HISTORICAL PHOTOGRAPHIC DEVELOPERS AND THEIR CHEMISTRY: THE LUMIÈRE’S CONTRIBUTION
Sara Carvalho; M. Estela Jardim; F. Madalena Costa
4TH INTERNATIONAL CONFERENCE OFTHE EUROPEAN SOCIETY FOR THE HISTORY OF SCIENCE
18-20 NOVEMBER 2010BARCELONA
SCIENTIFIC PHOTOGRAPHY:study of instrumentation and chemical-physical
processes during the period 19th-early 20th centuries
P R O J E C T P T D C / H I S - H C T / 1 0 2 4 9 7 / 2 0 0 8
f i n a n c e d b y
Capture the Image
LIGHT
PHOTOSENSITIVE SALT
LATENT IMAGE
PHOTOGRAPHIC RECORD
Developing
Latent Image: Mechanism
LATENT IMAGE
Invisible image formed by brief exposure of time revealed only
by the chemical action of a developing agent
Photographic PlateEmulsion of suspended
crystals of light sensitive silver halides(chlorides, bromides,
iodides)
Aggregate of metallic silver atoms
light
Early Historical Processes and the Latent Image
Collodion Emulsions Gelatine Emulsions
Photosensitive Salt
Wet and Dry Plates Dry Plates
Immediate use when prepared Pre-prepared
Gelatine Silver-Bromide Emulsion: a timeline
1850 Poitevin Use of gelatine as a biding agent for silver salts without success
1853 Gaudin Produce several emulsions testing different binding agents
1871 Maddox Obtains the first satisfactory images on gelatine silver bromide
1878 C. Bennet Studies on increasing sensitivity with potassium bromide and 30º C
1879 Monckhoven Studies in acceleration by ammonia: ammoniacal silver oxide process
1879 Abney Finds the necessity of precipitate and wash the excess of silver-bromide
Maturation Methods of Gelatine Emulsions: effects on latent image
Cold Emulsions Ammoniacal Emulsions (40-50ºC)
KBr + AgNO3or
NH4Br + AgNO3
•No grains of precipitate•Low sensibility to light
•High contrast
Heating
•Precipitate in grains•High sensibility
NH3 + AgNO3(Eder and Pizzighelli)
•Precipitate in grains•Very High sensibility
Hot Emulsions
Developer Classes in 19th Century
Organic Developers
Physical Development1839-1862
Chemical Development1860
Indirect reduction:the metal ion source is
external to the silver halide grain containing the latent
image
Direct reduction: use the metal ion reserve
present in the latent image containing grains
•Gallic acid (1839-1840)•Ferrous sulfate (1844)
•Pyrogallic acid (1850-1851)
1870 Pyrogallic Acid(Maddox)
1880 Hydroquinone(Abney)
1880 Pyrocatechin(Eder and Toth)
1884 Hydroxylamine(Carl Egli and Arnold Spiller)
1888 Phenylendiamine(Andresen)
1888 Iconogen(Andresen)
1891 Paraminophenol(Andresen)
Che
mic
al d
evel
opm
ent
The Lumière’s Research
Lyon Dry-Plate Factory
•Since the decline of the wet plates, the Lumièrebrothers saw in the new dry plates a great opportunityof success.
•The brothers study and experiment exhaustively thephotographic processes at the time. Results came soon.
•1883: Louis Lumière presents a new procedure for theuse of the AgBr gelatine and presents the plates“étiquette bleue extra-rapides”, patented in 1885.
•In 1900, three products are the “big thing” of theLumière factory:
-the Σ plates-the silver citrate paper for direct processes-the silver bromide paper for development
Lumière brothers: pioneers in Photography
Alphonse Seyewetz (1869-1940) worked inGermany with Carl Liebermann from BASF.
Extent work on artificial colourants.
Engaged by the Lumière factories in 1891, hebecame the head of their chemical services.
Together with Lumière brothers has morethan 200 publications on developers.
