Calotype
Calotype
Paper is coated with silver nitrate and potassium iodide, forming silver iodide. Prior to
use the coated paper is recoated with a solution of gallic acid, silver nitrate and acetic
acid. The gallinonitrate greatly increases sensitivity. When dry it is exposed to
ultaviolet light. It is developed with more of the gallinonitrate of silver solution. The
image is fixed with a weak hypo solution.
HAZARDS
Sodium thiosulphate (hypo) will release highly toxic sulfer dioxide gas if heated or if
acid is added.
PRECAUTIONS
Do not add acid or heat sodium thiosulphate
ALBUMEN PRINT
Paper is coated with a thin layer of albumen and sodium or ammonium chloride, and
then floated on a silver nitrate solution. When exposed to ultraviolet light the image
prints out without need for development. To obtain a better color, and to preserve the
image, the print is usually toned with gold chloride.
Hazards
The salting solution contains glacial acetic acid, which is highly corrosive to skin,
eyes and mucous membranes, and can cause respiratory problems from repeated
inhalation of vapours
Silver nitrate is moderately corrosive, eye contact can result in blindness.
Precautions for Albumen Printing
Wear gloves and goggles when handling concentrated acids.
Avoid skin and eye exposure and wear goggles when handling silver nitrate. Do not
inhale the dusts.
Acknowlegements:
The main source for this information has been
The Albumen and Salted Paper Book:
The History and Practice of Photographic Printing
James M. Reilly
Light Impressions
Rochester, NY 1980.
ISBN 0-87992-014-9 paperbound
ISBN 0-87992-020-3 cloth binding
Other Sources:
Care and Identification of 19th Century Photographic Prints
James M. Reilly
Eastman Kodak Company
Rochester, NY
Kodak Publication No. G-2S
CAT No 160 7787
ISBN 0-87985-365-4
Fundamentals of Photograph Conservation: A Study Guide
K. B. Hendriks, B. Thurgood, J. Iraci, B. Lesser, G. Hill
Lugus Productions Ltd.
Toronto, ON
ISBN 0-921633-80-7
CYANOTYPE
The cyanotype relies on the reaction of ferric or iron salts to light, where they are
reduced to the ferrous state. The ferrous salt reacts with the potassium ferricyanide to
from insoluble ferric ferrocyanide, also known as Prussian Blue. Separate solutions of
ferric ammonium citrate and potassium ferricyanide are made. Just prior to exposure
equal parts of the solutions are combined and the paper is coated. Once dry the paper
is exposed to UV light. The image is developed and fixed by rinsing the paper in
warm running water for about 10 minutes. The image will gradually darken as the
cyanotype completely oxidizes. The print can be oxidized by placing in a solution of
3% hydrogen peroxide. Other colors are possible by toning with a number of
solutions.
HAZARDS
Ammonium citrate and pottasium ferricyanide are only slightly hazardous. Pottasium
ferricyanide if exposed to intense heat, hot acid, or strong ultraviolet light may
decompose and release highly poisonous hydrogen cyanide gas.
Precautions for cyanotype
Do not add heat or acid to pottasium ferricyande and keep away from sources of
strong ultraviolet light.
Never mix ammonia and bleach which form lethal gases.
Wear gloves and goggles when handling ammonia solutions, and use good
ventilation.
If ferric ammonium citrate is used frequently, avoid skin contact.
A source for ready-made cyanotype paper is:
SOLARGRAPHICS
P.O. Box 7091P
Berkeley, California 94707
USA
(415) 525-1776
A Chemical Solution
The first three disadvantages could be overcome by using Ammonium Iron(III)
Oxalate instead of the citrate, because
It is more light sensitive.
It is not attacked by mould.
Its solution penetrates the paper fibres more readily (see my article on Paper).
But Ammonium Iron(III) Oxalate also causes a chemical problem, because when it is
mixed with Potassium Ferricyanide to prepare the sensitizer solution, the sparingly
soluble salt, Potassium Iron(III) Oxalate, crystallises out. A 'gritty' sensitizer is
useless, and if this happens within the sensitized paper it can cause quite pretty, but
totally unwanted fern-like patterns. The answer to the problem would be to use
Ammonium Ferricyanide instead of the Potassium salt, but this is unobtainable (so far
as I know) and rather troublesome to make.
Disadvantages (4) and (5) are due to the fact, already stated, that the cyanotype
process produces the so-called "soluble" form of Prussian Blue. Substitution of
ammonium ions for potassium ions in the structure would have the benefit of
diminishing this tendency, yielding an "ammonium blue" of good colour, which is
more resistant to peptization and alkalies.
All these problems (1) to (5) can therefore be overcome by the simple trick of
eliminating most of the potassium ions from the sensitizer; this is achieved by adding
finely ground solid Potassium Ferricyanide to an appropriate excess of a very
concentrated solution of Ammonium Iron(III) Oxalate, allowing it to crystallise then
filtering off and rejecting the solid Potassium Iron(III) Oxalate that results. The
biggest objection to this procedure is the present artificially high cost of Ammonium
Iron(III) Oxalate, but cheaper sources of this chemical are now becoming available.
The 'user friendly' sensitizer is a single solution with a very good shelf life, and it
provides excellent image quality.
The following recipe is not engraved on tablets of stone; it has given the author very
satisfactory results so far, but deserves to be more extensively tested, and may yet
allow room for improvement by fine-tuning the concentrations.
Choice of Papers
The cyanotype sensitizer is a delicate test of paper quality - especially if the coated
paper is left for some hours in the dark at normal relative humidity: any change of the
bright yellow coating towards a green or, worse, blue colour is an indication of
impurities or additives in the paper that are hostile to this process (and possibly to
other processes as well). I recommend Atlantis Silversafe Photostore 200 gsm, Arches
Platine 310 gsm, and Whatman Watercolour 290 gsm; but the best results (of course!)
are obtained on Ruscombe Mill's handmade 'Buxton' paper, (see my article on paper).
