Dual wavelength excitation for the time-resolved photoluminescence imaging of painted ancient Egyptian objects Comelli et al. Herit Sci (2016) 4:21 DOI 10.1186/s40494-016-0090-5 R E S E A R C H A R T I C L E Dual wavelength excitation for the time-resolved photoluminescence imaging of painted ancient Egyptian objects Daniela Comelli1†, Valentina Capogrosso1,2, Christian Orsenigo3 and Austin Nevin2*† Abstract Background: The scientific imaging of works of art is crucial for the assessment of the presence and distribution of pigments and other materials on surfaces. It is known that some ancient pigments are luminescent: these include pink red-lakes and the blue and purple pigments Egyptian Blue (CaCuSi4O10), Han blue (BaCuSi4O10) and Han purple (BaCuSi2O6). Indeed, the unique near-infrared luminescence emission of Egyptian blue allows the imaging of its distri- bution on surfaces. Results: We focus on the imaging of the time-resolved photoluminescence of ancient Egyptian objects in the Burri Collection from the Civic Museum of Crema and of the Cremasco (Italy). Time-resolved photoluminescence images have been acquired using excitation at 355 nm for detecting the ns-emission of red lakes and binding media; by employing 532 nm excitation Egyptian blue is probed, and the spatial distribution of its long-lived microsecond emis- sion is imaged. For the first time we provide data on the photoluminescence lifetime of Egyptian blue directly from objects. Moreover, we demonstrate that the use of a pulsed laser emitting at two different wavelengths increases the effectiveness of the lifetime imaging technique for mapping the presence of emissions from pigments on painted surfaces. Laser-induced luminescence spectra from different areas of the objects and traditional digital imaging, using led-based lamps, long pass filters and a commercial photographic camera, complement the results from photolumi- nescence lifetime imaging. We demonstrate the versatility of a new instrumental setup, capable of recording decay emission kinetics with lifetimes from nanosecond to microseconds. Conclusions: While the combined wavelength approach for the imaging of emissions from different materials has been demonstrated for the study of ancient Egyptian pigments (both organic and inorganic), the method could be extended to the analysis of modern pigments and paintings. Keywords: Photoluminescence imaging, Egyptian blue, Lifetime, Laser induced fluorescence, Pigments, Ancient Egyptian materials, Paintings © 2016 The Author(s). This article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The Creative Commons Public Domain Dedication waiver (http://creativecommons.org/ publicdomain/zero/1.0/) applies to the data made available in this article, unless otherwise stated. Background The imaging of paintings and painted objects relies on the interaction between radiation and matter and the detec- tion of reflected or emitted photons. Technical exami- nation and analysis of works of artworks typically relies on the integration of non-invasive imaging and suitable spectroscopic analysis, often followed by taking and ana- lysing samples. In this work we report an imaging study of Egyptian objects with a novel portable setup for time- resolved photoluminescence (TRPL) imaging and spec- troscopy, with a focus on the analysis of Egyptian Blue and lake pigments on artefacts. Photoluminescence (PL) of pigments and paint has received significant attention due to its practical use in the assessment of the condi- tion of works of art: for example, aged organic varnishes may appear more luminescent than freshly applied paint and some pigments, including semiconductor materials, Open Access *Correspondence: austinnevin@gmail.com †Daniela Comelli and Austin Nevin contributed equally to this work 2 Istituto di Fotonica e Nanotecnologie-Consiglio Nazionale delle Ricerche (IFN-CNR), Piazza Leonardo da Vinci 32, 20133 Milan, Italy Full list of author information is available at the end of the article http://orcid.org/0000-0003-1911-1045 http://creativecommons.org/licenses/by/4.0/ http://creativecommons.org/publicdomain/zero/1.0/ http://creativecommons.org/publicdomain/zero/1.0/ http://crossmark.crossref.org/dialog/?doi=10.1186/s40494-016-0090-5&domain=pdf Page 2 of 8Comelli et al. Herit Sci (2016) 4:21 emit characteristic PL signals [1]. Among ancient Egyp- tian pigments, Egyptian blue and madder-based red lakes are luminescent and are routinely identified with the aid of microscopic and spectroscopic analysis [2]. While the fluorescence observed in madder lakes is due to the anth- raquinone molecules purpurin and alizarin, the optical emission of Egyptian blue has been ascribed to Cu2+ in a solid calcium-silica matrix [3–5]. Recent research on the mineral pigment has reported that synthetic cuprori- vaite has a radiative emission with a maximum peaked at 910 nm and a lifetime of 107 μs and a  quantum yield of 10 % [6]. The imaging of PL from painted surfaces is often car- ried out to detect the colour of the emission, for which various approaches have been suggested. Whereas ultraviolet (UV) light sources based on Mercury lamps require filtering of spurious radiation emitted in the vis- ible to render them useful for imaging and photography, innovative uses of Xenon-flashes and digital photography have demonstrated the peculiar and noteworthy infrared emissions from Egyptian blue on paintings and painted objects from the British Museum and, more recently, on Fayoum Portraits [7–9]. Many other examples of digital imaging of Egyptian blue from objects have been documented. In addition to digital photographic  imaging, PL spec- troscopic imaging techniques have found multiple appli- cations for the analysis of paintings, including those carried out with a scanning Lidar approach [10, 11] and with light emitting diodes (LED) [12]. With these meth- ods, the detection of PL can be carried out with imaging spectrometers or suitably filtered imaging detectors [13, 14]. Another approach to the imaging of the PL from works of art relies on the detection of the emission life- time, which can be achieved by combining pulsed laser excitation with a time-gated imaging detector, known as fluorescence lifetime imaging or, more generally, TRPL Imaging [15]. Applications of TRPL imaging for the detection of organic materials on stone sculptures [16], wall paintings [17], and semiconductor pigments on paper [18] have been published, and demonstrate how TRPL imaging can map the  chemical composition of surfaces based on significant differences in emis- sion lifetime. In previous applications a ns Q-switched Nd:YAG laser emitting at 355 nm was employed as this wavelength can excite emissions from binding media and organic polymers and aforementioned fluorescent pigments. In this work we have modified our TRPL imaging set-up by adding excitation at 532  nm from the same Nd:YAG laser to allow the excitation of Egyp- tian blue. The combined wavelength approach has been applied to the imaging of painted objects from Carla Maria Burri Collection in the Civic Museum of Crema and the Cremasco (see sample description). Comple- mentary laser-induced PL spectroscopy from selected points on the objects has been carried out and digital photography using LED excitation complement images acquired with TRPL imaging. Results and discussion Preliminary PL spectroscopy analysis of a model sam- ple painted with the commercially available Egyptian blue pigment reveals a characteristic emission spectrum with a maximum emission at 920  ±  6  nm and a mono- exponential emission lifetime of 138 ±  4  µs (95  % confi- dence) (Fig. 1), in good agreement with the spectral data reported by others from pigments from the same sup- plier [7, 19]. The emission lifetime measured in our com- mercial pigment is in agreement with Borozov et al. [19] but differs with respect to that reported for the synthetic mineral calculated using single photon counting and 637 nm excitation (τ = 107 μs [6]). It is possible that the discrepancy in the PL lifetime is due to grinding of the pigment rather than to differences related to the methods used for the estimation of the PL decay [19]. PL imaging of the ancient Egyptian cartonnage (Fig.  2a) reveals the presence of different luminescent painted areas, effec- tively probed with the two lamp-based excitations: fol- lowing UV-excitation (Fig.  2b) an orange emission on red-pink areas and an intense bluish emission in white areas are observed. Conversely, excitation in the green and following inspection of the emission in the near- infrared reveals the use of an infrared luminescent pig- ment in most, but not all, of the areas painted with dark colours (Fig. 2c). Some of the areas