Chemistries for Holography

Since some are interested in the old Leroy paper, here is my - rudimentary - translation:

Excerpts from: M.N. Leroy, Préparation et sensitométrie de plaques photographiques à grain très fin (plaques pour la photographie interférentielle), Paris 1929

Summary. The following note presents a new way for the making of fine grain photographic emulsions, derived from colloidal silver, that allows for the spectral recording of remarkable brightness, comparable to Lippmann emulsions. It (the note) summarizes certain results achieved with silver chloride, bromide and iodide. The study of the density graphs indicates a maximum sensitivity at a particular lambda for each of the three cases and depends on the molecular weight of the specific salt used. Having established the characteristic graph of each emulsion at certain spectral levels, the author is studying the variation of gamma as a function of lambda, and points out that these plates, (though) having the qualities of any common plates, they can be sensitized to any wavelength and t can be used for color photography.
The present study tried to establish the sensitometric characteristics of Lippmann plates, prepared according the formula of the ingenious inventor of the only direct recording method of color photographs.
The results indicated too many variations and lacked the desired consistency. This is certainly due to fluctuations usually occurring (even) with the same composition (differing but on agitation, temperature, filtering, washing etc.). In one case, instead of being sensitive to the wavelength showing the strongest diffraction, we even observed sensitivity to radiation all over the visible spectrum. Without adding any sensitizers, it all the same behaved like an orthochromatic plate and, this was consistent for all plates of that batch, we do not have an explanation.
According to Mr. Cotton, who advised us to use colloidal silver, on which grounds he had managed to make plates for interference color photography, we succeeded to get light sensitive layers of very small grains and of great consistency indicated by the measurements we carried out in the case of silver chloride, bromide and iodide.
Preparation of the plates
To a tepid solution (filtered warm) of 2.5g special gelatin in 50 cm3 distilled water, 3 cm3 of a 10% colloidal silver solution are added. The resulting liquid of brown color, is poured on glass plates according to the methods used for collodion. The plates, arranged horizontally until gellation, are subsequently dried protected from dust. These operations are carried out under normal light, thus allowing for the production of a stock to be used occasionally as needed.
The transformation of the colloidal silver into halide salts is carried out under subdued light, such as that of a candle or some reduced gaslight. The plate is introduced into a bath for which - after numberless trials - we established the following compositions (note: the quantities given do not correspond with the completed reaction but proofed to work most conveniently for our experiments):
Chloride plates
sodium chloride.....2g
copper sulfate........2g
water................1000g
Bromide plates
potassium bromide....2g
copper sulfate ...........2g
water....................1000g
Iodide plates
potassium iodide..........2g
copper sulfate ..........2g
water...................1000g
"Bromination" is taking place equally well by using a diluted solution of cupric bromide; cupric chloride however, produced an opaque layer as well as did chlorine water (?) or iodine solution.
During the preparation of the iodine (? rather cupric iodide I suppose - MM) bath, a precipitation of cupric iodide is forming which can be eliminated by filtering.
As soon as the reaction stops - that is to say, when the yellowish color has vanished - one has to wash the plate, turned transparent meanwhile, exhaustively.
At this stage the plates are very little sensitive. A means to this nuisance is to insert them into a second bath of 50g water to which 2g of a silver nitrate solution (0.5g AgNO3 per 100g water) were added during 1 minute. They are washed with distilled water and dried in darkness.
The developer has the following composition:
water...............................100ml
sodium sulfite......................4g
Amidol...............................0,3g
Potassium bromide...........0,75g
The plates are fixed in sodium thiosulfate.
Conclusions
Due to the preliminary results, this study represents only some sort of beginning. Nonetheless, we are thinking the constants (?) introduced by Hurter and Driffield into photographic practice, can be applied to the fine grain plates we prepared.
We will continue our work, systematically studying the use of chemical sensitizers and try to realize a perfectly orthochromatic "interference" plate.
We meanwhile like to point out that the silver bromide plates prepared by flowing, are easily sensitized orthochromatically and allow for spectral recordings of the same brightness as Lippmann plates. The same is also valid for chloride. However, the sensitizers ("orthochromatisants") successfully applied to chloride and bromide, did not show any effect on iodide.
Concluding this work, it is an pleasant duty to express my appreciation to professor Cotton (directeur du Laboratoire des Recherches physiques à la Sorbonne), for his support and interest.
I equally thank my teacher, Mr. de Watteville, who introduced me into the delicate technique of interference photography... etc.

