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Before we go any further...If you're one who still insists on using Potassium Cyanide as a fixing agent for
collodion films, please recognize the hazards involved. This stuff is deadly. The following is an excerpt from
an AMES research safety document regarding Potassium Cyanide. The term LD50 references the Lethal Dose required
to produce a 50% death rate in a test population (in this case rats).
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Potassium Cyanide Health Effects:
Acute toxicity is high.
Ingestion of NaCN or KCN or exposure to their salts or their aqueous solutions by eye or skin contact can be fatal.
Exposure to as little as 50-150 milligrams can cause immediate collapse and death.
Symptoms of nonlethal exposure to cyanide include weakness, headache, dizziness, rapid breathing, nausea, and vomiting.
Cyanide salts are corrosive and toxic.
Decomposition products of HCN and nitrogen oxides are extremely hazardous.
LD50 (Lethal Dose for 50% of test subjects) is:
KCN (potassium cyanide), 8.5mg/kg (of body weight), orally injested – rat
NaCN (sodium cyanide), 6.4 mg/kg (of body weight), orally injested – rat
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The above excerpt refers to "decomposition products of HCN...". HCN is hydrogen cyanide GAS.
This is released if potassium cyanide comes in contact with acids (among other things).
Remember that your developers use acids as restraining agents... mixing
developers and potassium cyanide is a recipe for trouble.
Hypo (sodium thiosulphate) is an equally effective alternative
for removing undeveloped silver salts from the film and involves none of the hazards.
Please be safe. There is no reason whatsoever to use Potassium Cyanide.
Now, on with the show...
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This is where the rubber meets the road, as it were.
The place where science, chemistry in particular, plays a predominant role in the artistic process.
Because the darkroom, and to an even greater degree the wet-plate
collodion darkroom, is essentially a chemistry lab, there are a number of "good practice" techniques and safety habits that one
should be familiar with.
Because the wet-plate lab deals with a wide variety of potentially hazardous materials, the first
order of business is to learn about the materials, their hazards, and how to handle them safely.
Several chemicals used in the process are poisonous, carcinogenic,
extremely flamible, and/or potentially explosive.
Read and understand the MSD sheets for the particular chemicals you have in your darkroom, and seek counsel
from trained professionals (chemists, hazardous material handlers, specialized public safety officers, etc.)
who are familiar with proper handling and disposal of these chemicals.
THE AUTHOR AND PUBLISHER OF THIS ARTICLE DO NOT ACCEPT ANY RESPONSIBILITY OR LIABILITY RESULTING
FROM ERRORS, OMISSIONS, OR THE IMPROPER USE OF THESE CHEMICALS BY OTHER INDIVIDUALS.
USE OF ANY CHEMICALS OR METHODS MENTIONED ON THIS SITE IS AT YOUR OWN RISK.
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Safety Equipment
Safety glasses/goggles
Always, always, always wear safety glasses or goggles when working with chemicals of any kind.
You are a photographer. Your eyesight is crucial to the work you do (not to mention just
getting around in your daily life). Don't take chances. Wet chemistry can splash and/or spill,
and chemical dust can become airborne. Silver nitrate in particular, will permanently stain organic materials (think skin
and eyes!) when it comes in contact with them. If you get it in your eyes, it will blind you. Why take chances?
Gloves
Nitrile gloves are a good idea whenever you are working in the collodion darkroom. Remember, your skin is porous and you can
can absorb many of the chemicals you are working with into your blood stream through your hands. It's not that
inconvenient to slip on a pair of gloves. It's a good habit to get into, and at the very least will keep your fingers
and nails from picking up silver stains.
Respirator
Though, not absolutely necessary for all operations, it's not a bad idea to use a respirator
when handling dry chemistry that is powdery and can easily become airborne.
Measuring Liquids
For large volumes, pour the liquid into a graduated cylinder then raise the cylinder to eye level to view the
surface of the liquid (not the miniscus at the edge of the cylinder) to get an accurate reading of the volume.
For measuring smaller volumes, a graduated syringe provides the most convenient method. Plastic syringes are cheap and relatively
easy to get, and an indispensable item to have in your darkroom. To measure out and dispense small amounts of liquid, press the syringe
plunger all the way forward, then dip the tip of the syringe in the liquid to be measured and draw back on the plunger
until the plunger position is at the appropriate value on the graduated scale.
Weighing Solids
There are a variety of pocket sized digital scales available at very affordable prices. This is another must have for the darkroom.
When ever using a scale, always cover the weighing pan with a square of waxed paper. Tare (or zero) the scale after placing the
waxed paper on the pan, then place the dry chemicals on the paper to weigh them. The paper keeps the scale clean, and also makes it much
easier to move the chemicals from the pan to the beaker that contains the solvent.
Calculating Concentrations
When purchasing chemicals in solution, quite often their concentrations are given
in the form of Molar concentrations. To understand what this is, let's begin with a particular chemical compound,
such as Silver Nitrate, which is composed of three elements, Silver, Oxygen, and Nitrogen, bonded in a
very specific way. Each element has a very specific weight which can be found on a periodic table of the elements.
