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: