Microchemical Journal 114 (2014) 815

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Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

Characterization of unprocessed historic platinum photographic papers by Raman, FTIR and XRF
Silvia A. Centeno a,, Anna Vila b, Lisa Barro c
a b c

The Metropolitan Museum of Art, Department of Scientic Research, 1000 Fifth Avenue, New York, NY 10028, USA Statens Museum for Kunst, Center for Art Technological Studies and Conservation, Slvgade 48-50 DK-1307, Copenhagen K, Denmark The Metropolitan Museum of Art, Photograph Conservation, 1000 Fifth Avenue, New York, NY 10028, USA

a r t i c l e

i n f o

a b s t r a c t
Five unprocessed historic platinum photographic papers were characterized by a combination of Raman, FTIR and XRF spectroscopies to gain insight into their manufacturing processes and obtain information that can help identify the use of similar papers in works of art in a non-invasive manner. The analysis of one of these papers, Japine Platinotype for Sepia Tones, showed a sensitized surface layer in the recto consistent with the use of a parchmentization process of the paper substrate, and that the verso presents a slightly modied surface. Raman and FTIR measurements revealed that this surface layer in Japine is composed mainly of amorphous cellulose. No gelatin or other surface coatings were found to be present in Japine. In the rest of the papers studied, the sensitizer was found to have been applied directly onto the paper bers and no gelatin or gums were observed as sizings. Relatively larger amounts of mercury were detected in Japine, conrming the use of a Hg salt in a sepia-type platinum paper. The combined use of Raman and XRF provides information that can help discriminate platinum photographic processes involving parchmentization in works of art in a non-invasive manner. 2013 Elsevier B.V. All rights reserved.

Article history: Received 18 October 2013 Received in revised form 27 November 2013 Accepted 27 November 2013 Available online 4 December 2013 Keywords: Platinum photographs Raman FTIR ATR XRF Platinotype Japine Aristotype Sepia

1. Introduction Fine art photographers at the end of the nineteenth century and at the beginning of the twentieth century produced platinum photographs with a broad range of effects, from the soft atmospheric images of the Pictorialist era to the crisp cityscapes and abstract forms of early Modernism. Extraordinary platinum prints by Alfred Stieglitz and Paul Strand are among the many photographs within the world renowned collection at The Metropolitan Museum of Art. Platinum prints are currently being characterized in an effort to unravel the sophisticated engineering of commercial platinum papers and the photographers' many processing methods. The results will enhance dating, attribution, and broader art historical research in addition to playing a key role in the preservation and conservation of the works. The technique for making platinum photographs by using lightsensitive iron salts was patented by William Willis in 1873. He called these prints Platinotypes and by 1879 manufactured these papers in his London-based company with the same name. The most typical Platinotype photographs have neutral black image material dispersed among the paper bers of the substrate creating a rich, matte surface. Photographers enjoyed the beautiful long tonal ranges and the
Corresponding author.

presumption that platinum images were more permanent. By the 1890's the Platinotype company sold a small selection of paper types; Sepia Platinum papers were also introduced during this period. The sepia warm toned papers were made with mercury in addition to platinum salts in their sensitizers. By the early twentieth century, in addition to Platinotype papers, available in London and in the United States through the subsidiary Willis and Clements, the market for commercial platinum papers expanded to include Eastman Kodak and the American Aristotype Company among others [1,2]. At this time, the variety of papers blossomed and photographers could choose from a multitude of tones, textures and surface sheens. 1.1. Platinum prints chemistry The chemistry of the platinotype and palladiotype photographic processes has been discussed by several authors [3,4]. Basically, in these processes, a paper support is coated with a sensitizer containing an oxalato-complex of Fe (III), generally ferric oxalate, subsequently placed in contact with a negative and exposed to UV light. The oxalato-complex of Fe (III) is photoreduced, giving carbon dioxide and an oxalatocomplex of Fe (II): h 2FeC2 O4 3
3

2FeC2 O4 2

C2 O4 2CO2

0026-265X/$ see front matter 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.microc.2013.11.016

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The [Fe(C2O4)2]2 is a strong reducing agent that reacts with platinum and/or palladium salts present in the sensitizer to yield the metal/s that will form the image:
PtCl4
2

