SPECIAL REPORT

John L. Ennis,
Arthur D. Little Inc.

On Jan. 6, 1839, a leading Paris newspaper, Gazette de France, scooped its rivals by revealing that the following day, at a meeting of the Academy of Sciences, there would be an announcement of "An important discovery by our famous painter of the Diorama, M. Daguerre. This discovery partakes of the prodigious. It upsets all scientific theories of light and optics, and will revolutionize the art of drawing." The article, clearly planted, continued in a laudatory vein about the beauty and detail of the images made possible by Louis-Iacques-MandeDaguerre's discovery and looked forward to the time when travelers could acquire Daguerre's apparatus and bring back a record of their voyages. On the following day, Francois Arago, perpetual secretary of the Academy of Sciences, director of the Paris Observatory, famed astronomer, and member of the Chamber of Deputies, read a paper to the academy, reporting for himself and two other members: Alexander von Humboldt, physicist and explorer, and Jean Baptiste Biot, physicist and astronomer. Arago announced that the three of them had examined Daguerre's discovery-the process for producing daguerreotypes-and verified its authenticity. A comparison of its sensitivity to that of paper coated with silver chloride showed it to be of great and unusual sensitivity to light. He forecast immense value for the discovery and suggested the French government buy the process and make it generally available. Thus 1989 marks the 150th anniversary of the
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daguerreotype-generally thought of as the progenitor of photography. But the daguerreotype process was only one-although the most immediately successful and practical-of several photographic processes disclosed during that single eventful year. A distinctly different process had been worked out and used to prepare photographic images during the mid-1830s by an English gentleman, William Henry Fox Talbot, who never really had publicized his method. What is probably the first photograph had been prepared about 15years earlier by another Frenchman, Ioseph-Nicephore Niepce. The year 1839 also was the beginning of a 40-year period of progress in photographic chemistry that is characterized by processes in which light-sensitive materials with a short shelf life were prepared by photographers themselves (or by an assistant) for use at once. Photographers then were, of necessity, practicing craftsmen-chemists, whatever their academic training or interest in theory. To be successful, they had to be both dedicated experimentalists and skilled technicians. Later, with the discovery of light-sensitive coatings having greater stability, the production of photographic plates, paper, and (shortly thereafter) film was to pass into commercial hands-and the whole initial era of photographic technology faded into history. (All of the early photographic processes

were sensitive only to Tight at wavelengths shorter than 500nm-the blue and near-ultraviolet spectrum; not until much later did commercial dye sensitization extend the sensitivity of photographic materials into the green, yellow, and red portions of the visible spectrum for the practicing photographer.) The existence of a relationship between exposure to light and change in color of many materials had been known long before the 19th century, to be sure. Decomposition of silver salts to give black deposits, for example, had been observed by the alchemists, But the relationship between light and chemical change was only poorly understood; the distinction between the formation of silver metal by chemical reduction of silver halides or by photolytic means was not recognized. Even as careful an investigator as Robert Boyle had attributed the darkening of silver chloride to exposure to air. In 1727,[ohan Heinrich Schulze, professor of Greek, Arabic, and medicine at the University of Altsdorf in Germany, experimented with the preparation of phosphorescent barium sulfide, known as the "Bologna stone," a substance that had aroused considerable interest. By chance, Schulze discovered the light sensitivity of silver nitrate when he wetted chalk with nitric acid inadvertently contaminated with silver and obtained cl. thick slurry, which then darkened on the side of a flask when exposed to sunlight. Shaking the contents removed the dark area, but it reappeared on further exposure.

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Early processes followed diverse pathways to form a permanent photographic image

Early processes used to prepare photoeither the areas exposed to light (negaindicates that oyer the past 150 years of

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in the diagram on the opposite page. (positive working) and a ~ash-out proA light-sensitive medium-generally cess takes advantage of a difference in now a photosensitive coating on a supsolubility. port but earlier frequently a sheet of Furthermore, It is frequently necespaper that had been immersed in one or sary to follow up with a treatment that more baths to impregnate it with a phofixes the area surrounding .the image to tosensitive material and then dried-is ensure that the developed sheet is no prepared and exposed to sunlight (in- . longer affected by further action of light. cluding the near ultraviolet, which may Several washing steps may be needed, be transmitted by glass optical compoand often an additional toning step is nents). The image-forming light may be desirable to adjust the color of the imfocused on the surface of the medium age or preserve it from fading or discolby a lens (camera exposure) or passed oration with age. .through a stencil, such as a photographPhotographic speed is given as an ic negative, held in contact with the inverse function of the minimum quantisheet (contact exposure). ty of light needed to produce a negative Exposure produces an imagewise phothat will yield the most acceptable print. tochemical change in the medium; this Only an approximate comparison of the alteration may be stable indefinitely or relative speed various of photographic subject to reversal (fading). If impermaprocesses is possible. The table below nent, the altered state should be stable enough to permit carrying out subsequent processing steps conveniently. In some "printout" processes, the image is directly visible and the exposure of the print can be monitored by lifting a corner of the stencil and inspecting the image. In other cases, the exposed areas must be differentiated from unexposed areas by processing steps that take advantage of differences in physical or chemical properties produced by photochemical action. This process is generally referred to as "developing" the image. Thus, a differential staining technique might intensify

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research and improvement, photographic speed has increased dramatically and, since the introduction of the dry plate ' by Richard L. Maddox in the early 1870s, roughly doubled every 10 years. According to current theory, energy from light absorbed by a silver halide crystal (the original solid state detector) moves an electron into the conductance band, forming a mobile hole and electron pair. For a simple undyed, undoped silver halide crystal, such as were used in early photography, the electron is quickly trapped by a silver ion, forming atomic silver. Following the absorption of additional photons, a small stable speck of, silver metal-the latent image, consisting of a few atoms-will form at a defect site in the crystal. The efficiency of this process is decreased by recombination of electrons

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Carl Wilhelm Scheele, a brilliant Swedish experimenter and practicing pharmacist best known for isolating, purifying, and identifying many organic acids and for the discovery of chlorine, was also interested in the chemical effect of light. In experiments to support the thesis that light contains phlogiston, Scheele precipitated silver chloride from silver nitrate solution with ammonium chloride, then filtered and dried the precipitate. He darkened this dry material in sunlight and dissolved away the unaltered silver chloride in ammonia to isolate a black residue, which proved to be silver and which could be "dephlogisticated" with nitric acid to produce silver nitrate (lunar caustic) again. Experiments with it sprinkled over paper and illuminated with a spectrum from a prism showed that the silver chloride "liberated phlogiston sooner from the violet light than from other rays." By the beginning of the 19th century, the growth of a unified body of chemical information permitted experimentation better directed toward attaining functional goals. Several pioneers of photography derived
28 December 18, 1989 C&EN

their interest from a device known as the camera obscura (literally, darkened chamber). Light passing through a small opening into a darkened room or box will project a reversed image of objects outside onto the opposing wall. Although the phenomenon was known to the ancient Greeks, its practical use long was extremely limited. About 1550,however, addition of a biconvex lens and focusing tube allowed brighter images to be produced and the camera obscura was used to achieve true perspective in making drawings. By the 17th century, tents and portable boxes incorporating lenses and mirrors to rectify the image were in common use by artists, architects, and surveyors. In 1796,the renowned Wedgwood pottery works in England received an order from the imperial court of Russia for a china service to be decorated with more than 1200 scenes of British castles, estates, and country houses. Thomas Wedgwood, son of the world famous potter [osiah Wedgwood, had been experimenting since the early 1790swith making images of leaves by placing them on paper impregnated with

with holes and by the trapping of electrons by impurities, which do not contribute to the formation of a stable latent image. Concurrently, holes release elemental halogen, which can react with the interstitial atomic silver to reform silver halide unless intercepted by a halogen acceptor adsorbed to the surface of the crystal. The nature of the shell of adsorbed material greatly affects the probability of recombination and consequently the light sensitivity and resulting photographic speed of a coating. William Henry Fox Talbot'sincorporation of gallic acid in his calotype coating produced a sheath
of sliver gallate, a readily oxidized ma-

terial, around the halide crystal. This ensured the consumption of halogen and the formation of a stable latent image. Conversely, when he attempted to fix his early photolytic images by impregnating the paper with salt after exposure, he produced a double layer of ions around the crystal-chloride at the surface surrounded by sodium ions. This barrier prevents -reaction of the halogen at the surface and promotes recombination within the crystal. Although not thoroughly fixed, the residual halide crystals in the paper were stabilized against further rapid photolysis by amblent light. At a time when analytical chemistry was in its infancy and stoichiometric relationships not well understood, the range of light sensitivity obtained by dipping paper altemately into salt and silver nitrate solutions proved bewildering.

silver salts, a hobby which may have been suggested by Josiah's friend Joseph Priestley. Much of the artwork for the imperial china service would have to be commissioned to artists, who probably would rely on the camera obscura to get correct proportions and perspectives. Thomas Wedgwood hit on the idea of obtaining these sketches by the action of light on a sensitized sheet placed in the camera. His efforts were partially successful; by making contact prints he did obtain images of reversed tonality on paper or leather. But he was unable to fix the images; they continued to darken when removed from a drawer for examination. He also found that the -light sensitivity of the treated paper was too low for exposure in the camera. Thomas, in declining health, abandoned his studies. His researches were summarized by his friend Humphrey Davy and published in 1802 in the Journal of the Royal Institution, a recently founded organization dedicated to instructive public lectures. Critics have faulted Davy for not making use of ammonia, known as a solvent for silver chloride, to fix the

images and for not pursuing the matter further. In fairness, however, much of Wedgwood's experimentation had been done before he knew Davy. By the beginning of the 19th century, many other researchers were attempting to prepare lasting images by the action of light. For example, in 1828 [ames Wattles, a youthful art student in New Harmony, Ind., conducted photographic experiments. Wattle's description of his work, found in William Welling's "Photography in America: The Formative Years," begins, "I first dipped a quarter sheet of thin white writing paper in a weak solution of caustic (as I then called it) and dried it in an empty box, to keep it in the dark; when dry, I placed it in the camera and watched it with great patience for nearly half an hour, without producing any visible result; evidently from the solution being too weak. I -then soaked the same piece of paper in a solution of common potash, and then again in caustic water a little stronger than the first, and when dry placed it in the camera. In about 45 minutes I plainly perceived the effect, in the gradDecember 18, 1989 C&EN 29

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SpeCial Report

Swedish apothecary Carl Wilhelm Scheele (near right), who first isolated several organic and inorganic acids and was involved in the discovery of chlorine, oxygen, and other elements, also studied the effect of light on silver salts during the 18th century. Thomas Wedgwood (far right), son of famed .English potter Josiah Wedgwood, made images on paper impregnated with silver salts in the 1790s but was unable to fix them against darkening

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ual darkening of various parts of the view, which was. the old stone fort in the rear of the school garden, with the trees, fence, etc. I then became convinced of the practicability of producing beautiful solar pictures in this way; but alas! my picture vanished .... I began again by studying the nature of the preparation, and came to the conclusion, that if I could destroy the part not acted upon by the light without injuring that which was so acted upon, I could save my pictures. I then made a strong solution of sal. soda I had in the house, and soaked my paper in it, and then washed it off in hot water, which perfectly fixed the view upon the paper." .. Wattles used, in order, silver nitrate, potassium hydroxide, and silver nitrate again, exposed the soaked paper and then stabilized his image with sodium carbonate. Experiment indicates he would have obtained a chocolate-brown, negative image on a sepia background that was not so fully stabilized against further exposure to light as he reported. The opposition of his parents and "adverse circumstances" prevented his renewing his experiments and the passage of time and the clear success of others, of course, may have colored Wattles' recollection of the successof his work. Still later, unknown to anyone but his neighbors in the village of Sao Carlos, Brazil (100 km from Sao Paulo), Hercule Florence, working with limited resources, independently developed a system of photography between 1833 and 1837; His descendents have a few examples of his work and his notebooks reflect a wide-ranging familiarity with the chemical literature of his day. The notebooks show that in 1832 he also chose the word photography for his efforts. Florence, born in Nice, France, in 1804,was trained in both science and art and emigrated to Brazil at age 20. A year later, while working in a printing shop, he was hired as an artist on an expedition to the interior of the continent. Upon returning, Florence entered commerce and pursued invention as best he could. One invention was a form of hectograph: he saw a
30 Decembef 18. 1989 C&EN

need for a simplified means of printing with lightweight equipment but found no commercial backers. He recognized the possibility of a negative/positive process using silver chloride fixed with ammonia but discarded it and worked instead with papers sensitized with gold chloride, which he believed gave a darker and more acceptable image. These he fixed with ammonia, salt solutions, or urine to obtain a negative from which he then prepared positive prints. Although there are references to camera exposures in his notebooks, only his contact prints remain. The efforts of individuals like Wattles and Florence, whatever their success, suggest that a critical point had been reached in establishing an expectation for obtaining and fixing a photographic image. Such early efforts led to the events of 1839.