SM-6

Sodium Hydroxide 12.0g

Methyl Phenidone 6.0g

Ascorbic Acid 18g

Sodium Phosphate (dibasic) 28.4g

Water to 1L

From www.slavich.com

TITLE	CHEMICAL	FORMULA	Sigma Aldrich code	Fluka code
SM-6	Sodium Hydroxide	NaOH	S 0899	71690
	Phenidone	C₆H_5-C₃H₅N₂O	P 3441	79070
	Ascorbic Acid	CH₂OHCHOH(CHCOH:COHCOO)	A 7506	95212
	Sodium Phosphate (dibasic)	Na₂HPO₄	S 0876	71642
CW-C2	Catechol	C₆H₄-1,2-(OH)₂	C 9510	15890
	Ascorbic Acid	CH₂OHCHOH(CHCOH:COHCOO)	A 7506	95212
	Sodium Sulphite (anhy.)	Na₂SO₃	S 8018	71990
	Urea	NH₂CONH₂	U 1250	51460
	Sodium Carbonate	Na₂CO₃	S 7795	71351
PBU-Amidol	Potassium Persulphate	K₂S₂O₈	P 9392	60490
	Citric Acid	HOC(COOH)(CH₂COOH)₂	C 0759	27488
	Cupric Bromide	CuBr₂	-	61185
	Potassium Bromide	KBr	P 9881	60095
	Amidol	(NH₂)₂C₆H₃OH•2HCl	23,010-3	33230
Bath	Potassium Iodide	KI	P 8256	60400
Hardener	Formalin 37%	HCHO	F 1635	47608
Table 3: Chemical Formulas and suppliers codes.

Stop Bath

Acetic Acid 20g

Water to 1L

Safe Ferric Brilland Bleach ( rehalogenating Bleach designed by brilland)

Ferric III Sulfate 30g
Citric acid 30g
Potassium Bromide 30g
Deionized water to 1000 cc.

You can use it and store it for a very long time at room temperature. It gives very low noise results.

AAC

Ascorbic Acid 18g

Sodium Carmonate to give a pH of 10.5

Distilled Water 1L

AGFA 80

Metol 2.5g

Soduim Sulfite (anhydrous) 100g

Hydroquinone 10g

Potassium Carbonate 60g

Potassium Bromide 4g

Distilled Water 1L

GP-8

Metylphenidone .2g

Hydroquinone 5g

Sodium sulfite (anhydrous) 100g

Potassium hydroxide 10.6g

Ammonium thiocyanate 24g

Distilled water 1L

Mix 60 ml of developer with 400ml of distilled water. Develop for 6 minutes at 20C.

GP-2

Metylphenidone .2g

Hydroquinone 5g

Sodium sulfite (anhydrous) 100g

Potassium hydroxide 5g

Ammonium thiocyanate 12g

Distilled water 1L

Mix 15ml of developer with 400ml distilled water. Develop for 12 minutes at 20C without agitation. Develop with plate facing up and DO NOT agitate (you don't want to move the disolved silver away from the plate).

CPA1

Metylphenidone .02g

Hydroquinone .65g

Sodium sulfite (anhydrous) 13g

Potassium hydroxide 1.4g

Ammonium thiocyanate 3.1g

Distilled water 1L

Develop for 2 minutes at 22C. 3 seconds of initial agitation.

Metol .5g

Sodium Sulfite (anhydrous) 100g

Hydroquinone 45g

Sodium carbonate 30g

Potassium thiocyanate 5g

Potassium bromide 10g

Distilled water 1L

Mix 1 part developer to 8 parts distilled water.