2FeC2 O4 2

2C2 O4 Pt 2FeC2 O4 3

4Cl

2 In the platinum-based processes, generally the K2[PtCl4] or Na2 [PtCl4] was used. Precipitation of the bulk of the platinum or palladium metals to form the image occurs after the paper exposed to light is immersed in a developer, traditionally alkali metal oxalates, such as potassium oxalate, that keep [Fe(C2O4)2]2 in solution, thus driving the reaction [2]. Sources indicate that Willis may have added Hg, Pb and Cr-containing salts to the sensitizers in Platinotype papers [3,5,6].

is known to have waxed his prints on Platinotype KK paper because it had, as he described it, a disagreeable toothy surface [14]. Characterizing these photographic papers has an impact on dating and attribution in art historical studies in addition to playing a key role in conservation treatments and preservation evaluations. In the present study, ve unprocessed historic platinum photographic papers were characterized by a combination of XRF, Raman spectroscopy, FTIR and SEMEDS with the aim to obtain signatures that can help identify the use of similar photographic papers in works of art in a noninvasive manner. 2. Experimental 2.1. Samples The ve historic platinum photographic papers characterized for the present study are listed in Table 1, along with the manufacturers' descriptions, and are shown in Fig. 1 together with two advertisements from the period: from 1899 and 1902, respectively [16,17]. Of these ve papers, three were manufactured by the Platinotype Company and two by the American Aristotype Company. A Whatman lter paper sample was used as a pure cellulose reference for the FTIR, ATR and Raman measurements. All the historic samples are unprocessed commercial platinum papers found in their original commercial packing. The Japine for Sepia Tones was the only one found in a sealed, not previously opened tin. Typically, a freshly sensitized platinum paper has a bright yellow color, that turns brownish gray when exposed to light. The aged samples have a range of brown tones (Fig. 1). The Japine paper was very dark overall when removed from its sealed tin. Light exposure does not appear to be the cause of the image conversion. More likely, a chemical reducing agent may have been present in the paper and caused an overall change [18]. This is different from the KK paper which even after 100 years still appears to be slightly light sensitive and the image tone does not appear to have changed with exposure to light. With the exception of the Japine, all of the papers have smooth, compact matte surfaces. 2.2. XRF and SEMEDS X-ray uorescence (XRF) measurements were performed on the sensitized sides and on the versos of all the samples using a Bruker ARTAX 400 instrument equipped with a Rh tube, a 1.0 mm collimator, and a Si drift detector. All the samples were analyzed in a He atmosphere using both unltered Rh radiation and a 26 m lter, for a

1.2. The paper support The properties of the paper support, how this paper is dried after the sensitizer is applied, and the use of additives in the sensitizer are important factors that determine the quality of the nal image [3]. A platinum print is often described as a plain paper process in which the chemical solutions are soaked into a homogenous paper support. This is unlike other processes where a portion of the photoactive compounds is dispersed into a separate binder layer, such as gelatin or albumen. Typically a plain paper without a binder or coating gives prints with a more matte appearance. One signicant variant to this paper structure was the Japine paper. The Platinotype Company introduced Japine papers in 1906 [7]. Japine was a proprietary term indicating a glossier or semi-matte paper in comparison to the competing matte platinum papers. Based on their glossy appearance, Japine papers could easily be misidentied as ones with gelatin or albumen binder layers. As proposed in 1916 [8] and more recently hypothesized by Ware [9], the manufacture of the Japine paper substrate might involve a parchmentization process using concentrated sulfuric acid applied to the paper's surface that would generate a modied surface layer in which the sensitizer would be applied. A Platinotype patent from the period shows that the Willis and the Platinotype company were aware of the technique [10]. The parchmentization of paper has been known since the midnineteenth century, and consists in the treatment of ordinary paper by immersing it in sulfuric acid and washing it immediately to remove the acid [11]. The treatment of the paper sheet could result in the full parchmentization, or just in the modication of one surface. Acid hydrolysis of cellulose can result in different nal products depending on the conditions of the reaction. After homogeneous acid hydrolysis small molecules only, i.e. glucose, may result, or the process can come to stop at a macromolecular level, for example after an heterogeneous hydrolytic treatment with more dilute acids [12]. 1.3. Processing and nishing techniques By adjusting laboratory techniques and additives, photographers could change their prints' tonal range and contrast [5]. The surface gloss and effective saturation of the densities could be also be adjusted through nishing techniques such as waxing or varnishing [13]. These methods in combination with the selection of commercial papers and hand-sensitized papers lead to the production of a wide variety of effects. Among many others, eminent photographers Paul Strand and Alfred Stieglitz used Platinotype papers, including Japine. Stieglitz in his many letters and articles on technique stated that he preferred Platinotype papers although he also described using American Platinum [14,15]. Because of its glossier surface, Japine papers can be visually mistaken for coated platinum prints or possibly gelatin silver prints. Alfred Stieglitz

Table 1 List of historic photographic papers analyzed. Sample Brand, manufacturer's description # 1 2 Japine Platinotype Paper for Sepia tones, hot or cold bath process Platinotype Paper AA. For the cold-bath process, smooth paper, medium thickness Platinotype Paper KK. For the cold-bath process, smooth, thick paper, ne surface gives very bright prints American Platinum for Cold Development, Manufactured by American Aristotype Co. American Platinum for Cold Development, Manufactured by American Aristotype Co. Date Tin not dated. Produced from 1906 to 1937. Tin not dated. Based on product list found in the Japine tin: 1906 to 1937. ca. 1908

August 1903

June 1908

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Fig. 1. A- Historic platinum photographic papers analyzed: Japine Platinotype for Sepia Tones(a), Platinotype Paper AA (b), Platinotype Paper KK ca.1908 (c), 1908 Aristotype Co. American Platinum (d), and 1903 Aristotype Co. American Platinum (e). B- The Photo-Miniature magazine advertisements: 1899 (a) and 1902 (b), respectively.

300 second live-time, at 30 kV and 1000 A. The samples were analyzed air-backed, that is without any material behind the paper to eliminate potential interferences.

Scanning electron microscopyenergy dispersive X-ray spectrometry (SEMEDS) analysis was done using an Oxford Instruments AZtec Energy Microanalysis system with a X-MaxN 80 silicon drift detector,

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Fig. 2. XRF spectra acquired in the sensitized sides of the Japine Platinotype Paper for Sepia Tones (sample #1, black spectrum) and the Platinotype AA paper (sample #2, gray spectrum), respectively, using a Rh tube with a 26 m lter, at 1000 A and 30 kV, in a He atmosphere.

attached to a Zeiss Sigma HD variable pressure SEM operated at an accelerating voltage of 20.0 kV under high vacuum conditions. 2.3. FTIR and ATR Fourier transform infrared (FTIR) spectroscopy measurements were carried out with a Bruker Vertex70 spectrometer coupled to a Hyperion microscope equipped with a cryogenic mercury-cadmium telluride (MCT) detector. For measurements in the transmission mode, the samples were placed between the windows of a diamond anvil cell and observed with a 30 objective and a spectral resolution of 4 cm 1. Attenuated total reectance (ATR) measurements were performed using a Ge crystal with a refractive index of 4.01, which has an anvil design with an 80-m tip. A vertical sliding mechanism allows the crystal to be positioned out of the eld of view, to provide visualization of the sample. The lowest contact pressure level available (0.8 N) was used for all measurements. Spectra were acquired in the 4000650 cm 1

range with a 4 cm 1 resolution and 400 scans. The normalization of the transmission FTIR spectra was carried out by taking the integral of the absorbance of the CH band (ca. 2900 cm 1) in the range 3000 2800 cm 1 as an internal standard [19]. 2.4. Raman spectroscopy Raman analyses were carried out with a Renishaw System 1000 spectrometer congured with a Leica DM LM microscope, notch lters, and a thermoelectrically cooled charged-coupled device (CCD) detector, using a 514 nm laser line for excitation. The laser beam was focused on the different areas of the samples using a 50 objective. Neutral density lters were used to set the laser power at the sample to values between 0.5 and 2.0 mW. A 1800 lines/mm grating was used, and in each spot, 20120 scans were acquired. The wavenumber stability and the accuracy were checked by recording the Raman spectrum of a silicon wafer (520 cm 1).

Fig. 3. Raman spectra acquired in the sensitized side of the Japine Platinotype Paper for Sepia Tones (sample#1, spectrum a), in a pure cellulose paper sample (spectrum b), and in the sensitized side of the ca. 1908 Platinotype Paper KK (sample #3, spectrum c), respectively. 0 = 514 nm.

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2.5. ELISA Two separate ELISA screening experiments were performed on the seven historic platinum paper samples. In the rst experiment, samples were screened for collagen type I and gums. The collagen type I antibody has cross-reactivity to mammalian as well as sh collagen type I. The gum antibody has wide cross-reactivity to different classes of gums. In the second experiment, the screening was expanded to include antibodies to ovalbumin and gum tragacanth. In both experiments, a replica paper with a gelatin coating prepared by applying two layers of a 3% solution in water was used as a positive control for the presence of collagen type I. Internal positive and negative controls were run for each of the antibodies. For the rst ELISA experiment, the paper samples weighed between 180 to 250 g. For the second ELISA experiment, greater sample mass was taken for analysis. The samples weighed between 1.5 mg to 2.8 mg. The paper samples were extracted with ammonia bicarbonate buffer and triuoroethanol (TFE) with heat (60 C) and ultrasonication. Each of the samples was run in triplicate with serial dilutions. Extraction procedure took about 4 h and the antigen incubation was done overnight. The primary antibody incubation was performed overnight at 4 C after blocking the samples for non-specic binding. The secondary antibody application, colorimetric development and analysis were performed on the third day. 3. Results and discussion 3.1. XRF measurements The historic photographic papers analyzed are listed in Table 1, and are shown in Fig. 1. A comparison of XRF spectra recorded in the sensitized sides of the Japine Platinotype (sample #1) and the Platinotype AA (sample # 2) is presented in Fig. 2. Both photographic papers show Pt, K, Cl and Fe; Japine has relatively larger amounts of Hg and the Platinotype AA paper has relatively larger amounts of Pb. The rest of the photographic papers (samples #3 to #5) gave similar results to those obtained for the Platinotype AA, they showed larger amounts of Pb and smaller amounts of Hg than Japine. As mentioned above, in the platinotype process, an oxalato complex of Fe (III) and a platinum complex, typically [PtCl4]2 , are used in the sensitizer [3,4]. Therefore the observation of Pt, Fe, Cl, and K in the unprocessed papers is consistent with the presence of K2[PtCl4] and an Fe(III) complex. The presence of Hg likely originates in Hg (II) salts that were recommended as additives to the sensitizer in the platinotype process for obtaining warmer colors, lower contrasts, and smoother textures by improving the dispersion of the platinum in the cellulose bers. Also, Pb (II) salts were recommended for this purpose [3]. Small amounts of Cr were detected in Japine, Platinotype AA (shown in Fig. 2), and KK papers, but Cr was not detected in any of the two samples from the American Aristotype Co. It has been stated that small amounts of dichromate salts, such as the potassium or ammonium salts, were sometimes added to the sensitizer to increase the contrast in Pt prints [5]. Another potential Cr source is chrome alum, KCr(SO4)2 12H2O, that was typically used mixed with gelatin or starch as a sizing for the paper substrates in different photographic techniques [6,20,21]. It will be shown below that no gelatin or any other proteinaceous material, is present in any of the papers analyzed. It was not possible to determine by XRF if S was present in the Japine sensitized side due to the overlap of the K lines of S and the M line of Pb. However, S was observed by SEMEDS conducted under high