This is called the element's atomic weight, and although that's true, the number presented is actually the weight
of one Mole (6.02 x 10e23 atoms) of the element measured in grams.
The short of the story is, if we know the chemical formula,
in this case AgN03 we know we have one silver at 107.86 grams/Mole, one nitrogen at 14.006 grams/Mole, and three oxygen at 15.9994 grams/mole.
Add them all up and you have the formula weight for one Mole of Silver Nitrate at 169.873 grams. A silver nitrate bath for sensitizing
collodion is typically 0.4866M, or 0.4866 Moles of silver nitrate per liter of water.
To convert this to the number of grams of Silver Nitrate needed, simply multiply the
Molar concentration by the formula weight of Silver Nitrate, and the result is the number of grams
of Silver Nitrate, that was dissolved in one liter
of the solvent (in this case water). Crunching the
numbers gives us 0.4866 Moles/liter * 169.873 grams/Mole = 82.66 grams/liter.
A more "cook book" form of listing chemical concentrations may be found in many "recipe" style
books that call for a certain number of grams of a compound to be dissolved in a particular volume of
solvent, usually distilled water. In this case, changing the total volume to suit your needs is simply a matter of proportions.
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Traditional dimensions for glass plate collodion work are:
| Whole Plate: | 6.5" x 8.5" |
| Half Plate: | 4.25" x 5.5" |
| Quarter Plate: | 3.25" x 4.25" |
| 1/6th Plate: | 2.5" x 3" |
| 1/9th Plate: | 2" x 2.5" |
| 1/16th Plate: | 1.625" x 2.125" |
| Gem: | 0.5" x 1" |
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 |
 | The spectral sensitivity of
collodion is markedly different than what the
eye sees. The image on the left is a photograph of a solar spectrum captured on
collodion. A color image of the visible part of the same spectrum was also taken and overlayed on the
black and white image for reference. Note that the film's sensitivity extends far beyond the visible blue,
into the region of ultraviolet (UV). Also note that the lower end of collodion's sensitivity begins
to drop off in the middle of the visible spectrum, around blue/green. Thus, colors below green
(i.e. yellow, orange, and red) will not trigger an actinic response in the film, thereby leaving
those regions of an image containing these colors, black. Conversely, those regions of a scene that
are highly reflective in ultraviolet will appear bright white in a collodion photograph even though they
may appear dark to our own eyes in the original scene.
Okay, if you've been paying attention, you'll say..."but what about that bowl of red cherries I photographed?
They're not completely black. What's up?" Well, what the collodion is seeing there is the reflection of UV
light from the surface of the object. The object has color, yes, but it is also reflecting UV from it's surface, which
is what the film sees. |
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Here is a good general purpose collodion formula for making ambrotypes or negatives.
The total volume is 12 ounces.
| In a 16 ounce bottle, Pour: |
| 150 ml | USP standard collodion |
| 100 ml | Ethyl Ether |
| As you pour the ether into the collodion, you will notice a cloudy layer
form on the top of the collodion. Not to worry, this will dissolve as we proceed. |
| In a 50 ml beaker, dissolve |
| 3 ml | Distilled Water |
| 1.9 gm | Cadmium Bromide |
(For negatives, use 1.3 gm Cadmium Bromide) |
| The cadmium bromide is generally clumpy and hard and
will take a little time to completely dissolve. Gently heat the solution
on a hot plate while constantly swirling the liquid in the beaker to speed
the process along. Pour this solution into the collodion, cap the bottle and
shake vigorously. Rinse the 50 ml beaker with distilled water and dry.
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| 100 ml | Ethyl Alcohol (190 proof) |
| In a 50 ml beaker, dissolve |
| 3 ml | Distilled Water |
| 2.6 gm | Potassium Iodide |
(For negatives, substitute 3.2 gm Ammonium Iodide) |
| Swirl the liquid in the beaker until completely
dissolved. Pour this solution into the alcohol and swirl gently until mixed.
Pour the alcohol mixture into the collodion a
little at a time, capping and shaking the collodion after each addition.
When done, cap the collodion bottle and allow
to set undisturbed for a week. |
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At normal room temperatures, the collodion
will last 6 or 7 months. As it ages, the color will change from nearly clear,
to straw yellow, and eventually to redder hues as shown in the illustration where
collodion "A" is 1 week old and collodion "B" is 7 months old. As it ages, it may also begin
to loose sensitivity, and exposure times may increase. This color change is due to free iodine
being released into the collodion from the potassium iodide.
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Here is a good general purpose ferrous sulfate developer for collodion. (and it's easy to remember!)
