution A
Pyrogallol.............1 g
Water...............100 mlSolution B
Potassium bromide.....20 g
Aqua ammonia (NH4OH)..67 ml
Water...............200 mlWork solution: 10 ml sol. A + 20 ml sol. B + 70 ml water.
Time of develop 10 min (near).About reduce of edge fog: many years ago I used next formula for antifog (for PE-2):
Trilon B (for softening of water – (Tetra sodium EDTA?))...50 g
FeCl3*6H2O............25 g
Potassium bromide...0,25 g
Water...................1l
Need make filter of ready solution.
Time of bath – 3 min. Next – water, 5-10 min and develop.
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Martin
Holographs
"Yes, nonfix hologram may be stable many time (after good washout). But direct laser beam to this photoplate and you look dark spot after short time."This is very interesting, I never thought of that. It might be explained by the the effect of colloidal silver to shift sensitization to longer wavelengths."I worked to the next developers SP-4 of Petrov and Lumiere:
SP-4
Sodium sulphite (anhydrous)...........85 g
Hydroquinone.........8,9 g
Potassium hydroxide...7,2 g
Phenidone............0,3 g
Ammonium thiocyanate..22 g
Water...........before 1 l
Recommend water bath 5 min before develop.
Time of develop – 10 sec. (18C). Need test of time of develop for modern photoplates."Thank you for disclosing that formula! I am surprised to learn that developer involves using fairly "common" chemistry. Its pH seems to be rather high though.Regarding the composition of the "Lumiere developer", I was actually alluding to a composition designed by Lumiere/Seyewetz:A
Sodium sulfite......................180g
10% silver nitrate solution..7,5ml
Water................................1000mlB
Sodium sulfite........................20g
para-phenylendiamine..........20g
Water................................1000mlUse 150ml A + 30ml B
"About reduce of edge fog: many years ago I used next formula for antifog (for PE-2):
Trilon B (for softening of water – (Tetra sodium EDTA?))...50 g
FeCl3*6H2O............25 g
Potassium bromide...0,25 g
Water...................1l
Need make filter of ready solution.
Time of bath – 3 min. Next – water, 5-10 min and develop."Thanks for revealing this formula. It looks like a mild bleach. By the way, regarding bleaching, I am aware of rather good results when bleaching a GP-3 developed PFG-03 emulsion in a iodine bleach (and, to a lesser extend, copper sulfate bleaches). Iodine...................10g
Potassium iodide 1g
Ethyl alcohol....750ml
Water...............250mlHowever, I assume grain size of the developed emulsion has to be relatively large - otherwise, the bleaching does not work. Are there any other bleaches around that yield high DE at acceptable noise level on colloidal developed layers?
SP-4
Sodium sulphite (anhydrous)...........85 g
Hydroquinone.........8,9 g
Potassium hydroxide...7,2 g
Phenidone............0,3 g
Ammonium thiocyanate..22 g
Water...........before 1 l
Recommend water bath 5 min before develop.
Time of develop – 10 sec. (18C). Need test of time of develop for modern photoplates."Thank you for disclosing that formula! I am surprised to learn that developer involves using fairly "common" chemistry. Its pH seems to be rather high though.Regarding the composition of the "Lumiere developer", I was actually alluding to a composition designed by Lumiere/Seyewetz:A
Sodium sulfite......................180g
10% silver nitrate solution..7,5ml
Water................................1000mlB
Sodium sulfite........................20g
para-phenylendiamine..........20g
Water................................1000mlUse 150ml A + 30ml B
"About reduce of edge fog: many years ago I used next formula for antifog (for PE-2):
Trilon B (for softening of water – (Tetra sodium EDTA?))...50 g
FeCl3*6H2O............25 g
Potassium bromide...0,25 g
Water...................1l
Need make filter of ready solution.
Time of bath – 3 min. Next – water, 5-10 min and develop."Thanks for revealing this formula. It looks like a mild bleach. By the way, regarding bleaching, I am aware of rather good results when bleaching a GP-3 developed PFG-03 emulsion in a iodine bleach (and, to a lesser extend, copper sulfate bleaches). Iodine...................10g
Potassium iodide 1g
Ethyl alcohol....750ml
Water...............250mlHowever, I assume grain size of the developed emulsion has to be relatively large - otherwise, the bleaching does not work. Are there any other bleaches around that yield high DE at acceptable noise level on colloidal developed layers?
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Sergey Vorobyov
Holographs
Excuse my for my delay - my Internet line was damage.
About dark spot on emulsion - I think it is consequent of interaction between AgBr and remains of dye. If remove all dye from emulsion, it will be more stable, maybe.
I think many formulations have some variants. For example, I know two formulas of FMG diveloper.Standart formula:
Sodium sulfite.......40g
Metol.............2g
Hydroquinone.....5g
Phenidone........0,3g
Sodium tetraborate..15g
Potassium carbonate..20g
Potassium bromide...2g
Potassium thiocyanate..3g
Water..............1l
15 ml to 400 ml water. Time of develop 10 minFMG-2
Metol.............2g
Hydroquinone.....5g
Phenidone........0,3g
Sodium sulfite...40g
Potassium carbonate..20g
Sodium tetraborate..15g
Potassium bromide...2g
Potassium thiocyanate..5g
Potassium hydroxide...5g
Water..............1l
40 ml to 1l water. Time of develop 15 min.It is very complex formulas. Need search more simple formulas.I had try bleach to PFG-03 many time. The result is one - small brightness of holograms. So, I made conclusion: for PFG-03 need only physical(colloidal) develop. There are a little of AgBr in layer but for effective bleach need many more AgBr. In PFG-01 and VRP photoplates many AgBr, so this photoplates can be bleach.
About dark spot on emulsion - I think it is consequent of interaction between AgBr and remains of dye. If remove all dye from emulsion, it will be more stable, maybe.
I think many formulations have some variants. For example, I know two formulas of FMG diveloper.Standart formula:
Sodium sulfite.......40g
Metol.............2g
Hydroquinone.....5g
Phenidone........0,3g
Sodium tetraborate..15g
Potassium carbonate..20g
Potassium bromide...2g
Potassium thiocyanate..3g
Water..............1l
15 ml to 400 ml water. Time of develop 10 minFMG-2
Metol.............2g
Hydroquinone.....5g
Phenidone........0,3g
Sodium sulfite...40g
Potassium carbonate..20g
Sodium tetraborate..15g
Potassium bromide...2g
Potassium thiocyanate..5g
Potassium hydroxide...5g
Water..............1l
40 ml to 1l water. Time of develop 15 min.It is very complex formulas. Need search more simple formulas.I had try bleach to PFG-03 many time. The result is one - small brightness of holograms. So, I made conclusion: for PFG-03 need only physical(colloidal) develop. There are a little of AgBr in layer but for effective bleach need many more AgBr. In PFG-01 and VRP photoplates many AgBr, so this photoplates can be bleach.