painted dark are black and do not contain luminescent pigments. Results of PL spectroscopy of a dark painted area fol- lowing excitation at 532  nm (point 3 in Fig.  2a), is clear evidence of the use of the Egyptian blue pigment, as the detected emission spectrum closely resembles that of the Egyptian blue model sample (Fig.  3). TRPL imag- ing of details of the cartonnage painted with some of the dark colours reveals a monoexponential microsecond decay kinetic with a mean lifetime in the analysed area of 119  µs (7.7  µs interquartile range) and a negative skew- ness of −3.04, a reflection of the distribution of lifetime values that tend to be shorter than the mean (Fig. 4b). UV-induced optical emission of the cartonnage is associated with a nanosecond decay kinetic, typically ascribed to emission from organic molecules: follow- ing analysis of the first ten nanoseconds of the emis- sion decay profile, red-pink painted areas, white painted areas (as the face and the decorative heat) and the yel- low painted background have an effective lifetime close to 3.4, 3.8 and 3.1  ns, respectively (Fig.  4). Although the reconstructed lifetime values differ by hundreds of Page 3 of 8Comelli et al. Herit Sci (2016) 4:21 100 200 300 400 500 600 700 800 900 1000 0 1 2 3 4 5 6 x 10 5 Time / s P L e m is si o n c o u n ts data1 Monexponenatial fit = 137.9 s (133.8 s, 142.0 s) (95% confidential bounds) R2 = 0.999 Fig. 1 PL analysis of the Egyptian blue painted model sample. (top) PL emission spectrum and (bottom) PL emission lifetime following 532 nm pulsed excitation of the model sample painted with the commercial Egyptian blue pigment. A linear fit of the detected emission decay kinetic (black line) on the basis of a monoexponential model and goodness of fit in terms of R2. The sample exhibits an emission spectrum peaked at 920 nm and a monoexponetial decay kinetic with a lifetime of 138 μs Page 4 of 8Comelli et al. Herit Sci (2016) 4:21 picoseconds, the lifetime map allows the rapid discrimi- nation between the different painted areas, suggesting the presence of different organic pigments and binders. Specifically, the emission spectrum recorded on the red- pink painted areas (point 1 in Fig. 2a), peaked at 615 nm, resembles the spectral features of a red lake pigment, likely madder-based [4, 20] (Fig. 3). The broad spectrum recorded in the white painted area, with an emission peak at 590 nm, (Fig. 3) suggests the presence of a com- plex organic material, and is ascribed to emissions from binding media [1]. TRPL imaging of the stone mask, following visible exci- tation, suggests the presence of traces of the Egyptian blue pigment for decorating the areas of hair, beard and irises of the eyes  in Fig.  5. Blue used to paint the irises in polychromy has also been reported by Verri [7]. The clear identification of Egyptian Blue has been achieved through PL spectroscopy on a point on the hair of the mask: an emission spectrum comparable to that recorded on the commercial sample of Egyptian blue was recorded (data not shown). In terms of lifetime analysis, these painted areas show a microsecond decay kinetic close to that found from details on the cartonnage painted with Egyptian blue: here, we have detected a mean lifetime of 121.3  µs (6.6  µs of interquartile range) and a negative skew of −2.79 (Fig. 5). Conclusions The dual wavelength-excitation PL lifetime imaging approach reported here for the first time has been dem- onstrated to be valuable for probing the optical emission Fig. 2 Digital imaging of the cartonage from the Burri collection. (Top) Visible image; (middle) image of the PL emitted in the visible fol- lowing UV excitation, highlighting the presence of a fluorescence red pigment. Three points analysed with PL spectroscopy are indicated. (Bottom) image of the NIR-PL following excitation with green light, demonstrating the presence of a NIR emitting pigment, most prob- ably Egyptian Blue, in most of the areas painted in dark colours Fig. 3 Laser-induced PL spectroscopy of different analysis points of the cartonage: a red-pink painted area (point 1 in Fig. 2) (λmax 615 nm), flesh tones (point 2 in Fig. 2) (λmax 590 nm) following excitation at 355 nm. The PL emission spectrum of an area painted with dark colours (point 3 in Fig. 2) (λmax 920 nm) resembles the spectral features of Egyptian blue Page 5 of 8Comelli et