Coating Techniques
Coating by the rod method will require approximately 1.5 cc of sensitizer for a
10"x8"; brush coating consumes more, but try to avoid excess sensitizer which may
puddle and crystallise. I have to remind you that this sensitizer solution is toxic if
ingested (much more so than traditional cyanotype) and it will obviously stain skin,
wood, clothes, textiles, household pets and any other absorbent surfaces.
Drying
It is simplest to let the sensitized paper dry at room temperature in the dark for about
one hour; but there will be no difference if you prefer heat-drying at about 40°C for
10 minutes. Expose the sensitized paper within a few hours of coating, if possible. Its
storage life depends on the purity of the paper base, as mentioned above; it will keep
longer in a desiccated enclosure. The coated side should remain light yellow: if it has
turned green or blue reject it, because the highlights will be chemically fogged, and
look for a better paper.
Negatives
For a full tonal range in the print, the negative should have a long density range of at
least 1.8, like those for platinum-palladium printing; i.e. extending from base+fog at
around 0.2 to a Dmax of 2 or more. This is achieved by "overdeveloping" the negative
to the extent of 70%-80%.
The contrast of the sensitizer can be lessened by adding citric acid, so that it can even
accommodate a negative density range of 2.6 or so. Conversely, the contrast can be
increased by the addition of more ammonium dichromate solution.
Unlike the traditional cyanotype sensitizer, I have not encountered any problems with
this sensitizer damaging negatives during contact printing.
Exposure
Whether the light source is the sun or a UV lamp, exposure is much shorter than that
needed for the traditional Cyanotype recipes - this new sensitizer requires about five
minutes exposure under an average light source.
Since this is a print-out process, a traditional hinged-back contact printing frame
should be used; the image can then be inspected without losing registration and the
correct exposure reached without the need for preliminary test strips. The exposure is
continued until the high values just appear green, the mid-tones are blue, and the
shadow tones are substantially reversed to a pale grey-blue, giving the image a
"solarised" look.
If you do not mask your negative when printing (with ruby lith tape, for instance) but
expose the entire coated area, then you will never know if the print is properly
cleared. This is the disadvantage of 'showing the brushmarks' to prove it's a handmade
print.
Wet Processing
You can process the exposed paper most simply with nothing more than a few
changes of water, but a better gradation with stronger shadow tones is obtained if it is
treated initially in a bath of citric acid solution (strength1% to 2%) for 10 minutes.
This bath should be replaced after a few prints have passed through it: typically, 1
litre will process ten 10"x8" prints. The yellow stain of sensitizer should clear
completely from unexposed areas - it is worth holding the print up to a bluish light to
check that no yellow stain remains in the interior of the paper; if the stain persists, use
a second citric acid bath. Finally wash gently in running water for about 20 minutes.
Unlike prints made by the traditional recipe, there should be very little loss of image
substance during this procedure.
The reversed shadow tones usually regain their full values quite rapidly during the
wet processing, but if not they will do so during drying (24 hours). However, if you're
anxious to see the final result immediately, then immerse the print in a bath of 0.3%
hydrogen peroxide (50 cc of the 6% solution -so-called "20 volume"- diluted to 1 litre
of water) for no more than half a minute. This treatment makes no difference to the
final result.
Disclaimer
It is the responsibility of the user of toxic chemicals to take appropriate precautions to
avoid ingestion. The author cannot accept liability for any injury, sickness or damage
resulting from this process.
KALLITYPE
The kallitype is an iron-sensitive process that uses silver to form the image. The
kallitype emulsion is a mixture of ferric oxalate and silver nitrate, with the addition of
either oxalic acid or potassium oxalate. When exposed to light the ferric oxalate is
changed to the ferrous state, which reduces the silver nitrate to the metallic silver.
When developed the ferrous oxalate is dissolved and the metallic silver is left forming
the image.
The kallitype process is a very unforgiving one, great care must be taken. The
resulting prints are quite similar to platinum prints, however kallitype prints are not
nearly as permanent as platinum, although substantially cheaper to produce.
Hazards
Silver nitrate is corrosive to the skin , eyes and mucous membranes, eye contact can
cause blindness. Oxalic acid and ferric oxalate are highly corrosive. Gold chloride
used for toning is a moderately irritating compound that can cause severe skin and
respiratory allergies. The developer may contain potassium dichromate increasing
skin and respiratory hazards, causing skin and respiratory allergies and ulceration.
Potassium dichromate is a suspected human carcinogen. The fixer contains ammonia
which is highly irritating to the eyes and respiratory system.
Precautions for Kallitype Printing
Wear gloves when handling silver nitrate. Do not spray on silver nitrate sensitizer
unless done in a spray booth
Wear gloves and goggles when handling ferric oxalate or oxalic acid solutions. Mix
solutions in a fume hood or inside a glove box, or wear an approved toxic dust mask.
Wear gloves whenhandling potassium dichromate or pottasium oxalate. Mix solutions
in a fume hood or inside a glove box, or wear an approved toxic dust mask.
Kallitypes
Photography improves in a constant way, forever in the same direction. Films are
faster, lenses more luminous, shutters are working at 1/4000 s. Images of our world
that condescend to stay in our mind are such tiny moments, joined end to end, they
rarely excess a few minutes. The waves of images are invading our daily world
without giving us the time to really see them. Television, video, newspapers,
magazines, publicity and posters bring everyday a stupefying harvest of what some
still dare to call "choc des images" (image impact).