vacuum conditions. SEMEDS also conrmed the presence of Cl detected by XRF in Japine and in the rest of the papers. In the verso of all the papers studied, Al was observed by XRF. The presence of Al is typically associated with the use of an alum rosin sizing in the paper substrate. The darkroom processing will alter the amounts of Pt, Hg and Pb, and should in principle remove the Fe. We have detected Fe in some early 20th century artistic Pt photographs and this could indicate that the removal of Fe is not complete, however toning with iron ferrocyanides deposited from a ferricyanide solution has been mentioned by some sources [22]. 3.2. Raman measurements In the Raman spectra of celluloses the majority of the bands are not pure group vibrations [23,24]. In the 1500950 cm 1 range, only the bending vibrations of the internal methylene groups CH2 may be described as group modes. Raman spectra acquired in situ in the Japine surface layer and in a pure cellulose paper sample are shown in Fig. 3 (spectra a and b, respectively). The typical broadening and loss of resolution of the signals expected for amorphous cellulose are evident in the spectrum of the Japine, particularly for the bands in the range 1200 1000 cm 1, when compared to the spectrum of pure cellulose [25]. In the spectrum of the Japine sensitized layer, the band at ca. 900 cm 1, assigned to an increase in the amount of disorder in celluloses [23], also points out to the presence of amorphous cellulose. This band is not visible in the spectrum of the pure cellulose sample. In the Raman spectrum of the 1908 Platinotype KK paper (sample #3), sharper bands in the range 12001000 cm 1 and no band at ca. 900 cm 1 are indicating the presence of crystalline cellulose (Fig. 3, spectrum c). The rest of the photographic papers listed Table 1 (samples #2, #4 and #5) gave similar results to those obtained for the KK paper. In pure celluloses, bands at ca. 1455 and 14751477 cm 1 are assigned to HCH bending with a small proportion of COH bending [23]. A strong feature at ca. 1467 cm 1 is present in the spectrum of the Japine sensitized surface, while a weaker and broader band approximately at 1479 cm 1 is visible in the spectrum of the pure cellulose sample. A gradual increase in a Raman feature at ca. 1462 cm 1 with respect to those at ca. 1455 and 1481 cm 1 has been shown to indicate an increase in the mass fraction of amorphous cellulose with respect to that of crystalline cellulose by Schenzel et al. [25]. These authors and Willey and Atala observed this behavior in amorphous cellulose prepared from crystalline cellulose I [23]. Therefore, the band at ca. 1467 cm 1 would also indicate the presence of amorphous cellulose in the Japine recto surface. However, a feature at ca. 1473 cm 1 is observed in the Raman spectrum of the 1908 KK sample in Fig. 3. The intensity of the cellulose bands in this range depends on the polarization of the incident beam so an unambiguous assignment of these bands in the photographic papers requires polarized Raman measurements [23]. Raman bands expected for the complex [PtCl4]2 at 330, 312, and 171 cm 1 [26] are not observed in the spectrum acquired in the Japine sensitized side (shown for the range above 200 cm 1 in Fig. 3). For the Fe2(ox)34H2O complex, a very strong band has been reported in the FT-Raman spectrum at 1493 cm 1, along a strong feature at 556 cm 1 and three medium intensity peaks at 1623,1467 and 640 cm 1, respectively [27]. Even though a strong peak is observed at 1467 cm 1 in the Raman spectrum of the Japine, the rest of the bands expected for the Fe (III) oxalato complex is not present in the spectra recorded. A band is

Fig. 4. ATransmission FTIR spectra acquired in a scraping removed from the sensitized side of the Japine Platinotype Paper for Sepia Tones (a), in a paper ber removed from the verso of the Japine (b), and in a pure cellulose paper sample (c), respectively. BOverlay of the normalized transmission FTIR spectra acquired in the sample removed from the sensitized side of Japine (a, continuous line), and in the pure cellulose paper sample (b, dotted). CDetail of the FTIR spectra in the 1800600 cm1 range for the same samples shown in A: scraping taken from the sensitized side of Japine (a, blue spectrum), scraping from the Japine verso (b, red spectrum), and pure cellulose paper sample (c, black spectrum, dotted). Shown after normalization. All spectra have a 4 cm1 resolution. (For interpretation of the references to color in this gure, the reader is referred to the web version of this article.)

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visible at ca. 300 cm 1 in the spectrum of the KK paper, however no features at 312 and 171 cm 1 were observed that could help identify the [PtCl4]2 complex in this sample. 3.3. FTIR measurements FTIR measurements in the transmission mode and ATR were performed in all the samples listed in Table 1. A transmission spectrum acquired on a sample scraping removed from the surface layer in the Japine sensitized side, where care was taken not to remove any bers from the paper substrate, is shown in Fig. 4A together with transmission spectra acquired in paper bers removed from the verso of the Japine and in a pure cellulose paper sample, respectively. In Fig. 4B and C, overlays of the normalized spectra recorded in the sample taken from the Japine verso and in the pure cellulose sample in the 4000600 cm 1 range, and of the same samples shown in Figure A in the 1800600 cm 1 range, respectively, are presented. When the spectrum acquired in the Japine sensitized side is inspected no characteristic bands for waxes, tree resins, or proteinaceous materials are observed [28]. The IR spectra of celluloses have been fully assigned [12]. The bands at ca. 40002995, 2900, 1430, 1375 and 900 cm 1 are known to be particularly sensitive to cellulose molecular order [29,30]. Features between 3660 and 3125 cm 1 are assigned to free OH and bonded OH stretching; absorptions at ca. 29702853 cm 1 are due to CH and CH2 stretchings and those at ca. 1430 cm 1 to CH2 bending; the peak at ca. 1370 cm 1 has contributions from CH bending and COO stretching while the absorption at ca. 900 cm 1 is attributed to CH bending or CH2 stretching [12]. When the spectrum acquired in the scraping taken from the Japine sensitized side is compared that of pure cellulose (Fig. 4A and B), broadening of the bands mentioned is evident. This is shown in detail for the 1800600 cm 1 range in Fig. 4C. The broadening of these bands has been ascribed to a greater disorder in the cellulose phase morphology [31]. Furthermore, Carrillo et al., in a study of regenerated cellulose bers, report that the ~1335 and 1315 cm 1 bands in cellulose overlap and diffuse over to 1310 cm 1 in amorphous cellulose, and that the ~ 1278 cm 1 band broadens, as observed in our study; for the bers studied by these authors intensity changes are observed at ca. 1375 and 1278 cm 1 that are not visible in the spectra acquired in the Japine sensitized layer [32]. In Fig. 4A, it can be seen that some band broadening has also occurred in the spectrum of the sample taken from the verso of the Japine. As mentioned above, the parchmentization of a paper sheet with sulfuric acid could be carried out so as to modify both surfaces, or just one. Our results are indicating that the parchmentization process in the Japine manufacture leaves a photographic surface layer that is rich in amorphous cellulose and, to a lesser extent, the verso of the paper substrate is affected during this process. Also, important differences among the spectra of the Japine surface, Japine verso and cellulose sample can be observed in the 1750 1600 cm 1 range, where the vibrations of adsorbed water (1670 1635 cm 1), and of COO stretching (16501550 cm 1) are expected for celluloses, along with those of carbonyl and aldehyde functions arising from opened terminal glycopyranose rings or oxidation of OH groups (above 1700 cm 1) [12,19]. The relative increase in the absorption at ca. 1667 cm 1 may be explained as a change in the hydrogen bonding in the Japine sensitized layer, when compared to verso of the Japine and to the pure cellulose. It has been shown that the broad OH bending due to bound water in cellulose, with a maximum approximately at 16411645 cm 1, is resolved into two bands at 1663 and 1635 cm 1, respectively, in some treated celluloses [29]. The change in hydrogen bonding in the Japine surface layer is further supported by the increase in the absorption due to the OH stretch around 3400 cm 1 when compared to pure cellulose (Fig. 4B). The shoulder at ca. 1712 cm 1 could be assigned to products of a partial oxidation of cellulose during the acid parchmentization process in the Japine sensitized side. Carbonyl functions resulting from the

thermo-oxidative degradation have been detected in cellulose samples with a degree of oxidation as low as 0.12 [33]. However bands above 1700 cm 1 are observed in the spectra of other Pt photographic papers that do not have parchmentized surfaces, such as the Platinotype AA that has a shoulder at ca. 1707 cm 1 (spectrum not shown), and a peak at ca. 1723 cm 1 is present in the spectrum of the Japine verso. Therefore the 1712 cm 1 feature in the Japine sensitized layer cannot be assigned with certainty, and this is also the case for the 1707 and the 1723 cm 1 bands in the Platinotype AA and the Japine verso, respectively. As mentioned above, no bands characteristic of proteinaceous materials were observed in any of the IR spectra acquired. These results were conrmed by ELISA experiments that tested for collagen type I, and that were negative for all the samples listed in Table 1. ELISA experiments conducted to test for gums in general, and for gum tragacanth in particular, and for ovalbumin were also negative. Therefore, it is possible to assert that no gelatin or albumen is present in the Japine surface layer. These results allow to rule out speculations that Japine papers may have had a gelatin emulsion or coating [1]. The absorbency of the paper support would inuence the quality of the nal image, and this could be controlled by including a sizing agent, either during the manufacture of the paper or by applying a coating to its surface [3]. Proteinaceous materials such as gelatin and also alum rosin were commonly used at the turn of the twentieth century in photographic processes to size paper supports [20,21]. The ELISA experiments also allow to rule out the presence of gelatin or gum sizings in the historic papers studied. Because the entire paper sample disintegrates during the sample preparation process, poor extraction is unlikely to be the reason for the lack of antigenic response. The IR active modes expected for chloroplatinate complexes are below 400 cm 1, and for the K3[Fe(ox)3]3H2O complex bands have been reported at 1712, 1677, 1649, 1390, 1270, 1255, 885, 797, and 785 cm 1 [26]. D'Antonio et al. studied the Fe2(ox)34H2O compound, and reported strong features in its FTIR spectrum at 1736, 1655, 1612 and 1265 cm 1 [27]. No rm identication of these compounds can be made without the observation of all the relevant peaks reported for the reference materials. ATR spectra recorded in the samples listed in Table 1 showed features similar to those discussed for the transmission measurements (spectra not shown). ATR is used in conservation science as a nonsampling, minimally invasive technique for analyzing and characterizing photographic materials [20]. However, ATR may often times be considered inappropriate for photographs because it leaves in indentation that may be visible to the naked eye depending on the surface characteristic of the photograph. It can be concluded that the FTIR measurements support the identication of amorphous cellulose in the Japine sensitized side by Raman spectroscopy, and that the vibrational information obtained is not enough to identify the presence of oxalato or chloroplatinate complexes in the sensitized surfaces of the unprocessed photographic papers studied. We would like to stress that the Japine Platinotype sample studied is the only one in its original sealed container that has been so far discovered to our knowledge, that other variations may have been produced, and that also manufacturers other than the Platinotype Co. may have offered photographic papers on parchmentized paper supports [7,34]. 4. Conclusions The analysis of a historic Japine Platinotype Paper for Sepia Tones showed a sensitized surface consistent with the use of a parchmentization process. Raman and FTIR measurements revealed that the parchmentization process in Japine, most likely carried out in concentrated sulfuric acid, results in the formation of a surface layer composed mainly of amorphous cellulose, and that no gelatin or other surface coatings are present. It was also observed that the parchmentization process in Japine was carried out mainly in one surface but that the verso presents a slightly

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modied surface. No gelatin or gums were found to be present as substrate sizings in any of the other photographic papers studied either. The detection of relatively larger amounts of Hg in the Japine sepia paper sensitizer conrms the use of Hg salts in a sepia-type Pt paper, presumably to provide a warmer image tonality. While the relative amounts of Pt, Hg and Pb in the unprocessed papers are likely to vary during the darkroom processing, and certainly the total amounts of Fe will, this is not expected for the organic components. Among many others, eminent photographers Paul Strand and Alfred Stieglitz used Platinotype papers, including Japine. As more studies on historic photographic papers are published it would be increasingly possible to correlate their composition with features observed in masterworks of photography with the ultimate goal of understanding the artists' working practices and better caring for the works. Acknowledgments The authors are foremost grateful to Mike Ware who was the rst to suggest that the Japine surface may be the result of parchmentization. We are also thankful to Matt Clarke, Constance McCabe, and Christopher Maines at the National Gallery of Art, Washington DC, for the fruitful discussions. We are indebted to the following colleagues for generously sharing samples of historic platinum papers: Mike Ware for providing the Platinotype Co. KK sample; Dusan Stulik at the Getty Conservation Institute for a sample of the 1903 American Platinum for Cold Development (American Aristotype Co.), and Doug and Toddy Munson at Chicago Albumen Works for the 1908 American Aristotype Co. sample. We also want to thank Laura Harris, former Associate Museum Librarian, Joyce F. Menschel Photography Library at the MMA, for nding the Japine and AA tins, Julie Arslanoglu and Hae Young Lee for carrying out the ELISA tests, and Mark T. Wypyski and Federico Car for their assistance with the SEMEDS and XRF measurements. The support of Nora W. Kennedy, Katherine Sanderson, and Krista Lough from Photograph Conservation at the MMA, is greatly appreciated. This work was funded in part by an Annette de la Renta Fellowship to Anna Vila. References
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