Amidol 4g

Sodium sulfite (anhydrous) 30g

Silver nitrate 3g

Potassium bromide 2g

Sodium thiosulfate 45g

Distilled water 1L

Develop for 8 minutes. Fix for 2 to 3 minutes.

Metol 10g

Sodium sulfite (anhydrous) 100g

Silver nitrate 2g

Potassium bromide 2g

Sodium thiosulfate 30g

Distilled water 1L

Develop for 30 minutes. No fix is required.

SHSG for PFG-03C and PFG-03M

from: Transmission and Reflection SHSG Holograms - Kim, Choi, Choi, Kim, Kim, Bjelkhagen, Phillips - SPIE
and SHSG processing for three-wavelength HOEs recording in Silver Halide Materials - Kim, Choi, Bjelkhagen, Philips - SPIE

I have made some assumptions about their process. Please read the source if you are serious about this process.

Hardening bath

Formaldehyde (37%) 10ml
Potassium Bromide 2g
Sodium Carbonate (anhydrous) 5g
Deionized Water 1L

Stop Bath

2% Acetic Acid Bath

Bleach (pH 5)

Cupric Bromide 1g
Potassium Persulfate 10g
Citric Acid 50g
Potassium Bromide 20g
Borax 30g
Chromium (III) Potassium Sulfate 20g
Deionized Water 1L

Add 1g Metol after everything is mixed

Fix Bath

Ammonium Thiosulfate (anhydrous) 10g
Sodium Sulfate (anhydrous) 20g
Deionized water 1L

Process

Prehardening 6 min
Develop G282C Diluted 1 to 3 to 1 to 5 3 min
Rinse Running Deionized Water at least 3 Min
Stop
Wash?
Bleach (diluted 1:3) 15 min
Warm water bath (60C) 10 min
Wash?
Dehydrate 50% IMS 3 min
                   100% IMS 3 min
Dry in 45C oven 5 min
Vapor harden with Formaldehyde 25 min
        or 50% glutaraldehyde vapor 25min
Fix 2 Min
Wash
Dehydrate 50% Isopropyl 10 min
                                  100% 10 min
                                  100% 70C 2min
Dry in 45C oven.

Seal with Pascofix

From Martin:

The two developers mentioned in US 4108661 might be candidates for developers a la G284c:

I
hydroquinone: 16.5 g
potassium bromide: 1.7 g
sodium salt of EDTA: 1.7 g
potassium metabisulphite: 40 g
1-phenyl-5-mercaptotetrazole: 35 g
sodium hydroxide and water to make: 1 liter at pH 11.8.

II
hydroquinone: 25 g
potassium bromide: 2.5 g
sodium salt of EDTA: 2.5 g
potassium metabisulphite: 62.5 g
1-phenyl-5-mercaptotetrazole: 50 mg
potassium thiocyanate: 0.5 g
sodium hydroxide and water to make: 1 liter at pH 11.8

(Colin's Note: These developers have some of the features but the MSDS includes Potassium Sulphite and Hydroquinone as the only listable toxins. Info from Kim et. al. G282C is the high speed reversal prosess for AGFA Millimask Plates. "Such non-tanning developers usually contain halide solvents and encourage sharp developed edges."

by Martin

Maybe I should have pointed to another paper (also in SPIE 4659) by a Russian group (Evstigneeva, Drozdova, Mikhailov) dealing with SHSG.
The authors recorded pulsed holograms on VRP plates (which incidentally are said to come close to PFG-01). (Colin's Note: VRP is green sensitive and PFG-01 is Red Sensitive. For more details see www.slavich.com)

They describe the following processing steps:
1) Development in a non-tanning developer (SM-6);

2) rehalogenating bleach (permanganate);

3) intermediate alcohol (ethanol) drying;

4) uniform second exposure;

5) second development in diluted developer;

6) reversal bleaching (dichromate);

7) fixing;

8) dehydration in isopropanol.

The potassium permanganate bleach is formed by:
Pot. permanganate ................0,4g
Sulfuric acid ...................0,4ml
Sodium chloride....................10g
Water...............................1L

The second developer:

Sodium sulfite ......................5g
Metol................................5g
Hydroquinone........................10g
Ascoribic acid......................10g
Phenidon.............................1g
Sodium hydroxide....................10g
Water................................1L

From Martin:

The best formula I ever made for a colloidal developer was:

Stock solution MM-Collo 1:

Metol.............................2g
Ascorbic acid.....................7g
Methylphenidone.................0,5g
Potassium bromide.................3g
Potassium carbonate..............20g
Ammonium thiocyanate..............2g
Distilled water...................1L

Dilute 1 : 50 or up to 1:100 (with distilled water)

On PFG-03M it yielded extremely fine grains, resulting in a yellow emulsion (compared with the orange/red layer produced upon GP development). Development is quite slow, requiring > 30 min @ 20°C.

Russian VR-P developer:

Sodium Sulphite anhydrous 194 g
Hydroquinon 25 g
Potassium Hydroxide 22 g
Methylphenydone 1.5 g
Potassium Bromide 20 g
Potassium Metaborate 140 g
1,2,3-Benzotriazole 0.1 g
Distilled water to 1 L

Working solution: 1 part of VR-P Developer + 6 parts distilled water

Home
Please free to contact me at: colin@designerinlight.com

Solution B

Distilled Water 100 Deg. F 800 ml

Sodium Carbonate, Anhyd. 60 grams

Water 68 Deg. F to make 1 liter

Mix equal parts A and B just before development. Mix enough for one hologram only. ( I have developed 3, But the first one is best)

Bleach

Distilled Water 68 deg. F 750 ml

Potassium Dichromate 5 grams

Sodium Bisulfate 80 grams

Water 68 deg. F to make 1 liter

Dissolve potassium dichromate completely before adding sodium bisulfate. The bleach can be used for a long time. At least 5 months shelf life.

Develop 2 minutes

Rinse 3 minutes

Bleach till clear (less than two minutes)

Rinse

Photo flo

Air dry

JD-3 from Integraf

Developer

Part A

Water 750ml
Catechol 20g
Ascorbic acid 10g
Sodium sulfite 10g
Urea 75g

Water to make 1L

part B

Water 750ml
Sodium carbonate 60g

Water to make 1L

Bleach

Water 750ml
Copper sulfate 17g
Potassium bromide 55g
Succinic acid 2g

Water to make 1L

Post Treatment

Water 300ml
Ascorbic acid 10g

water to make 400ml

Mix equal parta A and B. Working solution has a life of 8 hours. Only develop one hologram. Develop for 2 minutes with agitation.

Soak in distilled water for 10 seconds.

Wash for 3 minutes.

Do not dilute bleach. Bleach emulsion side down till clear. Less than 2 minutes.

Wash for 3 minutes.

Dilute post treatment 1 to 10 with water. soak under bright light untill the hologram turns from pink to light brown.

Wash for 3 minutes.

JD-4 from Integraf for PFG-03M from Slavich

Developer Part A (1 liter)Quantity

Metol or Elon (p-Methylaminophenol sulfate) 4 g
Ascorbic acid (powder) 25 g

Developer Part B (1 liter)

Sodium carbonate, anhydrous 70 g
Sodium hydroxide 15 g

Bleach (1 liter)

Copper sulfate (pentahydrate) 35g
Potassium bromide 100g
Sodium hydrogen sulfate crystals 5g

Mixing instructions

Use three l liter (or larger)size clean glass or plastic bottles with leak proof caps. Label them A, B, and Bleach respectively.

Warm the distilled or de-ionized water to about 40o C (warm to the touch).

Fill the bottle marked A with 700 ml of warm water. Dissolve the Metol in it, then add the ascorbic acid. Add 300 ml of warm water to make 1 liter of Part A developer. Tightly cap the bottle. Part A will oxidized if it is exposed to oxygen. In time (over a few days to few weeks), the solution may turn yellow due to the oxidation of ascorbic acid; the solution is still useable. Once the solution turns dark brown, the potency is lost and should be disposed.

One way of protecting it from oxidation is to subdivide the solution into smaller bottles so that the unused portions are in fully capped bottles, with little or no air space on top. Refrigeration also slows down oxidation (exercise extreme caution to prevent its mistaken identity as food).

Follow the same procedure for Part B (add the sodium carbonate and sodium hydroxide in either order). This solution will keep for many weeks.

Follow the same procedure for mixing the Bleach. This solution has very long shelf life.

Metol-Ascorbate developer courtesy of Laser Reflections

The formula is as follows:
Metol-Acorbate Developer (Part A + Part B)
Part A:
Metol 10g
Ascorbic Acid 80g
Water to 1000ml
Part B:
Sodium Carbonate Anhydrous 120g
Sodium Hydroxide 14g
Potassium Bromide 4g
Water to 1000ml

Use it in combination with a Fe-EDTA bleach - a safe,
stable bleach which has a long shelf life.

Fe-EDTA Bleach
EDTA (2Na) 30g
Fe(III) Sulfate 30g
Potassium Bromide 30g
Sodium Hydrogen Sulfate Crystals 30g
Water to 1000ml

From Jeffrey:

When using Russian emulsions -

Pre-develop gelatin hardening bath -
Sensitizes and maintains colors, allows squeegee use

Distilled water 750 ml
Formaldehyde 37% (Formalin) 10 ml (10.2 g)
Potassium bromide 2 g
Sodium carbonate (anhydrous) 5 g
add distilled water to make 1 L

Processing time 6 minutes. Developing times may increase with harder gelatin.

From Jeffrey:

CWC2 DEVELOPER and PBU-AMIDOL BLEACH
- for all types of HOLOGRAMS
________________________________________________
CWC2 - two-part DEVELOPER

*PART A solution
500 ml. warmed distilled water.
(Pyro)Catechol

                   10   grams
L-Ascorbic Acid (Vitamin C)                5   grams
Sodium Sulfite (anhydrous)            5   grams
Urea

30 grams

*PART B solution
500 ml. warmed distilled water.
Sodium Carbonate

        30   grams
________________________________________________
Part A is good for one month, Part B indefinitely.
Add equal parts A & B to activate just a minute or two before use, just enough to cover one hologram. Mixed solution is active for 20 minutes. Discard after one use to assure each hologram has optimum development.
Develop time:
at least TWO minutes @ 68 degrees F. with constant agitation (AGFA).
    FIVE minutes for low power lasers, for HRT plates and PFG-03M plates.
Rinse in distilled water.
View a green safelight through rinsed plate to judge density - some variation is OK.
Adjust exposure/developing time to achieve a final developed density of:
      D 1.5 - 2 - medium gray (for an unbleached transmission hologram)
      D 2 - 3.5 - very dark (reflection holograms).
D 4 - appears mostly opaque (good for HRT reflection holograms).

Do not use fixer if it will be bleached (reflection holograms are usually bleached).

    Notes on developed density - this stage is where you figure if exposure, ratio, gleam spots, beam centering, even illumination, and overall light levels and their recorded patterns are OK for the next shot as well, or need adjustment. After the plate is bleached clear, these clues are gone. Although dark, wet, and hard to see, observation of different gray levels is important, hopefully understanding what caused each visible pattern. A good safelight is important. My favorite is a commercially available four-foot fluorescent fixture with plastic tube filters.

____________________________________________
PBU-AMIDOL re-halogenating BLEACH (Phillips Bjelkhagen Ultimate)

Potassium Persulfate

        10 grams
Sodium Bisulfate (or Citric Acid)               10 grams
Potassium Bromide

20 grams

Cupric Bromide

1 gram

Amidol (- add last ! -)

1 gram

____________________________________________
Mix one at a time, in sequence, into 500 ml. warmed distilled water,
then add another 500 ml. distilled water to make 1 liter.
*Wait at least 30 minutes for chemical activation.

- Bleach unfixed plate for 3-5 minutes @ 68 degrees F. 'til clear + 2 minutes. Rehalogenating (and image brightening) continues after clearing.
- Rinse, rinse, rinse in distilled water.
- With a drop of Photo-Flo in the final rinse, squeegee.
- Air dry, a low-heat blower or drying cabinet for around 15 minutes - not too fast, not too slow.

An acetic acid rinse after bleaching may help reduce print-out (the emulsion will darken a bit after you run out in the daylight to see your image). I prefer to avoid intense sunlight until aged a few days. Re-bleaching later will partially clear a darkened plate and give some immunity to further print-out.
    Bleach can be re-used a few times, and is usually good for two weeks - red color will fade to clear, indicating exhaustion.
     *Beware sediment as it ages - do NOT attempt to re-mix before each use - decant and do not dump dregs out onto emulsion.
        Bleach will leave permanent purple stains on everything - handle carefully !

    Many thanks to Cooke and Ward, Hans Bjelkhagen, Nick Phillips and Ed Wesly for the many trials to attain the basic formulation.

GP-9

Phenidone .026 g

Hydroquinone .665 g

Anhydrous Sodium Sulfite 13 g

Potassium Hydroxide 1.38 g

Ammonium Thiocyanate 3.12g

Distilled Water 1 L

GP-61 - transmission

Distilled Water 700cc

Metol 6 g

Hydroquinone 7 g

Phenidone .8g

anhydrous sodium Sulfite 30g

Anhydrous Sodium Carbonate 60 g

Potassium Bromide 2 g

Sequesterine Agent 1 g

Water to make 1 L

GP-62 - reflection (use Bleach)

Part A

Distilled Water 700 cc

Metol 15 g

Pyrogallol 7 g

Anhydrous Sodium Sulfite 20 g

Potassium Bromide 4 g

Sequestrene Agent 2 g

Water to make 1 L

Part B

Distilled Water 700 cc

Anhydrous Carbonate 60 g

Water to make 1 L

Kodak D-8

Ascorbic Acid 18g

Sodium Hydroxide 12 g

Sodium Phosphate Dibasic 28.4 g

Distilled water 1 L

Just before use add Phenidone .5 g

Transmission bleach

Water 1 L

Potassium Ferocyanide 1 tablespoon

Potassium Bromide 1 tablespoon or

Cupric Bromide 1 tablespoon (not both!)

Reflection bleach

water 1 L

potassium Bromide 30 g

Borax 15 g

Potassium dichromate 2 g

Just before use add PBQ (p-benzoquinone) 2 g (good for 15 minutes)

PBQ

Water 1 L

Mercuric Chloride 1 tablespoon

Potassium Bromide 1 tablespoon

Water 1 L

Potassium Bromide 30 g

Boric Acid 1.5 g

PBQ 2 g

Good for only 15 minutes!

Sulphric acid 1 g

potassium Bromide 5g

Methyl Paraben 2g

Hydrogen Peroxide 4 g (you have to figure the weight of the Hydrogen peroxide in you solution!)

Potassium Alum 5g (hardener)

PBQ 1 g

Phenosafranine 1g (desensitizer)

GP-431 Bleach

Water 600 cc

Ferric Nitrate 8-hydrate 150 g

Potassium Bromide 30 g

Dissolve .3 g of Phenosafranine in 250 cc of methanol and then add.

Water to make 1 L

Dilute 4 parts water to 1 part gp-431 before use.

Leroy
by Martin

Chemical	Price/Quantity	Diluted quantity	Quant/20 plates	Price/20 plates
AgNO3 (6%)	18,11/10g.	166 ml	60	6,55
LiBr (3%)	11,2/100g.	3300 ml	300(*)	1,02
Pinacyanol (0,1%)	16,81/250mg	250 ml	7,5	0,5
Ascobic Acid (1%)	2,11/30g	3000 ml	300(*)	0,21
Gelatin (15%)	9/1000g	6666 ml	100	0,14
Chrome Alum (2%)	3/100g.	5000 ml	300(*)	0,18
Silane (1%)	31,16/100ml	10000 ml	100	0,31
Glass (4x5)	12,5/20	-	20	12,50
Total for 20 plates	-	-	-	21,41 or 1,07/plate