As a reaction to this tendency of photography, I wanted very much to find a way to
depart, travel, photograph and send very personal and emotional images to some
friends. I wanted this photography to be quite elementary (rudimentary) and
concentrated. By concentrated, I mean that the concentration of the photographer,
between the exposure and the final result, should not relax. A complete cycle of image
creation would have to happen at the same place without discontinuity. The
photographic image would then be able to become impregnated with the location and
the confrontation of the photographer with his subject would last more than 1/125 of a
second. The pinhole camera is the only solution because of its exposure time of many
minutes.
All alone on my island with the pinhole camera, two hours rowing hard from the
civilisation, I was happy. I was thinking of the pioneers, Charles Nègre and others,
who much sooner than me, had enjoyed developing on location. Yes, processing on
site, that was important. Polaroid film, the only concession to modernism gave me the
possibility to do it. Have you ever tried to wash your negatives with seawater, you
should try it!
A small amount of watercolour paper, impregnated with kallitype emulsion, was my
printing paper, which was contact-exposed in broad daylight. The richness of tone of
the kallitype (sometimes enhanced with metallic brilliance due to silver excess), the
versatility of the process, and the free choice of the paper all persuaded me
Palladium
When exploring the use of other palladium chloride compounds in
the photographic process I came across a note which stated that
lithium chloride was perhaps the most hygroscopic material known.
I then surmised that its palladium salt would also display similar
traits.
A very strong print out image was produced, but the contrast was
very high, a great deal of graininess was produced, and the image
darkened considerably when washed in the water. After several
prints I noticed that the darkening was increasing with each print.
I suspect that this was due to the small quantity of EDTA
tetrasodium that we add to our standard ferric oxalate solution.
EDTA tetrasodium has a developing effect on any platinum print. I
switched to an EDTA-free ferric oxalate solution and the darkening
went away, but the prints remained grainy and contrasty.
The prints produced were neutral black, with a dead slate gray in
the mid tones and hint of brown. They appeared very much like
pure platinum prints.
Many people associate cesium with the atomic clock at the National
Bureau of Standards in Washington D.C.. That clock runs on a
radioactive isotope of cesium. Many normally non radioactive
elements have radioactive isotopes and cesium is one of them. The
cesium salt we use in non radioactive and in fact, the teeny tiny
portion of the hot stuff is removed before it ever gets to us.
Replacing all of the lithium chloropalladite with gold requires a double strength ferric
ammonium oxalate and 10% gold chloride. My suspicions are that a small quantity of
palladium is needed to strengthen the effects of the gold. There is little difference in
color or contrast between a 5 x 7 print made with 7 drops of 5% gold chloride and a
print made with 8 drops of 10% gold chloride.
Perhaps it is only a semantic argument that one print could be said to be pure gold,
while the other is only 80% gold and 20% palladium.
The addition of gold, however, increases contrast considerably,
especially at higher percentages. As information is obtained from
workers in the field, we'll pass it on it future Ziatype instructions.
Reports from the field are indicating that any exposure less than 2
1/2 minutes in a UV fluorescent light bank is probably too short
even if the overall exposure is good there may be some crushing of
the midtone values. In this case add more No. 2. ammonium ferric
oxalate or a drop or two of a 8% potassium chlorate solution. This
will boost the contrast, which you can then reduce by increasing the
length of exposure. This technique can be used to expand the
middle values. Since the Ziatype black can take large amounts of
No. 2 or "chlorate boost" without graining up, this can be a valuable
technique, however, printing times can increase at an alarming
rate.
Developing Out
This system has another remarkable property in that it will work as
a traditional developing out system as well as a printing out system.
I produced some interesting split tones with gold and palladium; the
shadows being brown-black, the mid-tones and highlights moving to
lavender-purple.
Clearing Baths
Use Either:
sodium sulfite 15 gm
*
water 1000 ml
citric acid 15 gm
*
water 1000 ml
Kodak Hypoclear 25 ml
*
water 1000 ml
EDTA tetra-sodium 15 gm
*
water 1000 ml
ferric ammonium
10.0 gm
Solution No. 1 oxalate
water 25.0 ml
ferric ammonium
10.0 gm
oxalate
Solution No. 2
potassium chlorate 2.0 gm
water 25.0 ml
Solution No. 3 palladium chloride 2.3 gm
Lithium chloropalladite: lithium chloride 1.7 gm
Charcoal Black water 25.0 ml
sodium tungstate 4.0 gm
water 25.0 ml
Solution No. 4 This solution may be diluted for smaller
Warm tone additive: prints.
1 drop of this concentration will produce
quite a bit of warmth in an 8x10 print.
Solution No. 5 potassium chlorate 2.0 gm
Contrast boost - 8%: water 25.0 ml
Solution No. 6 5%
gold chloride
Gold chloride: solution
For gray/blue/purple
tones
Clearing and Washing
Rinse in plain tap water. It will clear in about 1 minute.
The Procedure
The ratio of the coating solutions is the same as in normal palladium
printing. The total drops of ammonium ferric solution will equal the
number of drops of lithium chloropalladite or cesium chloropalladite.
Use the lithium chloropalladite for cold tones , for warm tones add 1
or more drops of sodium tungstate Solution No. 4.
* I prefer to coat with a glass rod, though a brush will work. The
trick is to get enough, but not too much emulsion on your paper.
When coating a 5 x 7 print with a glass rod I've found that 3 or 4
slow swipes across the print is enough. The last swipe pulls any
excess emulsion to the edge of the print or off the paper entirely iii.
* Dry with a hairdryer or use the method you've been drying your
standard platinum palladium prints .
Hold the print over the spout with the emulsion side facing the
spout and move the print around to steam the paper evenly.
* Expose the print either in the sun or with a UV light source. Within
a minute or two in the sun, or several minutes under artificial light
you will see the margins darken. In a few minutes more the
margins will darken to a dark purple black.
(You may want to use a piece of 1 mil Mylar or acetate between the
negative and the paper to prevent any damage to the negative.)
(A moist paper towel placed between the acrylic dam and the back
of the print frame helps retain moisture during exposure though it is
usually not necessary. The order: frame glass, negative, Ziatype
coated paper, plastic dam, damp paper towel, back of print frame.)
* Immerse the print in water and wash for 5 minutes. With some
papers there may be a yellow tint left in the paper. In this case
clear for 5 minutes in Kodak Hypo clear or equivalent, or sodium
sulfite, or any other platinum clearing agent, then rewash for 5
minutes.
* Sell for money, give to friends, or keep in a secret box under your
bed to be privately enjoyed when you're feeling down.
Color Control
Red/blue
Important!
Split tones
A lithium coated print that is fully steamed before exposure and the
humidity being preserved during exposure by the use of a plastic
dam between the frame back and the print will produce a neutral
black image with pure palladium. If the paper is slightly dried before
exposure, the resulting print will have a brown cast to it.
The print out image will not be as strong as a fully steamed print
but if re-steaming is done after exposure the print will darken. A
Ziatype palladium print that is dried and not steamed before
exposure will give little or no printout image. It will develop out fully
with steaming after exposure and will be sepia in color.
If Cold Bath Developer is used the print will be a rich brown-black.
Most other standard pd/pt developers will produce brown to sepia
images.
Platinum
* Better contrast control with less graining using No. 2 than with
developing out systems.
* Better paper tolerance, it's not as picky about the paper it's on.
Toxicity Issues
Since both Lithium chloropalladite and cesium chloropalladite are
very rare compounds and are not in general use in industry, there is
no available toxicity data. However groups of compounds usually
share similar toxic characteristics. For instance mercury
compounds, if water soluble, are all poisonous, as are most
cyanides. The lethal dose for cesium chloride is listed as 1.5 g per
kilogram in mice and lithium chloride as 1.06 gram per kilogram in
mice.
This roughly translates into 50-75 grams for a lethal dose in a 150
lb human. The are only modestly poisonous. Palladium chloride is
18 mg (thousands of a gram) per kilogram in rabbits as a lethal
dose. We can extrapolate that the cesium and lithium versions of
the palladium salts are only very slightly more poisonous than the
sodium tetrachloropalladite in common usage in palladium printing.
Disposal
Bostick & Sullivan will be happy to recycle any leftover quantities of
platinum or palladium salts. For small quantities , dilute with several
volumes of water and soak a piece of steel wool in it overnight. The
steel wool will become plated with the platinum or palladium metal
from the solution leaving the harmless chloride behind. There
should be some dark sludge which will be harmless iron compounds.
The steel wool can be safely disposed of and the chloride should be
sewer disposable, though you should check any local ordinances,
especially if you are on a cesspool.
i Named for the ancient Southwest Anasazi symbol for the sun, familiar as the circular
image with 4 sets of 4 rays seen on the flag of New Mexico and its license plates. It
seemed appropriate as we have just moved to New Mexico and I have been using its
sun to make the prints
ii Hygroscopic: readily absorbing moisture, as from the atmosphere
iii Too much coating will cause grain and splotchiness in the print, This is due to the
printing out nature of the process. The printed out portion will mask any sensitizer
underneath the exposed layer, and if tiny particles of the top layer flake off, the
bottom layer will not be exposed and show as white grain. There is no gain in dMax
obtained by heavy coating.
Ziatype Images provided
by Dick Sullivan
CARBON PRINT
A tissue is coated with a gelatine solution carrying a pigment sensitized with a
dichromate. When it is exposed to light the gelatin hardens and becomes insoluble.
The gelatin hardens only on the surface, to counteract this the exposed and washed
tissue is placed firmly on a final support and then peeled away, transferring the image
to the final support. This leaves the image flipped over on the final support and
exposes the unhardened gelatin.
The transfer tissue is the temporary support that holds the gelatin pigment mixture
during exposure. After exposure the gelatin and pigment are transferred to the final
support. There are no current manufacturers of transfer tissue. The pigment transfer
tissue can be made by hand. This makes the carbon process somewhat complicated.
A pigment tissue is made by coating a support with a mixture of gelatin and pigment
and other a number of other ingredients. After the pigment tissue has been coated it is
sensitized with a dichromate, and left to dry. The pigment tissue is the exposed to UV
light. The dichromate causes the gelatin to harden where it is exposed to light.
After exposure the tissue is soaked for a few minutes to allow the excess dichromate
to dissolve out and to allow the tissue to flatten. The tissue and final support are
placed face to face under water and aligned. The two sheets are then carefully pulled
out of the water, placed on a flat sheet (glass) and lightly squeegeed together.
The sheets are then weighed down for about 20 minutes. The two sheets are then
placed in water at about 40 degrees C. The soluble gelatin and pigment will begin to
ooze out. After another minute, carefully peel the pigment tissue off the final support.
At this point there is no visible image on the final support, it consists of a mass of
undissolved gelatin and pigment.
The final image is developed by agitating in all directions the final support in water in
a number of baths, until the image is fully developed. The image develops by the
unhardened unexposed gelatin dissolving in the water. The exposed gelatin is
hardened by the dichromate and made insoluable in water. After development is
complete the image is immersed in cold water to harden the gelatin. The resulting
image is made up of only gelatin and pigment, making the carbon print one the most
archival processes.
Hazards of Carbon Printing
The sensitizer contains pottasium or ammonium dichromate, which are both
moderately irritating to skin and highly irritating to the respiratory system.
Dichromates can cause skin and respiratory allergies and ulcerations. They are both
suspected human carcinogens. Ammonium dichromate is flammable and unstable
when in contact with many materials. The hardening bath conatins formalin which
ismoderately irritating to the respiratory system, causing severe skin and respiratory
allergies including asthma. Formalin is poisonous if ingested and is a suspected
human carcinogen.
Precautions for Carbon Printing
Wear goggles and gloves when handling pottasium dichromate or sodium dichromate.
Mix powders in a fume hood or dust box, or used an approved toxic dust mask.
Keep ammonium dichromate away from sources of heat and store seperately from
other chemicals.
Wear goggles and gloves when handling formalin baths. For large amounts use a local
ventilation system.
ULTRASTABLE
The UltraStable process is a direct descendant of the original tricolor carbon process.
While the original process used several transfers and manual registration techniques,
this new incarnation makes the possibility of obtaining beautiful permanent color
images much more easily.
The UltraStable process makes use of pre-sensitized pigment sheets. There is no
messy and dangerous handling of dichromate and the shelf-life of the materials is
about one year at room temperature or longer if refrigeration is used.
This process is relatively new. A computer is used to generate color separation
negatives from the original image. The original image is first digitized by using a high
resolution scanner. Computer software is used to produce four half-tone separation
negatives of the same type used in the printing industry. The closer the dots are
printed together the darker the image appears. This is the same technique used to print
images in books and newspapers only much more refined. One can get wonderful
separations and screened negatives with a high resolution scanner and printer. The
process can also be (and is) used with optically produced continuous-tone negatives
The exposure of the pigmented sheets and the development is very similar to carbon.
The main difference between the Ultrastable process and the traditional carbon
process is that the former uses convenient pre-sensitized pigmented sheets on
dimensionally stable polyester sheets so that automatic registration is possible. The
main drawback is that screened negatives are required and most people will have to
use a service bureau to have them made.
There is more information available on UltraStable in the book: The Permanence and
Care of Color Photographs : Traditional and Digital Color Prints, Color Negatives,
Slides, and Motion Pictures , by Henry Wilhelm with contributing author, Carol
Brower.
Ultrastable materials and information are available from:
UltraStable Color Systems
500 Seabright Ave. Ste. 201
Santa Cruz
95062 California
USA
Tel 1-408-427-3000
. Fax1-408-426-9900
CARBRO PRINT
In carbro printing a pigment tissue similar to that used in Carbon printing is brought
in contact with a bromide print. The gelatin in the pigment tissue loses its solubility
through the chemical reaction between the sensitizer on the pigment tissue and the
silver in the bromide print. The tissue is then transferred to the final support and
developed in the same manner as a carbon print.
The advantages of a carbro print is that the pigment tissue is never sensitive to light
and a UV light source in not necessary since the bromide print is made using
traditional silver-gelatin methods.
Most bromide prints made today are coated with a hard surface to protect the fragile
gelatin underneath. It is not possible to use these papers in carbro printing. Common
unsupercoated papers currently available are: Kodak Polycontrast Rapid RC matte
surface, Luminos RD Matte Bromide, Agfa Portriga Rapid No. 118, SupreBrome
Royal Portrait Matte Paper, Ilfobrome Semi-Matte paper.
Hazards of Carbro Printing
The main hazardsof carbro printing result from exposure to the bromide developer
and to the sensitizer for the carbon tissue. The developer can be a skin irritant causing
allergies. The sensitizer for carbon tissue contains potassium dichromate which is
moderately irritating to the skin and highly irritating by inhalation. It can causeskin
allergies and ulceration. It is also a suspected human carcinogen.
Precautions for Carbro Printing
Use the least toxic bromide developer.
Do not heat or add acid to sodium thiosulphate
Wear gloves when handling dichromate sensitizer. Mix in a fume hood, glove box or
wear an approved toxic dust mask.
Avoid inhalation of pottasium bromide powders.
Wear gloves when handling solutions during transfer and development of the carbon
tissue to avoid skin contact with pottasium dichromate and pigment suspended in
gelatin.
BROMOIL PRINT
by Rita Carnes, Albuquerque, New Mexico
[email protected]
Bromoil printing begins with a normally developed silver print. A non-hardening
developer, such as amidol or Ethol LPD, is preferred for processing. Subsequent
bleaching and tanning of the print removes the silver and results in selective
hardening of the gelatin. In other words, the non-hardened areas of the print (the
highlights) will absorb water and repel ink. The hardened parts of the print (shadows
and mid-tones) will accept ink, resulting in a positive image resembling the original
print. The advantages of bromoil are that (a) it allows a considerable degree of control
over final image quality and (b) it is permanent.
The bleaching/tanning solution is made of distilled water (1000 ml), into which 70 ml
of 10% solution copper sulphate, 70 ml of 10% solution potassium bromide, and 30
ml of 1% solution potassium dichromate is added. This solution will bleach out about
a dozen 5x7 prints.
The ink used in bromoil printing is similar to lithographic ink. Hard ink is used
initially, followed by soft ink, although the former alone will result in a lovely effect
resembling etching. Brushes are specially-made of either hog, bear or fitch hair. A
source for materials is provided at the end of this article.
The inking process involves first soaking the matrix (what the original print is called
after bleaching and tanning) in water to induce the differential swelling of the gelatin.
Test strips are used to determine optimal soaking times, starting with five minutes and
continuing up to about 20 minutes. The test strips should be completely free of
surface water before applying ink. The strip that accepts the ink most easily, with
good buildup in the dark areas and clear highlights, will determine the proper soaking
time.
The matrix is then soaked for the determined time and the surface water removed
(using a damp chamois). The matrix is then placed upon a support and ink is applied.
The inking process requires considerable practice to master the technique and
involves lightly coating the surface, pushing the ink into the shadows and mid-tones
and out of the highlights. The matrix may have to be re-soaked several times during
the inking process, especially if resin-coated paper is used. The final print is allowed
to dry for several days before matting and framing.
Bromoil supplies and materials can be obtained from David W. Lewis, 457 King St.,
Box 254, Callender, Ontario, Canada, P0H 1H0.
References:
History and Practice of Oil and Bromoil Printing, by Luis Nadeau
The Art of Bromoil and Transfer, by David W. Lewis
The Keepers of Light, by William Crawford
Hazards
Potassium dichromate and potassium bromide are moderately irritating to skin and
highly irritating by inhalation. They can cause severe allergies and ulceration, and are
also suspected carcinogens.
Copper sulphate??
Ink??
Precautions for Bromoil Printing
Use the same precautions followed in silver printing.
If amidol is used as the developer, then mix the solution outside the darkroom since
the powder can become airborne and contaminate paper, resulting in purple stains.
POLAROID TRANSFER
The Polaroid transfer uses Polaroid peel apart color films in an unconventional
manner. The Polaroid pack is peeled apart during processing, the positive image is
transferred to an alternative surface. The surface the image is tranfered to imparts a
different quality to the image. A receptor sheet is prepared, this will hold the final
image. If paper is being used it is thoroughly soaked, other media can be used such as
silk and other textiles.
The Polaroid negative is exposed, recording a new image, or by projecting a
previously made slide onto the Polaroid. The film is processed in the pack as normal
except the film is peeled apart after about 10 seconds. The negative containing all the
dyes is then placed on the prepared receiving sheet. The negative is then firmly
pressed onto the receptor sheet using a roller or your hands. It is critical to use even
pressure. After waiting 90 seconds to two minutes the negative is peeled off the
receptor. The dyes have now been transferred to the recieving sheet transferring the
image to the receptor sheet. The quality of the transferred imaged depends on the
method of transfer and the nature of the receptor sheet. A wide variety of papers and
textiles can be used for receptor sheets.
Polaroid makes a variety of peel apart films in different sizes. Transfers will not work
with black and white polaroids or with the SX70 style instant polaroids or other
"integral" film types
Polaroid has produced a publication on Polaroid Transfer. They can be reached at
Toll Free at 800-225-1618
Hazards of Polaroid Transfer
The main hazard of Polaroid films is exposure to the highly caustic processing jelly,
which contains sodium hydroxide or pottasium hydroxide. It remains at a high pH on
the discarded portion (the non-image and negative area) for up to two hours. It is
highly corrosive to the skin eyes and mucous membranes.
Precautions for Polaroid Transfer
Avoid skin or eye contact with residual processing fluid.
Dipose of wet negatives in a closed waste container to prevent further contact.
If children chew or ingest film flush with water and contact a poison control center.
1. The Colloid. Mix 1/4 cup non fat powered milk with 8 oz. hot water. Mix 3 cc
Glacial Acetic Acid with 7 cc water. Add to the milk mixture. A curd will form
immediately. Separate the curd from the whey using a fine strainer or a piece of fine
mesh and gently wash the curd under cool water until the acid smell goes away. This
should take five minuets. Put the washed curd in a beaker and add 75 cc of household
Ammonia. Buy a fresh bottle, it loses its strength quickly once the bottle has been
opened. It takes about 24 hours for the curd to dissolve in the Ammonia. Put it in a
small jar after it is completely dissolved. I never add any preservative. I use it before
it goes off.
2. The Basic Mix. For pigments I use Winsor Newton transparent watercolors. I have
a gunpowder scale so I measure in grains. Each color requires a different amount of
pigment. Not all colors work well. As an example Chrome Oxide gives unpredictable
results. It stains and does not react well with Ammonium Bichromate. I had best
results with Lampblack. I do not know how you measure so you will have to
experiment. As is true in the gum process, too much pigment causes staining.
Mix 40 grains or 2.6 grams WN Lampblack to 50 cc of the Casein. Put this in a small
jar.
For other WN colors try these proportions
Color For 50 cc of colloid
Alizarin Crimson 52 grains or 3.5 grams
Thalo Blue 40 grains or 2.6 grams
Cadmium Yellow 60 grains or 4 grams
Hansa Yellow 12 grains or .8 grams
Burnt Sienna 60 grains or 4 grams
Burnt Umber 60 grains or 4 grams
Solution A:
Potassium Bromide 168 g
Potassium Iodide (5% solution) 62.4 ml
Inert Gelatin 160 g
Distilled Water 3500 ml
Solution B:
Silver Nitrate 160 g
Solution C:
Gelatin 20 g
Solution D:
Distilled water 50 ml
Immediately chill the emulsion using an ice bath. Chill until the
emulsion is very solid, whack the side of the container, there
should be a distinct 'jiggle' feeling.
Final Prep:
Add solution D, mix. The Tartrazene dye is used to absorb blue light to cause the
depth penetration exposure effect, and to minimize scattering. A wetting agent
(saponin) is added to promote even coating.
Use care when making the emulsion. Completely scrub the mixing vessel, beakers,
stirring paddle, stirring rods, etc. Use soap, and an abrasive scrubber. Rinse
thoroughly, final rinse with distilled water. Filter the emulsion with 5um filter paper
using a vacuum filter before coating. A filter must be installed in the coater, placed in
a position before the emulsion passes through the slot. Thoroughly clean all mixing
vessels, and other utensils as you go, and carefully clean the coater after a coating run
to prevent buildup of gelatin which would re-melt into subsequent emulsions. The
coater must be repeatably rinsed with hot water between uses. All operations are best
carried out using the light of a sodium safelight, which provides adequate light for
working for long periods of time.
About Gelatins:
The gelatin greatly affects the sensitization of the emulsion. In the past, less refined
gelatins which contained sulfur compounds were used. These are termed 'fast'
gelatins, and they sensitize the emulsion without the need to add a thiosulfate
sensitizer. The problem with this is that each batch of gelatin will have a different
effect. In modern emulsions, either a highly refined inert gelatin is used, or the gelatin
is artificially synthesized. This allows a controlled sensitization by addition of sulfur
and gold compounds to the mix. I find that the lot controlled Kind and Knox
photographic gelatins work very well. They harden well in the tanning developer,
withstand vigorous washoff, have low fog characteristics, and absorb and transfer the
dyes readily. Use of other gelatins will probably yield very different results!
The Dyes I am using are as follows:
HL reducer: 20 g Sodium Hexametaphosphate in 1.0 L Dist. Water.
Cyan:
Acid Blue # 25 1 g
HL Reducer 10 ml
Set pH to 4.80
Magenta:
Acid Red # 289 1.5 g
HL Reducer 100ml
Set pH to 7.00
Yellow:
Acid Yellow # 23 3.2 g
HL Reducer 10 ml
Set pH to 4.00
Mix the dyes with about 100 ml of distilled water and heat to near boiling. Add a few
crystals of Thymol as a preservative. Add most of the remainder of water. Titrate the
solution to the specified pH using Acetic acid and Trieth. Be careful not to let
magenta dye solution become more acidic than pH 4.0 at any time, as this will ruin
the dye. Top off with distilled water to make 1L of dye. Filter before use. Check the
pH frequently, and adjust. Filter frequently during use. You may make up a more
concentrated replenishment dye, which is added as the dyes are removed from the
working solution. Thanks to Andy Cross for determining these dye mixtures.
Developer:
Expose the film through the base (Emulsion down), and develop in the following
tanning developer:
Solution A:
Benzoatriazole 2.0 g
Metol 28.0 g
Pyrogallic Acid 30.0 g
Water to make 4L
Solution B:
Mix 1 part A to 2 Parts B for normal contrast, develop for 2 minutes @ 68 deg F.
Make sure you presoak the film for 1 minute. Rinse film in cold water for 30 sec, and
fix in a non-hardening fixer for 5 min. Wash off unhardened gelatin using four of five
vigorous rinses at 120 deg. F. Dry. Soak matrices in 120 deg. F water for 1 minute
prior to soaking in dye for at least 5 minutes. Transfer the image for at least 5 minutes
for the cyan and magenta, and 2 minutes for the yellow.
Condition the paper in paper conditioner for about 15 minutes before transferring the
image. This is Bob Pace's formulation, I haven't tried it.
Triethanolamide 60 ml
Water to make 4L
For a complete discussion making separations, exposing and developing the matrix
film, and rolling the prints and retouching, please refer to the books mentioned. This
area is where DT printing really shines, and printers develop their own unique
methods for controlling the print during the rolling process.
Some of the controls you can add to the first rinse are:
A simpler method of coating should work well with smaller sheet sizes. Make an
aluminum blade longer than the width of film to be coated. The blade can be
rectangular in crossection, with a triangular point, or it could be a simple cylinder.
Wrap a wire around the blade tightly over the full length. By adjusting the gauge of
the wire, you can control the amount of emulsion passing through the gaps between
the wraps, thus controlling the emulsion thickness. The emulsion and film should be
hot enough to allow the emulsion to flow after doctoring it with the blade. Pour a
supply of emulsion in front of the blade, and draw it through the emulsion, and over
the full length of the film. The ideal thickness of the emulsion will b e enough to
allow heavy exposure of the matrix film without having the image appear appreciably
during development. A too thick emulsion will reticulate when chilled or during
drying, which will pattern into the image. A too thin emulsion will 'print through', and
the rough surface of the film will texture the image, as well as limiting the DMAX of
the print. Start with 100 ml of emulsion for a 16x20" film.
Tips:
The dyes transfer very well, but as with all matrix film transfers, you need to maintain
the temperature at least at 70 deg. F, with higher temperatures working better. The
magenta dye does have a tendency to stain the fil m base slightly, but this should not
affect the image. It also may be necessary to use an ammonia / calgon matrix cleaner
on the magenta matrix to remove the last bit of dye. highlight clarity may be
controlled by using a small amount of the highlight reducer (Sodium
Hexametaphosphate) to get the clearest highlights, near paper white. Use a good
quality fiber based paper - I have used Ilford Multigrade FB, fixed out with a non-
hardening fixer. I have also used Arches hot pressed paper which I treat with a silic
one water repellent, and then size with gelatin, and harden. You may mordant the
paper with an aluminum salt, but the image transfers well, is sharp, and has good
water fastness without the use of a mordant.
Materials Cost:
The cost of materials is about $8 per sheet of 30x40" film, most of the expense is in
the silver, I buy the inert photographic gelatin from Kind and Knox in minimum 25
LB lots costing $ 10 / LB, and the polyester film cost about $ 0.50 / foot of the 50"
wide rolls. The Silver Nitrate is from First Reaction at $ 277.00 / Kg.
About making Seps:
I am creating my separations digitally using a laser based film scanner / film recorder
I designed and built a few years ago. I typically use 150mb files, which make 20x24"
prints which are completely sharp, and show no digital artifacts. The recorder both
scans the originals (Up to 150 l/mm) and records onto 8x10" film (EPN, VPS, TMX).
The film is held on registration pins, which allows exposing three seps in perfect
register.