The total volume is approximately 7.5 ounces.
| In an 500 ml beaker, Pour: |
| 210 ml | Distilled Water |
| 10 gm | Ferrous Sulfate |
| Stir the Ferrous Sulfate into the distilled water until it's completely dissolved, then add: |
| 10 ml | Acetic Acid |
| 10 ml | Alcohol |
| Mix thoroughly, and filter the solution into an 8 ounce bottle. |
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To better understand what the developer is actually doing and to make the recipe
a little less mysterious, let's look at the function of each component individually
and see what it does.
The first ingredient is water. This is merely the solvent which allows the various chemicals
to blend and provides a measure of dilution.
Next on the list is Ferrous Sulfate. This alone, is the developing (or reducing) agent. It acts to reduce
the exposed metallic salts (silver iodide) into metallic silver. Ferrous sulfate is an aggressive
developer, and by itself, without dilution or restraining, would begin reducing silver salts that
had not been exposed by the image forming light, thus resulting in a fogged plate.
The action of the developer can be restrained by the addition of an acid. The usual choice
for this is acetic acid, although other acids (such as Nitric Acid which tends to brighten the
surface of the metallic silver deposits) can also be used. Although if the amount of
silver iodide in the collodion is too little, or if insufficient silver
nitrate is present on the plate at the time of development, the use of nitric acid may prevent the
deposition of metallic silver in various regions of the plate.
Another commonly used restraining agent is sugar. When dissolved into the developer, the sugar
acts to thicken the fluid slightly, making it more viscous and thus slowing the physical agitation
of the developer on the plate, slowing the rate at which the developer comes in contact with the exposed silver salts.
Alcohol can be also be added to the developer as necessary to act as a "wetting agent" if it is found
that the developer has an oily appearance when poured onto the surface of the plate.
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Bromo-Iodizing Formulas for Collodion, 5%, USP |
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Ommeganck Port/Land) |
Ambrotype |
Ambrotype 2 |
Disderi Winter |
Disderi Winter 2 |
Disderi Spring |
Disderi Spring 2 |
Disderi Summer |
Copy Engraving |
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| Total Volume: |
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500 ml |
500 ml |
500 ml |
500 ml |
500 ml |
500 ml |
500 ml |
500 ml |
500 ml |
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| Collodion |
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110 ml |
110 ml |
215 ml |
100 ml |
100 ml |
95 ml |
95 ml |
75 ml |
85 ml |
| Ether |
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270 ml |
270 ml |
140 ml |
240 ml |
240 ml |
195 ml |
195 ml |
260 ml |
200 ml |
| Alcohol |
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120 ml |
120 ml |
140 ml |
160 ml |
160 ml |
210 ml |
210 ml |
165 ml |
215 ml |
| Distilled Water |
|
4 ml |
4 ml |
4 ml |
4 ml |
4 ml |
4 ml |
4 ml |
4 ml |
4 ml |
| Ammonium Bromide |
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. |
. |
. |
0.23 gm |
0.38 gm |
0.38 gm |
0.19 gm |
0.19 gm |
. |
| Ammonium Iodide |
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2.24 gm |
. |
. |
2.26 gm |
1.88 gm |
1.90 gm |
1.90 gm |
1.88 gm |
. |
| Cadmium Bromide |
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1.12 gm |
1.12 gm |
2.73 gm |
0.15 gm |
. |
0.38 gm |
. |
0.08 gm |
. |
| Cadmium Iodide |
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2.24 gm |
2.24 gm |
. |
1.50 gm |
. |
1.90 gm |
. |
1.13 gm |
3.80 gm |
| Iodine |
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. |
. |
. |
0.19 gm |
0.19 gm |
0.19 gm |
0.19 gm |
0.08 gm |
0.08 gm |
| Potassium Bromide |
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. |
. |
. |
. |
0.38 gm |
. |
0.19 gm |
. |
. |
| Potassium Iodide |
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. |
. |
3.64 gm |
. |
1.88 gm |
. |
1.90 gm |
. |
. |
| Zinc Iodide |
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. |
2.24 gm |
. |
. |
. |
. |
. |
. |
. |
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The formulas above were interpreted from data contained in The Silver Sunbeam, and converted to be used with
standardized pyroxyline solutions. Enter the total volume of iodized collodion needed in the text box, then click on the
'calculate' button. Find the column that corresponds to the type of Bromo-iodizing solution
appropriate for your application, then read vertically downward to determine the type and amount
of chemistry required.
Mixing of the chemistry is generally done as follows: Pour the collodion into a bottle large enough to contain
the total volume of chemistry. Pour the ether into the collodion. Cap the bottle and set aside. Pour the
water into a small beaker or shot glass. Weigh out the appropriate dry chemistry and place this into the water.
Stir this mixture with a glass rod, carefully crushing the solid pieces, until it is completely dissolved.
Pour this into the alcohol and stir until it is completely dissolved. Finally, pour the alcohol mixture into the
collodion a little at a time, shaking the collodion between additions to thoroughly mix the solutions.
Avoid mixing chemistry near open flames due to the extremely flamable nature of the alcohol, ether,
collodion, and their vapors.
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