Lumière and Seyewetz: a chemical collaboration
ORGANIC DEVELOPERSRESEARCH
The Lumière brothers research on organic developers leads to the following conclusions:
I. Aromatic compounds developing capacity dependson the number of groups OH e NH2:It should present at least two groups OH, or twogroups NH2, or one of each.
II. The position (ortho, meta, para) of the groups havea great influence in the developing capacity: ismaximum in para position; minor in the orthoposition; null in the meta position.
III. The presence of more than two OH or NH2 groupsgives developing capacity to aromatic substances.
IV. When the molecule has more than two aromaticrings, the properties mentioned just apply if the groupsOH or NH2 belong to the same ring.
Presented and patented in 1891 by Andersen as a organic developer.
With the general conclusions about aromatic compounds Lumière brothers focus on paraminophenol and start a research on this compound. This research lead to the following:
I. Great and rapid developing capacity.II. Developing properties not influenced by
temperature.III. The oxidation products don’t interfere with the
latent image and present no coloration of the gelatin, thus allowing the reutilization of the bathfor a great number of images.
These properties make of paraminophenol a very important developer, even when compared with hydroquinone or iconogen.
PARAMINOPHENOL(named Paramidophenol
using the organic nomenclature in 1891)
A comparative study on the reduction effect of organic developers
STUDY ITEMS DONE WITH Σ PLATES
Temperature Effect
Dilution Effect
Soda Content
Bromide Content
Contrast’s Methods
NO ACALINE DEVELOPERS
Temperature Effect Dilution Effect
Contrast Resolution Contrast
Métoquinone(4-methylaminophenol)
No appreciable
variation
Great variation
Low diminution until the 3rd
water volume
DiaminophenolNo
appreciable variation
Great variation
Very high diminution on the 3rd water volume
ALCALINE DEVELOPERS
Temperature Effect Dilution Effect
Contrast Resolution Contrast
GlycineLow diminution High
augmentation
High diminution on the 3rd water
volume
Iconogen
Low diminution Low augmentation
High diminution on the 3rd water
volume
PyrocatechinLow diminution Very Low
augmentation
Very Low diminution until
the 3rd water volume
ALCALINE DEVELOPERS
Temperature Effect Dilution Effect
Contrast Resolution Contrast
Pyrogallic AcidLow diminution Very high
augmentation
Very high diminution on the 3rd water volume
Paraminophenol
Low diminutionVery low
augmentationVery high
diminution on the 3rd water volume
MetholLow diminution Low augmentation
Notable diminution on the 3rd water volume
HydroquinoneVery high
diminutionVery high
augmentation
Low diminution until the 3rd water
volume
ALCALINE DEVELOPERS
Temperature Effect Dilution Effect
Contrast Resolution Contrast
Methol-HydroquinoneLow diminution Very high
augmentation
Low diminution until the 3rd water
volume
Hydramine(2-diphenylmethoxy)
Low diminutionVery low
augmentation No effect
AdurolVery Low
diminutionHigh
augmentation
Low diminution until the 3rd water
volume
The triumph of colour
Period Inventor Procedure Description
1891-1894 Lippman
DIRECT INTERFERENCE PROCESS: • Colours created through the creation of interference patterns between light waves• Used neither dyes or pigments• Neither additive nor subtractive process
In 1908 Lippman was awarded the Nobel Prize for Physics for the demonstration of OndulatoryTheory in his colour photographic work.
1894-1900Louis Ducos du
Hauron
TRICHROME PROCESS OF COLOUR PHOTOGRAPHY:• Three black and white glass negatives usingseparate yellow, magenta and cyan filtersoriginate three identical images. These threeimages were superimposed and a recognizableimage was achieved.
Lumière’s three-colour process (1893-1900)
Format: 8,5 x 10cm; 8,5 x 18 cmLow sensitivity to abrasion and pollutantsMedium sensitivity to light and humidity
Yellow gelatine
Magenta gelatine
Cyan gelatine
Glass
The Autochrome and the Science of Development1907-1935
•The first fully practical method of colour photography•Patented in 17 December 1903•Presented at Académie des Sciences in 1904•Launched into the market in 1907
1st varnishglass
glass1st varnish
1st varnish
1st varnish
1st varnish
glass
glass
glass
Charcoal black
Tinted potato starch grains
Charcoal black
Laminated tinted potato starch grains
Tinted grains
Charcoal black
2nd varnish
Charcoal black
Tinted grains
2nd varnish Silver suspended in gelatin
A roller submitted the plate to a pressure of 5 tons/cm2 in order to spread the grains and flatten them out.