1839, the eventful year

The eight months following Arago's report to the academy on Daguerre's success are a remarkable example of how, when the spirit of the times is right, the same problem will engage the interest of many individuals, precipitating a rush of activity to establish the priority of independent efforts .: Neither Arago nor Daguerre could have foreseen the extent of the controversy that would break out before the day when full disclosure of the daguerreotype process took place, nor the welter of competing claims that would be made while the public of Paris waited for details. Daguerre was well known as the impresario of the Diorama Theater, a famous Parisian attraction, of which he was principal stockholder. Born in 1787 into a lower class family in Cormeilles-en-Parisis, a rural

Special Report

village 12 km north of Paris, Daguerre's formal education was scanty. At the age of 17, he was apprenticed to a scene painter for a Paris theater. Talented, dedicated, and ambitious, he advanced himself to become set designer for the Opera and the Opera Comique while also working on several panoramas. The. panorama, a major urban amusement in the early part of the 19th century, consisted of a circular building in which the audience faced outward to look at an encircling realistic painting prepared with care- . ful attention to perspective. In 1822, Daguerre conceived the Diorama (from the Greek "to see through"), an elaborate spectacle with music, tableaux vivants, and special lighting effects featuring scenes painted on thin, open-weave fabric that were essentially transparent until selectively illuminated. The Diorama became a hit attraction and as its popularity increased so did Daguerre's fame. While interest in Daguerre's discovery was still fresh, the academy in Paris received a letter from a botanist and botanical illustrator, Franz Bauer, who was living near London. Bauer stated that in 1827 he had met Niepce, who at that time had already produced images in the camera by the action of light. Niepce was born in 1765 to a landed country family in the Burgundy region of France. Since childhood, Niepce and his elder brother Claude had been tinkerers and whittlers of toys and mechanical devices. Although much of the family estate had been confiscated after the French Revolution, in 1801 the brothers had a comfortable income and returned after military service to the family home near Chalon-sur-Saone, in part to pursue the development of an invention suggested by Claude. The invention, the Pyreolophore, was an internal-combustion engine designed to be fueled with powdered coal and intended to power a

paddle wheelboat. Although Sadi Carnot, the physicist, commented favorably on the design, the brothers were ahead of their time, and promotion of the Pyreolophore by Claude in Paris and later in London . proved a great financial burden. Meanwhile, an interest in the newly introduced process of lithography and a desire to simplify the preparation of imaged lithographic stones started Nicephore's photographic researches. When none of the quarries of Burgundy produced a commercially attractive stone, he turned to a metal support, with the goal of making an engraved printing plate by the action of light. Letters between the brothers reveal Niepce to have been a persistent, ingenious, and fearless experimenter. He must have constructed most of his equipment himself, and he appears to have invented the iris diaphragm for controlling the aperture of lenses; certainly he was the first to incorporate one in a camera. Niepce experimented with a wide variety of materials reported to exhibit some form of change on exposure to light, including silver salts, ferric chloride, gum guaiac, manganese oxide in an atmosphere of chlorine, and, in a notable series of trials, elemental phosphorus. He prepared a prototype leather glove box containing air depleted of oxygen in which he attempted to cast coatings of white phosphorus melted in hot water onto paper, stone, and metal. He not only was plagued by accidental fires but also found the moist coatings that changed in direct sunlight were insensitive in the camera. Finally, after severely burning his hand, he abandoned this "perfidious combustible." Between 1816 and 1826, Niepce worked out a process using a coating of asphalt (bitumen of [udea) dissolved in Dippel's oil (bone oil) applied to metal. Prolonged exposure to light hardened (cross-linked)

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Working alone in Brazil, Hercule Florence, shown left at age 70, developed a system of photography in the mid-1830s; he made the contact prints of pharmacy labels shown at right probably in 1833
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Spscial Report

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Using a type of asphalt, Nicephore Niepce was able to make crude photographs, such as the barnyard scene shown in the heliograph on pewter taken in 1826, that required several hours of exposure so that shadows were indistinct .

the coating so that unexposed areas could be preferentially dissolved and washed away with a solvent (oil of lavender). The metal thus laid bare could then be etched with acid to produce an intaglio plate that could be inked and printed on paper. Exposures were lengthy (eight hours in the camera)and most plates were contact prints from images on oiled paper and even then required retouching by hand to make them fit for the press. Niepce found white metals (pewter, tin, and silver) to be preferable to copper. This was the state of the heliograph process when Nicephore and his wife were summoned to England by news of Claude's severe illness. While in Paris arranging transportation and passports, Niepce met Daguerre. On reaching England, Niepce learned that much of the money sent to his brother to support continuing work on the cherished Pyreolophoreactually had been spent on a perpetual motion device, so that Claude's finances were in total disarray. Niepce's attempt to present his images and prints to the Royal Society in England was prevented by his insistence on keeping it a proprietary process. He tried, through displays of plates and prints and by giving samples to a number of people, to awaken the interest of George IV and obtain royal patronage, but again was unsuccessful. Niepce returned home disheartened and with mounting debts in February 1827,shortly before the death of Claude. After extensive negotation and with much trepidation, he signed a contract on Dec. 14, 1829, to enter into a lO-year joint research partnership with Daguerre under the name Niepce-Daguerre. Daguerre visited Niepce and received a written summary of the latest version of the heliograph process, a technique in which a silverclad copper plate was coated with asphalt, exposed, washed in solvent, and the image darkened with io_ dine vapor. . Niepce received essentially nothing except the prom34
December 18, 1989 C&EN

ise of moral support and access to improved optics from Daguerre. Later, Niepce's son Isidore, in a polemic pamphlet defending his father's name and attacking Daguerre, described Daguerre's investigations prior to the partnership as nothing more than work on the well-known Bologna stone. It appears that Niepce-aging and in financial difficultiesknowingly struck a deal with a successful entrepreneur who exhibited a commitment to the same goal of permanently fixing the action of light in a camera. The two never met again, although they maintained a formal correspondence. Niepce died on July IS, 1833, and his place in the firm was taken by Isidore, his heir. The technical effort from this point was carried out by Daguerre alone .. At Daguerre's insistence, his contract was renegotiated with Isidore in 1835 to recognize that the firm now controlled a new process that had been developed by Daguerre alone and named after him. Further modifications of the contract in 1837 included provisions for selling the assets of the firm in its entirety or by subscription to shares that entitled purchasers to a full revelation of the processes after 400 shares were sold. However, a sales offering, made on March 13, 1838,was a complete failure and Daguerre and Niepce agreed to try to sell the process to the French government, which could then make it public as a gift from an enlightened nation to the world. In the fall of 1838, they secured the assistance and sponsorship of Arago for this endeavor. . Little record of Daguerre's experimental work remains. On March 3, 1839, the Diorama burned down while he was at a hotel visiting Samuel F. B. Morse, the American painter, inventor, and entrepreneur, who was in Paris promoting his telegraph. Daguerre lost many of his records, samples, and personal effects. Interestingly, Morse also seems to have had an earlier interest in a process to obtain images. Writing to

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his brothers, he reported his growing friendship with Daguerre and commented on the exquisite detail, even under magnification, of daguerreotypes he had seen. Morse then went on to say, "You may recall experiments of mine at New Haven many years ago [1811 or 1812] when I had my painting room next to Professor Silliman-experiments to ascertain whether it were possible to fix images of the camera obscura. I was then able to produce different degrees of shade on paper dipped into a solution of nitrate of silver, by means of different degrees of light, but finding that light produced dark, and dark light, I presumed the production of a true image to be impracticable and gave up the attempt." The investigations Daguerre conducted prior to his partnership with Niepce in 1829 may have been directed in part to improvement in the Bologna stone, as the Niepces claimed. This is supported by a paper that Arago read to the academy on Feb. 19, 1839, after the announcement of the daguerreotype, that contains a recipe of Daguerre's, dated 1824, for a phosphorescent composition prepared by calcining degreased marrow bones with barium sulfate. At the same meeting, Biot described papers suitable for photometry that were sensitized with silver salts prepared by a technique disclosed by Daguerre and attributed to the year 1826. In this method a sheet of paper was immersed in "muriatic ether," thoroughly dried, immersed in silver nitrate solution, and dried

again to produce a sensitized paper that darkened under the action of light and that could be fixed by washing with water. Muriatic ether apparently is a liquid of uncertain composition obtained by distilling a mixture of ethyl alcohol and hydrochloric acid. If

the paper treated with ether were thoroughly dried

before being treated with silver nitrate, only small quantities of silver chloride would be formed. Images prepared on this paper, as well as samples of the paper, were shown at the meeting. The following week Biot read a paper describing photometry through filters using light-sensitive papers supplied by Daguerre. After this lecture, Daguerre's light-sensitive paper was no longer mentioned. Nothing is really known, in fact, of Daguerre's work after the partnership period; he apparently shared none of it with his partner. From Niepce he obtained the idea of using a silver plate and the technique of treating with iodine fumes. However, Niepce had made no use of the light sensitivity of silver iodide, but instead introduced iodine fumes as a means of darkening a bare metal image obtained with his crude photoresist. Meanwhile, in England, Talbot, a country gentleman with a wide range of interests, had for some

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The most immediately practical and successful of the early photographic processes was developed by Jacques Deguerre, portrayed in a daguerreotype made in 1848; Daguerre produced the daguerreotype of a Paris street in 1839. The camera (center) was made by Daguerre
December 18, 1989 C&EN 35

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years been experimenting with paper impregnated with silver chloride. Upon hearing of Arago's announcement of Jan. 7,1839, he immediately sent samples of his work to the Royal Institution, where they were displayed by Michael Faraday at the weekly meeting on Jan. 26. Talbor reported his work on photogenic drawings in a letter to the Royal Society published Jan. 30. These actions set the stage for a continuing rivalry with Daguerre in which the nationalistic adherents to each camp contributed as much as the principals. Talbot, born in 1800, had been educated at Harrow and at Trinity College, Cambridge, where he interested himself principally in physics and mathematics (an interest in archaeology developed later). It was for his mathematical studies that he was admitted to the Royal Society in 183l. During a trip to Italy in 1833,Talbot used a camera lucida (a device that, using a prism or mirrors, casts the image of an object on a plane surface so that an outline can be traced) as an aid in sketching Lake Como, without success. Dissatisfied with this device, he resolved to secure the image by chemical means and in 1834 began experiments with paper sensitized with silver salts. These early photographic studies were carried out intermittently during a period when his attention was also directed to studies of diffraction phenomena, publication of papers on integral calculus, classical and antiquarian researches, and a study of the antiquity of the Bookof Genesis. Experimenting with silver chloride, bromide, and iodide, he obtained the greatest sensitivity when he coated his papers with an excess of silver nitrate, obtained by first saturating the paper with a solution of an alkali halide and then, after drying, treating it with silver nitrate solution. An excess of chloride, he reported, greatly reduced light sensitivity. After exposure, he used a bath of sodium chloride or (less successfully) sodium iodide as an imperfect means of stabilizing the image. What distinguishes Talbot from most others who experimented with silver-salt-sensitized paper was his appreciation of the utility of an image with reversed tonal values (the negative). By placing a negative obtained in a first exposure face down against another sensitized sheet, he could obtain a copy of the image that was not reversed left to right and in which dark in the original scene was dark and white was white. The concept of negatives from which positive prints are made now seems obvious. In reality, it was revolutionary. Talbot wrote letters to his friend Biot in Paris describing his results, which were reported during February 1839in Compte rendu des Seances de l'Academie des Sciences, the weekly journal of the academy. He suggested sodium thiosulfate (then known as hyposulfate), which had been drawn to his attention by Sir John F. W. Herschel, as an excellent fix, noting that "these solutions dissolve all silver halides and allow them to be washed out of the image." . Herschel, astronomer and son of a famous astronomer, had just returned to England from making astro38
December 18. 1989 C&EN

nomical observations in South Africa when the announcement of Daguerre's discovery by Arago was brought to his attention. To satisfy his curiosity, he investigated the use of silver salts on paper independently, thus duplicating much of Talbot's work, and also prepared thin deposits of silver salts on sheets of glass. Although these coatings were difficult to process because of poor adhesion, use of them indicated that the presence of paper or other organic material was not essential to the process. Herschel's results, with examples fixed with ammonium thiosulfate (including prints from a negative), were submitted to the Royal Society during a meeting on March 14, 1839.Herschel introduced the term photography at this time, as well as, later, positive and negative; all three terms were adopted universally. On Feb. 2, meanwhile, Friedrich Cerber, professor of veterinary surgery at Berne University in Switzerland, claimed in the local paper that in 1836 he, too, had secured images on silver-sensitized paper using the camera obscura. Details of the process and samples of his work have not survived. Duplication of Talbot's work was not difficult and was done in short order by Johann Enslen in Germany. Other reports of successful use of silver-sensitized paper came from Vienna and New York. For example, John Draper of the University of New York (later first president of the American Chemical Society) noted that in 1837, when he
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These direct positive processes appear nearly identical to a process developed and successfully exhibited by Hippolyte Bayard, whose notebook enclosing sequential samples has been preserved. Bayard, born in 1801,was a civil servant in the Ministry of Finance in

Paris who Iwas friendly with members of the artistic

communitYr,where talk of Daguerre's activities was common. ~hese rumors led him to begin photographic experimentation about 1837.Arago's announcement of Jan. 7 sturred Bayard to action, and early in 1839 he perfor~ed a series of experiments. By Feb. 5, he displayed crude samples of images to Cesar Desprets, a physicist lmdmember of the academy. And by March 20, he exhibited pictures to his friends and apparently was quite open about his success. In May, ~boking for financial support from the government, h~ approached Arago with samples. Arago, keeping hi~ protege Daguerre in mind, urged Bayard not to publlish a description prematurely and secured him a grant of 600 francs from the Ministry of the Interior to buy equipment. An exhibit of Bayard's pictures on June 24 at a charity bazaar got favorable reviews. However, like Daguerre, he kept his process secret in the hope of getting official recognition and Fox Talbot, shown with one of his cameras, invented the rewards. calotype process in the late 1830s. The camera shown Despite the surprising number of competitors who lower left was used by Talbot about 1836. The calotype of had sprung up, Arago continued to promote Daguerre. a lady (left) was made about 1850 . His efforts bore fruit on June 14 with the signing of . a contractbetween Daguerre,IsidoreNiepce,and Charles Marie Du Chatel, Minister of the Interior, that providwas teaching at Hampden-Sydney College, he had ed annual pensions of 6000 francs for Daguerre (2000 used paper sensitized with silver chloride for spectral of which was for disclosing the secrets of the Dioraphotometric investigations. Two undergraduates at ma) and 4000 for Niepce to be paid when enabling Harvard-Edward Everett, later to become an ardent legislation was passed-this in exchange for full written abolitionist, and Samuel Longfellow, younger son of disclosure of Niepce's and Daguerre's processes in a the poet-made successfulprints. However, the quality sealed envelope and a promise to keep the informaand artistic merit of these and many other demonstration secret until a bill submitted in the king's name tions are questionable; practically all were contact passed both houses of the French legislature. (A thouprints rather than negatives made by camera exposure. sand francs approximates $5000in current purchasing During the spring of 1839, two other photographic power.) processes were announced in Edinburgh. Mungo PonOnce pensions were secured, all was set for a discloton, a lawyer and secretary of the Bank of Scotland, described to the Society of Arts how paper impregnatsure of both the heliograph and the daguerreotype ed with sodium dichromate, when dried and exposed processes to a joint meeting of the Academies of Science and of BeauxArts on Aug. 19. Daguerre declined to light under a stencil, turned brown in the exposed to speak. However, Arago, in his element, spoke at areas. The remaining unexposed unaltered dichromate then could be easily washed away. The brown length to an overflow house, and with great acclaim, the daguerreotype was given to the world (except for image, probably consisting of a complex mixture of chromic chromates recent research by M. Susan Barger . Great Britain and Ireland, where a patent in Daguerre's name had issued on Aug. 14). of Iohns Hopkins University suggests, turns slowly to dull green chromic oxide, an insoluble permanent pigA manual detailing the daguerreotype process,which ment. No immediate use was made of this process, appeared in 30 editions in six languages by the end of despite several investigators' efforts. 1839, was issued on Aug. 21. It described a process Another process was revealed to the Society of Arts that was easy to duplicate for purposes of initial demby Andrew Fyfe, physician, author of "Elements of onstration but demanding if pursued with expectaChemistry," and later professor of chemistry at tion of uniform results. The process can be summarized in the following Aberdeen University. On Feb. 17, Fyfe described a steps: direct positive process based on the use of potassium A sheet of copper clad with silver is thoroughly iodide and silver phosphate. In Paris,meanwhile, the editor of L'Echo du Monde Savant on April 10, 1839, polished to a mirror surface with pumice, buffed, washed with nitric acid, and rinsed with distilled described a direct positive process displayed by a M. water. Lassaigne (probably Jean Louis Lassaigne, a professor of chemistry at 0'Alfort, the national veterinary school. The silver surface is sensitized by being placed,
December 18, 1989 C&EN 37

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silver side down, over a container of iodine until it acquires a golden yellow color. Then, protected from light, within the hour the plate is placed in a camera and exposed for a period of three to 30 minutes. Again protected from light, the sheet is developed by transferring it to a wooden box placed at an angle of 45 over a basin of mercury heated to 60 "C with an alcohol lamp. Mercury vapor condenses only on the portions struck by light. The operation, which takes about two minutes, can be monitored through a window in the box. The sheet is then fixed to remove residual silver iodide by immersing it in a bath either of common salt or (more often) of sodium thiosulfate. Finally, the sheet is washed thoroughly with distilled water. As soon as full reports of the daguerreotype process were available, experimenters duplicated and modified the technique. Within a few months, the advantage of using bromine and chlorine, in addition to iodine, to produce halides of greater light sensitivity (thereby greatly reducing exposure time) was announced by several individuals. Soon afterward, Armand Hippolyte-Louis Fizeau announced that, after fixing, a daguerreotype could be treated with a dilute solution of gold chloride in sodium thiosulfate and then heated over an alcohol lamp, which darkened the silver mirror and increased the contrast of the image. Such gilding soon became a standard processingstep. A daguerreotype image consists of extremely fine crystals of silver metal formed during and shortly after development where photolytic decomposition of the silver halide coating on the plate has produced nuclei of silver metal on which mercury vapor condenses preferentially, studies by Barger indicate. The mercury, which is transient, serves as a solvent or vehicle in the accumulation of the silver. After they are fixed with sodium thiosulfate, the crystallites scatter visible light efficiently, producing a white, frosty image on the mirror surface of the daguerreotype plate. For proper viewing, the plate should be held at an angle away from direct illumination so that the mirror surface presents a dark background to the eye on which the image appears to float. For 20 years, daguerreotypes dominated photographic markets, both technically and commercially. They had several drawbacks, however: a heavy, expensive, silverplated, copper sheet was needed for making each picture; copies could not be made; the fragile image had to be mounted behind protective glass; and it was a mirror image. But daguerreotypes also had distinct advantages: very good image resolution, so that details undetected by casual inspection could be seen clearly under magnification; short exposures, at first, in comparison with. the paper processes; and, particularly important for the daguerrean artist, controlled and reproducible vapor-phase coating and development without manipulation. The cleaned silver plate was iodized by vapor under inspection until the proper thickness of
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December 18, 1989 C&EN

silver iodide was formed, which was readily determined by watching the change of color resulting from interference. Development with mercury vapor, too, could be watched through a window, and the plate could be removed for inspection and returned. All these operations required cleanliness and meticulous care in handling the plate but could be performed without having to measure any of the chemical reagents-silver, iodine, mercury-all of which were available at the time in a relatively pure form. But what of Bayard? In the excitement following the public disclosure of the daguerreotype, he and his process were forgotten. As a defensive measure, Bayard published an account of his process on Feb. 24, 1840. A few days later, Lassaigne pointed out that his process had been described on April 10, 1839. Biot and Arago attempted to moderate the ensuing controversy, and at the meeting of the academy on March 16, 1840, they announced that the processes were the same and did not differ from that which Fyfe had described to the Society of Arts of Edinburgh the year before. They implied a priority for Lassaigne; Arago seems conveniently to have overlooked the pictures displayed in February 1839by Bayard. In October,as a protest, Bayardprepared self-portraits of himself as a corpse pulled wet from the Seine with a letter explaining why, when Daguerre was rewarded, this wretch had met such an untimely fate. Three copies of this macabre remonstrance, each of which may have required a 30-minute exposure, still exist. Bayard became a proficient amateur photographer, using most of the early processes expertly but remaining in the civil service to become chief clerk in the Ministry of Finance. He was a founder of the Photographic Society of France and lived out his life without acclaim, dying in 1887. Bayard's process is straightforward but requires long exposures. A sheet is impregnated with silver chloride by conventional immersion techniques and the silver salt is thoroughly photolyzed to a dark metal deposit. The uniformly dark sheet is immersed in potassium iodide solution and exposed to light while moist. The action of light dissociates potassium iodide, producing iodine, which oxidizes the adjacent silver to silver iodide. Afterward, the iodide is removed with hyposulfate to leave a direct positive print. It is surprising that different individuals would have discovered the same photographic process independently in such a short time. Possibly news of Bayard's experiments spread around Paris, but Fyfe's announcement must represent independent effort. The advantages of the negative/positive system were not yet apparent, and its use must have been counterintuitive because sentiment favored the more obviously straightforward direct positive approach. Talbot's report may contain an insight required by an investigator looking for a direct positive process. Talbot, in discussing the use of sodium chloride solutions for fixing images on salted paper, observes that although sodium iodide can be used, it is apt to lead to the fading of the image. The use of sodium chloride as a fixative by both Daguerre and Talbot has amazed a number of histori-

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ans. Silver halides form slightly soluble, complex halide ions, such as AgICl- and AgICli-, which can remove the thin deposit of silver iodide from the daguerreotype plate. In the paper print, although some silver chloride may be washed out in the chloride bath, the principal function of the salt seems to be to stabilize the residual silver halide in the sheet by surrounding the silver salts with a sheath of halide ions that promote recombination of any photolytic products that may be produced in subsequent exposure to light. Ammonium hydroxide does not dissolve silver iodide and was not an option for Daguerre.Talbot, Florence, and Fyfe tried aqueous ammonia as a fix for salted paper and commented adversely because they found it reduced the density of the developed image.

Hippolyte Bayard, shown in the self-portrait made about .1855 on albumen paper from an albumen plate negative, developed his own photographic process in the late 1830s; discouraged when the priority of his work was not recognized, in protest he made the direct positive selfportrait of himself (above) in 1840, modeling as a corpse drowned in the Seine

Print processes after 1839

Throughout the 19th century, the vast majority of paper prints were made by processes not depending on the formation of a latent image that then is developed chemically. For 12 years after Talbot's first announcement, simple salted papers containing a precipitate of silver chloride were used to make contact prints from paper negatives, which were commonly waxed for increased transparency. In 1850, Louis Blanquart-Evrard, a photographer in Lille, adapted to paper the albumen technique introduced for camera use by Claude Felix Abel Niepce de Saint-Victor, a cousin of [oseph-Nicephore Niepce. The albumen coating gave a smooth, glossy surface and kept the image at the surface, producing an attractive print with enhanced retention of detail. Success came rapidly, and Blanquart-Evrard established a substantial business making prints for inclusion in expensive travel books. The majority of paper prints

until the turn of the century were made on albumenized paper formed when sheets of paper were coated with egg white, dried, and then floated on an aqueous solution containing chloride ion and citric acid. These were manufactured in quantity and supplied to photographers for sensitizing by floating them again on a solution of silver nitrate prior to use. These silver images had to be toned with gold chloride in sodium thiosulfate solution to avoid fading. Herschel described the use of iron salts for photographic purposes in a paper he presented to the Royal Society on June 16, 1842.Complex ferric salts, such as ferric citrate, when exposed to light in the presence of an oxidizable matrix, are readily reduced to ferrous salts. Because the image of ferrous ion in the exposed area is barely distinguishable from the darker unaltered ferric ion, a variety of reagents, such as potassium ferricyanide for a negative and gallic acid for a positive, have been used to differentiate the two areas. When the differentiating reagent produces a colored precipitate with ferrous ion but not with ferric ion, the reagent can be incorporated in the sensitized sheet. Color forms during exposure and is completed when the exposed sheet is bathed in water to remove unaltered ferric salts and excess reagent. .Herschel described a sheet containing ferric ammonium citrate and potassium ferricyanide. Iron reduced to the ferrous state reacts in the exposed areas with the ferricyanide to give a blue image with a long tonal range. This he named cyanotype (from the Greek cyan, meaning blue). Two weeks later, he described chrysotype (from the Greek chrysos, for gold). In this process, after he exposed the sheet to light, Herschel differentiated the exposed areas of ferrous ion by treatment with a weak solution of gold chloride, which
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single transfer yields an image with left-to-right reprecipitates metallic gold through reduction by the versal, a problem solved in 1864 by Sir Joseph W. ferrous ion. The color depends on the size of the Swan, who developed a reliable double-transfer techcolloidal gold, but generally is purplish blue. A siminique. Until after World War I, carbon was widely lar silver image, named kallitype, is produced by reemployed for display prints and large portraits. duction of silver nitrate. . Although there are many variations and elaboraCamera processes after 1839 tions of the iron processes, three processes have received greatest attention: cyanotype (blue print), Only a limited number of acids were available from kallitype (brown print), and platinotype (in which which silver salts might be prepared for experimentaplatinum rather than gold is deposited as a nontion. It is probable that the Rev. [oseph Bancroft Reade, tarnishing deposit to produce prints of exquisite quala microscopist and founder of the Royal Microscopical ity).The Prussian blue pigment image of the cyanoSociety in England, first found that gallic acid, reacted type process yields prints of great stability and resiswith chlorides, gave silver salts with high sensitivity tance to fading that long were used for draftsmen's drawings and plans and for Claude Niepce de St. Victor making proof prints of negatives in the (left) invented glass plates graphic arts. The brown print, or Van Dyke, coated with albumen containing process was not used for artistic purposes silver halides in 1847. Sir John but from 1890 to 1960 was a route to sepia Herschel (below) developed masters for blueprints. several long-used photographic Although Ioseph Dixon. an inventor processes from Marblehead, Mass.. and champion of graphite for all purposes, used dichromates to make lithographic plates in the 1840s, practical use of dichromates in photography and the graphic arts stems from TaJbot's discovery in 1852 of their ability to selectively cross-link gelatin and similar colloids. Talbot prepared solutions of potassium dichromate in gelatin, which he used to coat burnished steel plates. After drying, exposure under a photographic Frsncois Arago, shown below negative to direct sunlight produced a faint lecturing at the Paris Observatory, image in the exposed areas that proved first announced Daguerre's process less soluble in warm water than the 'publicly and promoted its purcbese unexposed areas. Talbot found that he by the French government could wash away the softer unexposed areas, leaving a high-resolution raised image of gelatin which.. when dried, served as a protective stencil through which the metal could be etched to produce a steel engraving. After refinement, the dichromate process and its variants became the principal photomechanical means of preparing printing surfaces for photogravure, photoengraving, and photolithography until displaced in the past 30 years. In 1855 in Paris, Alphonse Poitevin obtained prints in a variety of colors by incorporating pigments into gelatin-dichromate solutions that were coated on paper. Since carbon black, which produces a permanent nontarnishing image, generally was used, the technique is referred to as carbon printing, regardless of the color. The insolubilization of the gelatin is greatest at the front surface of the coating and is attenuated by the absorption of actinic light by the dichromate. Only areas fully exposed are hardened through to the support; intermediate tones are not adherent to the base and wash away. The gelatin layer, therefore, must be inverted to adhere the front surface of the sheet to another support and wash the unhardened gelatin away from the back. A variety of release coatings and permeable supports have been used to permit wash-off after transfer to a second support. A
40 December 18. 1989 C&EN

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.. .. .. . to light. Reade did not publish his photographic work of early 1839 or b~fore, but it ~as ct.escrib~d orally in :!several lectures gIven by a friend In April and May .'. 1839. Certainly Talbot, using gallic acid in a series of investigations during 1840 and 1841, made fundamental discoveries relating to the latent image and the formulation of developing solutions. Paper impregnated with a silver salt can produce a stable, invisible latent image when exposed to small amounts of light. Talbot's discovery of this phenomenon in 1840 occurred when he was comparing the exposure of both wet and dry sheets containing gallic acid. In a letter, he observed: "The paper, when taken out of the camera, presented hardly any thing visible; but ... I continued to observe it by candle light, and had soon the satisfaction of seeing a picture begin to appear, and all the details of it come out one after the other .... I know few things in the range of science more surprising than the gradual appearance of the picture on the blank sheet, especially the first time the experiment is witnessed." Study of the latent image, imperceptible until placed in a developing solution that both reveals its existence and destroys its unseen character, has engaged photographic theorists ever since. For the next 30 years solutions containing silver nitrate and gallic acid (the gallonitrate of silver) were commonly used to develop the latent image. These so-called physical developer solutions act much like a silver mirroring solution, depositing silver selectively where minute deposits of photolytic silver occur. The process utilizing a developable latent image and a physical developer was first named calotype, from the Greek for beauty, by Talbot, who patented. the process in 1841 and renamed it Talbotype. Camera exposure time was reduced by a factor of several hundred, making the negative/positive process competitive with daguerreotypes for a skilled worker. Although camera exposures were made with this process, prints were made on salted paper from waxed negatives. It was apparent that glass would be a better support than paper but preparing functional coatings with the necessary adhesion to glass, dimensional stability during processing, and adequate clarity was a challenge. Niepce de Saint-Victor succeeded in 1847 in coating glass with egg albumen containing halides and then precipitating silver salt in the coating by bathing in silver nitrate solution after it had dried. Becauseof its slow speed; this material was generally unsuited for camera work but was the coating chosen for lantern slides for many years. Glass supports became practical in the early 18505, however, with the introduction of the collodion wet plate process by Frederick Scott Archer, an English sculptor who was experimenting with better ways to ~repare photographs of models. In Archer's process, silver halides are precipitated in a swollen coating of cellulose nitrate (collodion) containing cadmium and ammonium bromides and iodides on glass just prior to exposure. The sensitized plate must be exposed and .. ..pro~essed while the coating is wet. The developer was 1'; '. .
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The typical image structure for a gilded daguerreotype is shown in these secondary electron micrographs taken by M. Susan Barger of Johns Hopkias University. The micrograph on the left depicts a highlight region. The small white particles are silver crystals with a small portion of gold. These image particles are typically 0.1 um to 1.0 um in diameter and spacing; there can be as many as 200,000 particles per square millimeter in very white portions of a daguerreotype image. The righthend micrograph shows particles typical of a dark gray or black region of a daguerreotype image. The regions of deepest shadow have particles that can range in diameter from 5 to 50 um, with 50 to 100 particles per sq mm. These larger image particles are primarily silver crystals with gold. Larger image particles may contain very small portions of mercury. The gray field with dark holes in the righthand micrograph is the underlying silver plate. The pattern of holes and grain boundaries is the result of cyanide etching from some past cleaning treatment in a cyanide bath. The scale bar is equal to 10 usn.

a weakly acidic solution of ferrous sulfate, and the commonfix was a solution of sodium cyanide.Likemany of his contemporaries, Archer made no attempt to capitalize on his discoveries but published them in detail. The wet plate technique is cumbersome and demands great manipulative skill, but it produces negatives that have good resolution and great detail. Its introduction marked the end of the daguerreotype, although the latter lingered several years longer in North America (until the Civil War)than in Europe. The continuing demand for portraits in the da-: guerreotype mode was met, especiallyin the US., by the production of ambrotypes (from the Greek for durable) and tintypes, both of which were packagedin cases to resemble daguerreotypes. In both of these processes, a weak negative silver image is prepared by the collodion wet plate process and viewed against a dark background to produce the visual effect of a positive. The tintype, or more correctly melainotype, was invented in 1856 by Hamilton Smith, professor of chemistry at Kenyon College in Ohio. It consists of a
December 18. 1989 C&EN 41

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dilute wet plate collodion coating on a thin steel sheet enameled black. Smith charged a one-time fee of $20 for use of the process. The special black support required for the process allowed suppliers to control this market more fully than the ambrotype on glass. The tintype survived beyond the turn of the century as an' inexpensive means of making portraits and novelties for immediate delivery. The daguerreotype, despite its initial supremacy, was a dead end; the wet plate only hastened its disappearance. The negative/positive approach championed by Talbot is far more flexible than a direct positive technique, as Bayard ultimately perceived. Exposures fora direct positive must be precise, but with a negative modest over- or underexposure can be compensated for in the printing step. Multiple prints, too, can be made from a negative using a variety of print processes. If the printing operation fails to satisfy, the negative is available for further trial; this permits a wide range of creative darkroom manipulations that can be pursued-experimentally to achieve the desired final image. Talbot's grasp of these benefits may have been incomplete at first, but his perception respecting the latent image and dedication to experiment make him the true father of photography. In his lifetime, his other accomplishments, including his role in deciphering the cuneiform writing of the Babylonian clay tablets, overshadowed his photographic work and at his death his most detailed obituary was in a journal of biblical archaeology. In 1871, Richard Leach Maddox, an English physician and microscopist, reported experiments on coatings of silver bromide in gelatin that gave dry plates with surprising storage life. Within 10 years, dry plates were available from a number of firms, and photographers were freed from the daunting task of coating wet plates. The heroic age of photography was ending, although still lamented by some; a letter to the British Journal of Photography in 1880 reads: "This new fangled idea of ready-made plates takes all the fun out of photography. The next stage might be a shop to produce prints and lantern slides to order-but that is too distressing to anticipate." 0

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Suggested readings
Crawford, William, "Keepers of Light: A History and Working Guide to Early Photographic Processes," Morgan, Dobbs Ferry, N.Y., 1979. Eder, Joseph-Maria, "Gesichte der Photographie" reprint of 1932 translation by E. Epstean, Ayer, Salem. N.H.1979. Grantrand, Jean-Claude, "Hippolyte Bayard-Naissance de l'lmage Photographique," prepared for an exhibit on Hippolyte Bayard for La Societe Francalse de Photographie. Jenkins, Reese V., "Images and Enterprise: Technology and the American Photographic Industry 1839-1925," Johns Hopkins Univ. Press, Baltimore, Md. 1975. Jussim, Estelle; "Visual Communication and the Graphic Arts: Photographic Technologies in the Nineteenth Century"; R. R. Bowker, N.Y., 1974. Kosar, Jaromir, "Light Sensitive Systems," John Wiley, N.Y., 1965. Kossoy, Boris, "Hercule Florence," Livraria Duas Cidades, Sao Paulo, 1980. Ostroff, Eugene, editor, "Pioneers of Photography," Proceedings and papers 1st Int'1 Congress: Pioneers of Photographic Science, Published by SPSE, The Society for Imaging Science and Technology; distributed by Northeastern University Press, Boston, 1987. Potanniee, Georges, "The History of the Discovery of Photography," Reprint of 1936 Translation by E. Epstean, Ayer, Salem, N.H. Sturge, J., Walworth, V., and Shepp, A., editors, "Imaging Processes and Materials," Neblette's 8th Ed., Van Nostrand Reinhold, N.Y. 1989. Welling, William, "Photography in America, The Formative Years 1839-1900," University of New Mexico Press, Albuquerque, N.M., 1978; Paperback edition, Thomas Y. Crowell, N.Y., 1987.
42
DeCember 18, 1989 C&EN

John L. Ennis is a member of the product technology section of Arthur D. Little Inc., a contract research and consulting firm in Cambridge, Mass. After receiving his B.S. degree from Beloit College in 1948, he did graduate work in organic chemistry at Boston University. Ennis joined A. D. Little in 1950, where he has worked on a wide range of technical/ economic and industrial chemical problems, concentrating on light-sensitive imaging systems (including both silver halide and nonsilver photographic and reproduction systems), graphic arts, inks, and the non textile use of dyes. A senior member of the Society of Photographic Scientists & Engineers, Ennis has served on the society's board of directors and as president of its Boston chapter. In the A. D. Little lead balloon contest of 1977, a whimsical effort by several of the company's employees to loft balloons having a skin of lead foil and inflated with helium, he was cocaptain and designer for the team that successfully flew the smaller (9 feet in diameter) Ofthe two balloons to lift off. Ennis wishes to acknowledge the help of colleagues Valerie Zebedee, Christilla Segerand, and Luverci Sachs of the A. D. Little International offices in London, Paris, and Sao Paulo.
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