Alternately, seps can be made by exposing TMX (Tmax-100) film using red, green,
and blue filters. Red and Green exposed color correction masks should be used when
making the seps. Develop the seps to a higher gamma than the old Kodak film, Dmax
should be about 1.50 above base fog. Make a highlight bump mask with about a 0.30
density which records only the highlights. Print each sep with it's associated highlight
mask onto the matrix film. Develop in the tanning developer. The masking for this
dye set will be different than the old Kodak dyes, but I haven't yet determined the
correct masking for this dye set. I'll supply this information when I have it.
Some Phone Numbers:
Unique Photo 800-631-0300 (best prices on film - use TMX for
seps)
VWR Scientific 800-932-5000 (General chemical supplier)
Photographer's Formulary 800-922-5255 (General
Photographic chemical supplies)
Condit Mfg. 203-426-4110 (Warren Condit) Makers of pin
registration equip.
Carolina Color and Chemical 704-333-5101 (Supplier of Dyes)
ICI 800-648-1926 (maker of Melenex polyester film stock - I
recommend Melenex 583, this doesn't pick up dye, and has an
anti-static coating on the back.)
First Reaction 603-929-3583 Best price on Silver Nitrate.
Specializes in compounds of precious metals.
Kind and Knox - 800-223-9244 (maker of Photographic
gelatin)
Bob Pace 11534 Francisco Pl. Apple Valley, CA 92308
619-247-0795. E-Mail: [email protected] Bob is a leading
expert in dye printing, and has helped many in the past with
his newsletter Keeping Pace, which unfortunately, he has
discontinued. Ask Bob about his Dye Transfer book, and back
issues of Keeping Pace.
Dr. Jay Paterson 713-768-4581 (head of Dye Transfer Co.
Houston) They are making matrix film for sale. I have had a
chance to test this film, and I find that it works quite well.
They also have a very nice paper. They are still working on a
dye set at the time of this writing (Nov '97), but they should
be available soon.
You should try to buy the book :
The Dye Transfer Process by David Doubley. Condit used to sell this book.
If you need some advice about DT printing, or matrix film coating, please feel free to
contact me:
[email protected]
Digital Mask
187 Stevens Rd.
Lebanon, NH 03766
603-448-6241
PRINTMAKING
Etching . . Ultraviolet exposure . . Etched plate . . Etching papers and Japanese washi
Prints are made in limited editions from inked plates pressed against special papers.
With woodcuts and lithographs, the ink is transferred from a raised or treated surface.
To make an etching, ink from the incised lines or points of a copperplate is pressed
into specially prepared etching paper while the copperplate travels on a bed between
the two rollers of the etching press. Gravure prints, also known as photogravure,
heliogravure, or gravure a l'aquatinte, are a type of etching with aquatint ~ where the
image is created from a photographic source and realized in permanent ink on paper.
The aquatint ground, consisting of very fine asphaltum particles fused to the
copperplate, creates minute unetched 'lands.' In the crevices between these 'lands,' ink
remains and forms the image in a variety of tones corresponding to the depth of
etching.
The variable depth of the etched copperplate is one of the unique qualities of a
gravure print. This is made possible by the use of sensitized gelatin as an etching
resist. Etching resists are usually binary ~ they either resist the etchant completely or,
where incised by lines, allow etching to occur unimpeded. But gelatin absorbs the
etchant and allows it to seep through to the copperplate. The thinner resist allows
etchant to seep through first and etch deepest ~ these areas correspond to the darkest
areas of the image. Thicker resist holds the etchant back longer, so that only light
etching occurs. By moving the plate through various etching baths, it is possible to
adjust how deeply each tone is etched in relation to other tones. The illustration shows
an enlarged cross-section of the copperplate ready for etching, with aquatint grain
(black dots) fused to the plate and the permeable gelatin resist (bright orange) above
that.
Pre-etch copperplate
How does the resist get thicker or thinner? Ultraviolet light (UV) sets off a chemical
reaction that hardens or crystallizes the gelatin. When exposed in contact with a
transparency, the highlights admit more UV, the shadows less, and this difference in
UV exposure causes different thicknesses in the gelatin.
After drying the resist and masking the plate to confine etching to the image area, etching is done in a
series of ferric chloride baths. The first and strongest etches only the shadows but does not penetrate
the thicker resist of the midtones and highlights. More dilute etchant, having more water, soaks through
the thicker resist and starts etching midtones and highlights in succession. If the resist has been over-
exposed, the etchant will never get through to the highlights. But highlight etching, when it occurs,
must be brief to retain the impression of sunlight, as in Ogatama-2, or clouds (Enoshima, Oze Path), or
snow (Three Friends, Gate of Zuisenji, Snow Country, other Snowscapes).
After etching, we take a proof and if OK, remove the resist and aquatint grain, and file and bevel the
edges of the plate to prepare it for printing on the etching press. Here is the etched copperplate from
which the Hokokuji print was made >
Etched plate, Hokokuji
The image is laterally reversed when printing. The dark areas of the copperplate, having been etched as
much as 20 or 30 times more deeply than the light areas, hold that much more ink and create superb
tonal variety in the print. For each impression, the plate is inked, wiped, and printed on the etching
press. This involves clearing the ink from the aquatint 'lands' and image highlights with gradually
decreasing wiping pressure. Finally a very light passage over the plate, known as retroussage, and the
plate is ready to roll through the press ~ always an exciting moment.
Etching papers differ in how they take the ink, how absorbent they are, tone, and
surface texture. I use harder, less absorbent papers such as Lana Gravure and Magnani
for lighter images of sand and snow. Deeply etched plates that transfer a lot of ink
print well on more absorbent papers such as Fabriano, Kyokushi, or Ganpi. The thinnest
Ganpi (middle illustration, front) can be attached to a heavier sheet during printing for
a unique gossamer effect. Shown below are some of my favorite etching papers and
Japanese washi >