al. Herit Sci (2016) 4:21 of different materials, of organic and inorganic nature, for the study of Ancient Egyptian artefacts. The same approach could be extended to the analysis of modern pigments and paintings, allowing an in-depth investiga- tion of the emission properties of organic and inorganic artist materials, including Cd-based pigments, in a com- bined way [13, 21]. Whereas the PL properties of the naturally occurring cuprorivaite mineral have been widely investigated in terms of both spectrum and decay kinetics [3, 6] and its brilliant emission has been exploited for the rapid detec- tion of the presence of the pigment in artworks from the Ancient Egypt [7], the near-infrared emission in Egyptian blue-painted ancient objects is not completely under- stood [19]. The intense and long emission recorded with PL imaging which is on the order of 120 μs is nonetheless diagnostic for the presence of Egyptian blue. Differences in lifetime in objects with respect to that reported and detected from that of the pure mineral and the synthetic commercial pigment are noted. The reasons behind life- time differences are beyond the scope of this work and require more refined analysis. Research in the future should address different degrees of crystallinity of the pigment in ancient objects following ancient synthesis Fig. 4 Luminescence lifetime imaging of the cartonage. (Left panel, top) False colour map of the effective PL lifetime reconstructed on details of the Cartonage following 355 nm pulsed laser excitation. The map is superimposed over the UV-induced fluorescence image of the artwork. (Right panel, top) The distribution of lifetime values in the cartonage in pixels (counts) vs. lifetime; the lifetime histogram shows a tri-modal behaviour, suggesting the presence of three different fluorescent materials with effective lifetime values of 3.1, 3.4 and 3.8 ns. (Left panel, bottom) False colour map of the PL lifetime reconstructed on details of the Cartonage following 532 nm pulsed laser excitation. The map is superimposed over the visible-induced NIR-PL image of the artwork, and show the use of Egyptian blue for different details of the cartonage painted in dark colours. (Right panel, bottom) The distribution of lifetime values in the cartonage in pixels (counts) vs. lifetime, showing a unimodal behaviour with a mean lifetime of 119.3 μs (7.7 μs of interquartile range) Page 6 of 8Comelli et al. Herit Sci (2016) 4:21 processes, grinding or sintering of the pigments and determine if chemical interactions between the pigment and the surrounding matrix in objects affects the emis- sion lifetimes. Further analyses with complementary methods sensitive to impurities which could account for differences in lifetime would be required to better refine these hypotheses. Methods Description of the collection and objects The antiquities collection of the late Carla Maria Burri (1935–2009), Director of the Italian Cultural Institute in Egypt from 1993 and 1999, was donated to the Museo Civico di Crema e del Cremasco in Winter 2010/2011 [22]. In 2013, Christian Orsenigo was charged with the study of the artefacts, under the supervision of Dr. Francesco Muscolino of the Soprintendenza Archeologia della Lombardia. The collection consists of about eighty objects and covers a vast time span; ranging from the most ancient item—a faience tile once belonging to the decoration of the walls of the galleries underneath Djos- er’s Step Pyramid at Saqqara (ca. 2630–2611  B.C.E.)— excluding some flints actually under study—to Islamic glass dating to the 11th C. (Orsenigo 2016, forthcom- ing). The collection includes objects belonging to differ- ent typologies, such as funerary statuettes (shabtis) from the late New Kingdom, masks and parts of sarcophagi, bronzes and amulets, other than Hellenistic and Roman terracotta figurines and lamps. In this work we examine a Cartonnage and a Mask. The cartonnage The polychrome cartonnage fragment probably comes from the back terminal of a mask, depicting a human- headed ba-bird, crowned with solar disc and holding two maat-feathers at each wing. Unfortunately noth- ing is known about the provenance of this object, as is the case for a very similar fragment kept at the Petrie Museum, UCL (accession number  UC45900), that is a particularly good comparandum [23] The material is linen covered with plaster and then painted. Car- tonnages such as this can be dated from Ptolemaic to Roman Periods [24] The mask Even if preserved only in its upper front part, the object is likely a miniature painted terracotta comic mask of an actor playing a slave character in the New Com- edy. It shows a broad nose, brows flying up to the sides and wrinkled forehead. It can be dated to the Ptolemaic Period. See references for comparisons with similar objects [25, 26]. Fig. 5 Luminescence lifetime imaging of a mask from the Burri collection. Left panel False colour map of the PL lifetime reconstructed on details of the stone mask following 532 nm pulsed laser excitation. The map, superimposed on the visible-induced NIR-PL image, outlines the use of the Egyptian blue pigment for decorating the mask’s hair and eyes. Right panel related distribution of lifetime values in the mask, showing a unimodal behaviour with a mean lifetime of 121.3 µs (6.6 µs interquartile range) Page 7 of 8Comelli et al. Herit Sci (2016) 4:21 Reference sample A painted model sample of Egyptian blue pigment (Kre- mer pigmente, GmbH) was prepared and analysed. The pigment, dispersed in Plextol, was applied as a painted layer on a glass substrate. Time‑resolved photoluminescence imaging The TRPL imaging device is, described in detail else- where, and is summarized below. A schematic diagrame of the setup can be found elsewhere [16]. The device is comprised of a ns laser excitation source combined with a time-gated intensified camera (C9546-03, Hamamatsu Photonics, Hamamatsu City, Japan), capable of high speed gating to capture images of transient phenomena. A custom-built trigger unit and a precision delay genera- tor (DG535 Stanford Research System, Sunnyvale, CA, USA) complete the system, which has a net temporal jit- ter close to 0.5 ns. The Q-switching laser source (FTSS 355-50 Crylas GmbH, Berlin, Germany), based on the third harmonic of a diode-pumped Nd:YAG crystal (λ =  355  nm, Pulse energy  =  70  μJ, Pulse duration  =  1.0  ns, repetition frequency  =  100  Hz), has been modified in order to obtain the second harmonic of the same source emis- sion (λ  =  532  nm, Pulse energy  =  60  μJ, Pulse dura- tion =  1.0  ns). By using both wavelengths we probe the PL emission of materials with different absorption spec- tra. The two emission lines of the laser source are col- linear; hence it is easy to switch between them during measurements. In order to spectrally clean laser emis- sions, proper bandpass filters (FL355-10 or FL532-10, Thorlabs GmbH Germany) are employed at the exit of the laser source. The laser beam, coupled to a silica optical fibre, is magnified with suitable silica optics in order to illumi- nate a circular area of about 25 cm diameter on the sur- face of the object, with a typical fluence per pulse below 140  nJcm−2. This very low power density does not lead to detectable changes in the intensity of emission due to photooxidation in samples following typical measure- ments. The kinetics of the emission is detected by the gated intensified camera, which is based on a GaAs pho- tocathode with spectral sensitivity from 380 to 900  nm. The gate width of the camera is adjustable from 3  ns to continuous mode, depending on the kinetic properties of the surface under investigation. In this work a gate width of 5  ns was employed to detect the nanosecond kinetics of the emission from organic materials. Long-lived decay kinetics ascribed to emissions from areas painted in Egyptian blue have been effectively sampled by increas- ing the width to 100  µs. A proper optical highpass filter w placed in front of the camera lens in order to remove excitation light: the B + W UV/IR Cut 486 M MRC filter (Schneider Optics), with high transmission from 380 to 720  nm, was employed for lifetime analysis following 355  nm excitation, whereas the Kodak Wratten 23A fil- ter transmitting light beyond 550  nm was employed for measurements at 532 nm excitation. As has been shown in previous research, the short tem- poral jitter of the system is key to the estimation of ns lifetimes which may be used to differentiate organic bind- ing media and pigments [16]. TRPL imaging is achieved through the reconstruction of the effective lifetime map based on a simple mono-exponential decay model [14]. Laser‑induced photoluminescence spectroscopy A compact spectrometer and the same dual-wavelength laser source employed in the TRPL imaging device were used for detecting emission spectra from selected points on objects. The compact spectrometer (TM-CCD C10083CA-2100, Hamamatsu Photonics) mounts a back thinned CCD image sensor and a transmission-type grating, recording spectra between 320–1100  nm with a spectral resolution of 6  nm. Through fibre optics both the laser and the spectrometer are remotely connected to an optical probe, working in the 45–0° configuration mode. Proper transmission high-pass filters (FEL420 or FEL550, Thorlabs GmbH Germany) are mounted on the probe which, that allow excitation and collection of photons from a point on surface of approximately 1 mm diameter at a distance of 35  mm. The probe is equipped with a proper transmission high-pass filter (FGL420 or FELH550, Thorlabs GmbH Germany) depending on the employed laser wavelength. Spectra are reported follow- ing background subtraction (mainly related to the sensor read and dark noise) and correction for the spectral effi- ciency of the device. Digital imaging As proposed in past research [7, 8], a commercial Nikon D7100 digital camera (D60) was employed for record- ing UV-induced digital images of the PL emission of objects. Excitation was provided from a Xenon-based flash equipped with an UV bandpass filter (DUG11, Schott AG), whereas a transmission filter blocking light in the UV and in the NIR spectral range (W UV/IR Cut 486  M MRC filter, Schneider Optics) was mounted in front of a 50-mm focal camera lens [7, 8]. Similarly, infra- red digital photography of the emission of Egyptian Blue painted objects was performed using the commercial digital camera without the infrared blocking filter (sup- plied by Advanced Camera Services, UK) and mounting an). An infrared transmission filter (R72, HOYA) was placed in front of the camera lens [8] for detection only of the infrared emission. Excitation of PL emission was achieved using a 15 W Watt green LED-based lamp with Page 8 of 8Comelli et al. Herit Sci (2016) 4:21 emission in the green (4000 lx @ 1 m) (FLAT PAR CAN RGB 10 IR WH, Cameo (Germany)). Authors’ contributions Analysis was carried out by DC, AN, VC and SM. Historical context and information has been provided by CO. All authors read and approved the final manuscript. Author details 1 Diparitmento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milan, Italy. 2 Istituto di Fotonica e Nanotecnologie-Consiglio Nazionale delle Ricerche (IFN-CNR), Piazza Leonardo da Vinci 32, 20133 Milan, Italy. 3 Dipartimento di Studi letterari, filologici e linguistici, Biblioteca e Archivi di Egittologia, Università degli Studi di Milano, via Festa del Perdono 3, 20122 Milan, Italy. Acknowledgements Research was partially funded through the Bilateral Project between Italy and Egypt coordinated by Daniela Comelli (Politecnico di Milano, Italy) and Abdelrazek Elnaggar (Univeristy of Fayoum, Egypt) (Progetti di Grande Rilevanza, Protocollo Esecutivo–EGITTO, PGR 00101.) Authors thank Daniela Gallo Carrabba and Fiorenzo Gnesi (Associazione Carla Maria Burri), Francesca Moruzzi and Simone Riboldi (Museo civico di Crema e del Cremasco), Franc- esco Muscolino (Soprintendenza Archeologia della Lombardia) and Patrizia Piacentini (Università degli Studi di Milano, Chair of Egyptology). Competing interests The authors declare that they have no competing interests. Received: 14 December 2015 Accepted: 30 May 2016 References 1. Nevin A, Spoto G, Anglos A. Laser spectroscopies for elemental and molecular analysis in art and archaeology. Appl Phys A. 2012;106:339–61. 2. Scott DA, Warlander S, Mazurek J, Quirke S. 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Accessed 1 Dec 2015. http://dx.doi.org/10.1117/12.2067388 http://dx.doi.org/10.1016/j.microc.2015.11.019 http://petriecat.museums.ucl.ac.uk/ http://www.britishmuseum.org/research/collection_online http://www.britishmuseum.org/research/collection_online Dual wavelength excitation for the time-resolved photoluminescence imaging of painted ancient Egyptian objects Abstract Background: Results: Conclusions: Background Results and discussion Conclusions Methods Description of the collection and objects The cartonnage The mask Reference sample Time-resolved photoluminescence imaging Laser-induced photoluminescence spectroscopy Digital imaging Authors’ contributions References