Inside the Autochrome
On every square inch of the surface of an Autochrome plate there are about four million transparent starch grains, each one of which acts as a tiny coloured filter.
Format: 4,5 x 10,5 cm; 9 x 12 cm; 13 x 18 cm; 18 x 24 cm; 18 x 30 cmLow sensitivity to abrasion
Medium sensitivity to light, humidity, pollutants
Developing Autochromes
Darkroom:1. First development
2. Washing3. Dissolving the developed image
Daylight:4. Washing
5. Developing positive image6. Washing
7. Destroying developer8. Washing
9. Intensification10. Washing11. Clearing12. Washing
13. Fixing14. Final washing
Image Reversal
Pyro-ammonia
Acid permanganate
solution
Paradiaminophenol
Negative
Positive
“The possibilities of the new process seem to beunlimited…soon the world will be color-mad, andLumière will be responsible.”
Alfred Stieglitz
Spread Out
Uses
Autochrome’s Disadvantages
•Fragile support
•Long time exposure
•Expensive process
•Light susceptibility
Improvements and Alternatives
In Spain, Jaume Ferran published in 1907 two articles in La Fotografia Prática where he suggest some alternatives to the Lumière Autochrome process:
“Una variante del procedimiento autocrómico de los hnos. Lumière”(August 1907)
“Algunos perfeccionamientos de que son susceptibles las placas autocrómicas Lumière”(September 1907)
The suggestion concerns the use of different microorganisms, like penicillium glaucum instead of potato starch
“In 1932 the Lumière factory switched theautochrome emulsion to a sheet-film base, Filmcolorand then to roll film, Lumicolor.
However by this stage colour photography hadmoved on, after 30 years, autochrome technologydeclined but, as the first commercially successfulcolor process, its influence on 20th Century colourvision was incalculable.”
Pamela Roberts
Bibliography
•ABNEY, W. (1885). Photography with Emulsions, London, Piper&Carter.
•BRAUN, Ad. (1904).Dictionnaire de Chimie Photographique, Paris, Gauthiers-Villars.
•EDER, J. (1881). Modern Dry Plates ; Emulsion Photography, London, Piper&Carter.
•KENNEL, Sarah (2009). In the Darkroom – An illustrated guide to photographic Processes before the Digital Age, National Gallery of Art, USA, Thames&Hudson.
•LAVÉDRINE, B. (2007). (re)Connaître et Conserver les photographies anciennes, Paris, Éd. Comité des travaux historiques et scientifiques.
• LAVÉDRINE, B; GANDOLFO, J. (2009). L’Autochrome Lumière. Secrets d’ateliers et défis industriels, Paris, Études photographiques, Notes de lecture
•LUMIÈRE, Auguste et Louis (1893). Les développateurs organiques en photographie et le paramidophénol, Paris, Gauthiers-Villars.
•LUMIÈRE, Auguste et Louis, SEYEWETZ, A. (1907). Sur le développement des plaques autochromes, Bulletin de la Société Française de Photographie, pp. 515-528.
•MATHET; L. (1912). Traité de Chimie Photographique, Paris, Charles-Mednel.
•ROBERTS, P. (2007). A century of Colour Photography, Andre Deutsch.
•SAULEDA, S. (2007). Ferran I Paulí: La Instantaneidad en Fotografia, Quaderns d’Historia de L’Enginyeria, Vol VIII.
•SEYEWETZ, A., (1899). Le dévellopment de l’image latente en photographie, Paris, Gauthiers-Villars.
•www.autochromes.culture.fr•www.nationalmediamuseum.org.uk/autochrome
Acknowledgments: