Chrysotype: Introduction Gold has always played a role in photography as the ultimate Photography in means of stabilizing and protecting the silver image, the universal commercial medium. Since the dawn of the art- science of photography around 1840, a gold complex salt Nanoparticle Gold (1), sodium bisthiosulphatoaurate(I) was used to ‘gild’ the images of daguerreotypes by depositing gold metal on the surface of the silver: Mike Ware 3- 3- 20 Bath Road, Buxton, SK17 6HH, UK Ag + [Au(S2O3)2] Au + [Ag(S2O3)2] e-mail: [email protected] In 1847, this was also recommended for the stabilization of silver photographic prints on paper. In this way, vulnerable Abstract silver images were protected from the sulphiding action of the The printing of photographs in pure gold, rather than polluted industrial atmospheres of the Victorian era, which the ubiquitous medium of silver, was first achieved in otherwise caused them to tarnish or fade. From 1855 onwards, 1842 by Sir John Herschel, but his innovative the gold toning of silver salted paper and albumen prints ‘chrysotype’ process was soon consigned to obscurity, became standard practice, such that the British Government owing to its expense and uncertain chemistry. In the Photographer in India, Linnaeus Tripe, was moved to advise his 1980s some modern coordination chemistry of gold colleagues “Not to spare the sovereigns!” (2). This important was applied to overcome the inherent problems, application of gold in photography has previously been enabling an economic, controllable gold-printing reviewed in the Gold Bulletin by P Ellis (3). process of high quality, which offers unique benefits But if gold is such a stable image substance, why not by- for specialised artistic and archival photographic pass the use of reactive silver altogether, and make purposes. The colour of the gold image depends on photographs entirely in gold in the first place? Technically, the dimensions of the nanoparticles, which are there are difficulties: none has ever been usefully produced controlled by the parameters of the photochemical in the camera, owing to a much lower photochemical process. sensitivity of gold salts compared with the halides of silver, which can be uniquely ‘fast’ in development, providing us with near-instantanous negatives. Today, we owe the high Keywords speed of camera film emulsions to the use of gold(I) nanoparticle gold, chrysotype, aurotype, alternative compounds as sensitizers for the silver halide grains (4). photographic printing, iron-based process, siderotype, Printing positives from the negatives, however, is less photochemistry of iron(III), thioether complexes of gold(I), critical: exposures can be lengthy and light sources intense, Sir John FW Herschel especially if enlargers are not employed, which opens the door to using less sensitive photochemistry. The purpose of this review is to describe the chemical evolution of an economic and controlled process for photographic printing of pictures in pure gold in the nanoparticle state. The history of this process finds its origins in the dawn of photography, but it lay forgotten – until recent times – because it did not prove economic in the face of the competing metal, silver. In this account, the historical developments will be re- interpreted with the wisdom of hindsight, using modern chemical nomenclature, equations, and concepts, rather than the original nineteenth-century chemical language. For those readers who would like to see the original writings, which are sometimes cryptic and obscure, an historical review is recommended (5). Sir John Herschel’s Chrysotype Process The announcement of the invention of silver photography on paper in January 1839, by William Henry Fox Talbot, inspired Gold Bulletin 2006 • 39/3 124 his colleague, Sir John Herschel to begin an energetic pursuit liberates free citrate ions. Citrate is an excellent reductant for – of a whole variety of potential photographic processes (6). converting gold(III), as in [AuCl4] , to the metal, so the two Unlike Talbot, Herschel showed little interest in recording components could not be pre-mixed without images in the camera; he was concerned with the decomposition. Consequently, Herschel was obliged to coat photochemical effects of the optical spectrum on a wide his papers only with ammonium iron(III) citrate by itself, make range of substances, organic and inorganic, with the ultimate the exposure, then ‘develop’ the picture by treating the sheet objective of trying to print permanent photographs in colour. with a solution of sodium tetrachloroaurate(III), which, of In 1842, a young fellow-member of the Royal Society, course, became rapidly contaminated by the soluble Dr. Alfred Smee, introduced Herschel to a substance that had substances leaching out of the sensitized paper. This was a lately been attracting the attention of pharmacists as an iron very uneconomic and wasteful way to proceed, because it tonic: ammonium iron(III) citrate. Herschel soon discovered produced images of uncertain, and frequently inferior quality, that this salt was very sensitive to ultraviolet and blue light at considerable expense. There was also an aesthetic (7), and he recognised that the iron(III) was reduced difficulty at the time with photographic images that were not photochemically (8) to iron(II): the conventional brown or black of silver and platinum in the finely-divided state; the reds and purples of nanoparticle gold hn photographs were an unacceptable shock to Victorian (III) (II) + 2Fe + C6H8O7 2Fe + C5H6O5 + CO2 + 2H pictorial sensibilities. which could then react further to form permanent images in a variety of ways: Later Attempts at Printing in Gold i) by coupling with hexacyanoferrate(III) to make Prussian blue, iron(III) hexacyanoferrate(II), as in Herschel’s Throughout the nineteenth century, there were sporadic cyanotype process, which later assumed enormous attempts to revive, improve, or re-invent, Herschel’s commercial importance as the first reprographic process chrysotype (10). Three of the more chemically interesting – for making blueprints: investigations of alternative methods of printing in gold deserve mention. Robert Hunt in 1844 found a mixture of (II) (III) 3- (III) (II) – Fe + [Fe (CN)6] Fe [Fe (CN)6] silver nitrate with potassium dicyanoaurate(I), K[Au(CN)2], to be light-sensitive – the latter was prepared from fulminating ii) by reducing a salt of a noble metal to the metal, as in gold and potasssium cyanide! – but it is uncertain how far the Herschel’s argentotype (silver), celaenotype (mercury) and image was composed of gold, or of silver (11). chrysotype (gold) processes: John Mercer around 1855 converted the Prussian blue of cyanotype images into Purple of Cassius (12) – the long- (II) (III) – (III) – 3Fe + [Au Cl4] 3Fe + Au + 4Cl celebrated ceramicists’ pigment, consisting of colloidal gold dispersed in tin(IV) hydroxide – its history has been fully iii) later in 1873 William Willis, using the same principle, described in this Journal (13). Mercer first converted the reduced salts of platinum(II) or palladium(II) to the metals, iron(III) hexacyanoferrate(II) into silver hexacyanoferrate(II) by but with iron(III) oxalate rather than citrate as the treatment with silver nitrate, after which he reduced it to photosensitive component. This was the celebrated silver metal by sodium stannite, Na2[SnO2], and finally by platinotype process, which became a great commercial treating this in a bath of sodium tetrachloroaurate(III), the and artistic success (9). Purple of Cassius was precipitated. Herschel’s chrysotype process did not win acceptance into Charles Burnett in 1857 employed photosensitive salts of the photographic repertoire, dashing his hopes, in the face of uranium(VI), instead of iron(III), to make images in gold (14): competition from Talbot’s more tractable and less expensive silver processes, even though these suffered from hn 2+ – + 4+ acknowledged impermanence. What exactly was the UO2 + 2e + 4H U + 2H2O problem with Herschel’s chrysotype? His difficulties began 4+ – 2+ + with the photosensitive substance, ammonium iron(III) 3U + 2[AuCl4] +6H2O 3UO2 + 2Au + 4H + 8HCl citrate, which is amorphous and uncrystallizable, and therefore of unknown structure even today; it displays a The only significant improvement in the chrysotype process highly variable composition, with an iron content varying itself arose in 1897 when a ‘green’ form of ammonium between 28% and 14%, depending on the method and iron(III) citrate was first prepared (15), which was less reactive conditions of preparation; it can be obtained in basic or towards tetrachloroaurate(III) and could be pre-mixed with it acidic forms, varying in colour from brown to green. All in all, before coating, but the outcome was seldom pictorially it is a highly ‘ill-characterised’, polymorphic, irreproducible acceptable (16). In contrast to the equally costly platinotype substance! It appears that the variety available to Herschel process, which proved highly reliable, the expense of was one of the ‘brown’ forms, which is basic, and easily frequent failure with the chrysotype medium precluded it Gold Bulletin 2006 • 39/3 125 from general use. It was deemed inadequate, and by the platinotype and palladiotype processes due to Willis (21), close of the century, gold had been totally written off as an which used iron(III) oxalate. However, this second, image- imaging substance per se, nothwithstanding its widespread forming reaction does not take place in the dry sensitized